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Sample records for oxygen deficient perovskite

  1. Enhancing perovskite electrocatalysis through strain tuning of oxygen deficiency

    SciTech Connect

    Barron, Sara C.; Lee, Ho Nyung; Petrie, Jonathan R.; Jeen, Hyoungjeen; Meyer, Tricia L.

    2016-05-27

    Oxygen vacancies in transition-metal oxides facilitate catalysis critical for energy storage and generation. However, promoting vacancies at the lower temperatures required for operation in devices such as metal–air batteries and portable fuel cells has proven elusive. Here we used thin films of perovskite-based strontium cobaltite (SrCoOx) to show that epitaxial strain is a powerful tool for manipulating the oxygen content under conditions consistent with the oxygen evolution reaction, yielding increasingly oxygen-deficient states in an environment where the cobaltite would normally be fully oxidized. The additional oxygen vacancies created through tensile strain enhance the cobaltite’s catalytic activity toward this important reaction by over an order of magnitude, equaling that of precious-metal catalysts, including IrO2. Lastly, our findings demonstrate that strain in these oxides can dictate the oxygen stoichiometry independent of ambient conditions, allowing unprecedented control over oxygen vacancies essential in catalysis near room temperature.

  2. Enhancing perovskite electrocatalysis through strain tuning of oxygen deficiency

    DOE PAGES

    Barron, Sara C.; Lee, Ho Nyung; Petrie, Jonathan R.; ...

    2016-05-27

    Oxygen vacancies in transition-metal oxides facilitate catalysis critical for energy storage and generation. However, promoting vacancies at the lower temperatures required for operation in devices such as metal–air batteries and portable fuel cells has proven elusive. Here we used thin films of perovskite-based strontium cobaltite (SrCoOx) to show that epitaxial strain is a powerful tool for manipulating the oxygen content under conditions consistent with the oxygen evolution reaction, yielding increasingly oxygen-deficient states in an environment where the cobaltite would normally be fully oxidized. The additional oxygen vacancies created through tensile strain enhance the cobaltite’s catalytic activity toward this important reactionmore » by over an order of magnitude, equaling that of precious-metal catalysts, including IrO2. Lastly, our findings demonstrate that strain in these oxides can dictate the oxygen stoichiometry independent of ambient conditions, allowing unprecedented control over oxygen vacancies essential in catalysis near room temperature.« less

  3. Enhancing perovskite electrocatalysis through strain tuning of oxygen deficiency

    SciTech Connect

    Barron, Sara C.; Lee, Ho Nyung; Petrie, Jonathan R.; Jeen, Hyoungjeen; Meyer, Tricia L.

    2016-05-27

    Oxygen vacancies in transition-metal oxides facilitate catalysis critical for energy storage and generation. However, promoting vacancies at the lower temperatures required for operation in devices such as metal–air batteries and portable fuel cells has proven elusive. Here we used thin films of perovskite-based strontium cobaltite (SrCoOx) to show that epitaxial strain is a powerful tool for manipulating the oxygen content under conditions consistent with the oxygen evolution reaction, yielding increasingly oxygen-deficient states in an environment where the cobaltite would normally be fully oxidized. The additional oxygen vacancies created through tensile strain enhance the cobaltite’s catalytic activity toward this important reaction by over an order of magnitude, equaling that of precious-metal catalysts, including IrO2. Lastly, our findings demonstrate that strain in these oxides can dictate the oxygen stoichiometry independent of ambient conditions, allowing unprecedented control over oxygen vacancies essential in catalysis near room temperature.

  4. Redox activity of surface oxygen anions in oxygen-deficient perovskite oxides during electrochemical reactions.

    PubMed

    Mueller, David N; Machala, Michael L; Bluhm, Hendrik; Chueh, William C

    2015-01-19

    Surface redox-active centres in transition-metal oxides play a key role in determining the efficacy of electrocatalysts. The extreme sensitivity of surface redox states to temperatures, to gas pressures and to electrochemical reaction conditions renders them difficult to investigate by conventional surface-science techniques. Here we report the direct observation of surface redox processes by surface-sensitive, operando X-ray absorption spectroscopy using thin-film iron and cobalt perovskite oxides as model electrodes for elevated-temperature oxygen incorporation and evolution reactions. In contrast to the conventional view that the transition metal cations are the dominant redox-active centres, we find that the oxygen anions near the surface are a significant redox partner to molecular oxygen due to the strong hybridization between oxygen 2p and transition metal 3d electronic states. We propose that a narrow electronic state of significant oxygen 2p character near the Fermi level exchanges electrons with the oxygen adsorbates. This result highlights the importance of surface anion-redox chemistry in oxygen-deficient transition-metal oxides.

  5. An oxygen-deficiency modulated multiferroic: Cobalt-substituted perovskite

    NASA Astrophysics Data System (ADS)

    Florez, Juan Manuel

    In this work, we use density functional theory to model recently demonstrated room temperature ferromagnetism and ferroelectricity in polycrystalline and single crystal Cobalt-substituted SrTiO3 thin films (SrTi0.70Co0.30O3-d), deposited at different oxygen pressures to change their oxygen vacancy concentration. The modeling indicates an origin for both magnetism and electric polarization in the interactions between oxygen vacancies and the B-site cations. The magnetization saturation increases with the oxygen deficiency as a result of valence spin states changes, which depend on whether the oxygen octahedral of the respective local B-site cations are complete or not. On the other hand, a finite electric polarization appears as a result of a non-centrosymmetric distribution of different resulting local charges and such a polarization increases when the oxygen vacancies increase. Increasing of both order parameters, magnetic and ferroelectric, are analyzed respect to all possible Co-sites and O-vacancies distributions, showing that these results suggest a class of multiferroic materials with properties controlled by their oxygen stoichiometry. Agreement and discrepancies between experiments and modeling are discussed. 1J M Florez and P Vargas thank Fondecyt 1130950 and 11130128, all authors thank the MISTI MIT-Chile, and CAR thanks the (S3TEC) and DoE under DE-SC0001299.

  6. Mechanical control of magnetism in oxygen deficient perovskite SrTiO3.

    PubMed

    Zhang, Yajun; Wang, Jie; Sahoo, M P K; Shimada, Takahiro; Kitamura, Takayuki

    2015-10-28

    Mechanical control of magnetism in perovskite oxides is an important and promising approach in spintronics. Based on the first-principles calculations, we demonstrate that a negative pressure leads to a great enhancement of magnetic moment in deficient SrTiO3 with oxygen vacancies, whereas a positive pressure results in the gradual disappearance of magnetism. Spin charge density, Bader charge analysis and electronic density of states successfully elucidate the origin and underlying physics of the enhancement and disappearance of magnetism. It is found that the split electronic states of dz(2), dyz and dzx in the 3d orbitals of Ti atoms remarkably contribute to the occupancy of majority spin states under negative pressure, which induces a large magnetic moment. Under positive pressure, however, the equal occupancy of both majority and minority t2g and eg states leads to the disappearance of magnetization. In addition, both negative and positive pressures can largely lower the vacancy formation enthalpy, suggesting that the oxygen vacancy is preferable with pressure. Our findings may provide a mechanism to achieve the pressure control of magnetization in nonmagnetic perovskite oxides.

  7. La 6BaYCu 8O 20: A New Oxygen Deficient Perovskite

    NASA Astrophysics Data System (ADS)

    Cava, R. J.; Zandbergen, H. W.; Van Dover, R. B.; Krajewski, J. J.; Siegrist, T.; Peck, W. F.; Roth, R. S.; Felder, R. J.

    1994-04-01

    La 6BaYCu 8O 20 is a new three-dimensional oxygen deficient perovskite related to the well-known three-dimensional material La 4BaCu 5O 13. The inclusion of a small rare earth results in an extension of the layerlike areas within the three-dimensional network. The same structure is also found for La 6BaDyCu 8O 20. The structure can be doped with Sr for La, or Ca for the small lanthanide. No superconductivity is observed down to 0.3 K. La 4BaCu 5O 13 and the new compound form the first two members of a new three-dimensional homologous series La 4+2 nBa LnnCu 5+3 nO 13+7 n through the addition of "123" type structural units.

  8. The physical properties of oxygen-deficient perovskite SrPbO(3-δ).

    PubMed

    Hadjarab, B; Bouguelia, A; Kadi-Hanifi, M; Trari, M

    2006-09-20

    The transport properties of oxygen-deficient perovskite SrPbO(3-δ) with mixed lead valency were investigated down to 4.2 K. The small δ-value (0.059), determined from iodometry, is due to the inert lone pair Pb(2+) that does not enjoy regular octahedral coordination in spite of collective electron behaviour. The oxide exhibits a temperature-independent magnetic susceptibility consistent with itinerant electrons. The sign of carriers like polarons is that of n-type conductivity coming from the balance charge via oxygen extraction. The thermal variation of conductivity and thermopower reveal the existence of an energy gap. The conduction mechanism occurs by polaron hopping in conformity with small activation energy. The metal-insulating transition seems to be of Anderson type, resulting from the disorder of oxygen vacancies. At low temperature, the conductivity was fitted to a variable range hopping [Formula: see text]. A comparison with SrSnO(3) will be reported. The covalency of Sn-O raises the antibonding conduction state of 5s parentage and increases the forbidden gap from 1.78 to 3.30 eV.

  9. Structural and Magnetic Phase Coexistence in Oxygen Deficient Perovskites (Sr,Ca)FeO 2 . 5 + δ

    NASA Astrophysics Data System (ADS)

    Carlo, J. P.; Evans, M. E.; Anczarski, J. A.; Ock, J.; Boyd, K.; Pollichemi, J. R.; Leahy, I. A.; Vogel, W.; Viescas, A. J.; Papaefthymiou, G. C.

    A variety of compounds crystallize into perovskite and similar structures, making them versatile laboratories for many phenomena and applications, including multiferroicity, superconductivity, and photovoltaics. Oxygen-deficient perovskites ABOx have attracted interest for use in fuel cells and related applications due to high oxygen mobility and the possibility of charge disproportionation. Vast chemical flexibility is obtained through reductions in lattice symmetry and rotation/distortion of the BO6 octahedra, as well as ordering of oxygen vacancies. We have synthesized and studied the structural and magnetic properties of oxygen-deficient perovskites (Sr,Ca)FeO2 . 5 + δ using x-ray diffraction and Mossbauer spectroscopy. While the ideal perovskite has δ = 0.5, this requires Fe4+, and hence strongly oxidizing environments. When grown in air, Fe3+ is favored, yielding δ ~ 0. SrFeO2 . 5 + δ exhibits cubic symmetry and paramagnetism at 300K, but CaFeO2 . 5 + δ crystallizes into the orthorhombic brownmillerite structure, and is magnetically ordered at 300K. In the doped intermediaries we find coexistence of cubic/paramagnetic and orthorhombic/magnetic phases over a wide range of Ca content. Financial support from the Villanova Undergraduate Research Fellowship program and the Research Corporation for Science Advancement.

  10. New oxygen-deficient cationic-ordered perovskites containing turquoise-coloring Mn5+O4 tetrahedral layers

    NASA Astrophysics Data System (ADS)

    Han, Yifeng; Ye, Xuanhong; Zhu, Hong; Li, Yuexiang; Kuang, Xiaojun

    2017-03-01

    Ba6Na2M2Mn2O17 (M=Nb, Ta) oxides were synthesized by high-temperature solid-state reaction. The compounds adopt 6-layer perovskite-related structure (referred to as 6C) in P 3 ̅m1, analogous to Ba6Na2Nb2P2O17. The 6C structure consists of cubic (c) BaO3 layers and pseudo-cubic (c') oxygen-vacancy-ordered BaO2 layers stacked according to a sequence of c'ccccc. Ordering of oxygen vacancies in oxygen-deficient c'-BaO2 layers leads to two successive isolated tetrahedral layers, which stabilize an unusual +5 oxidation state for Mn cations in the tetrahedral sites. In Ba6Na2M2Mn2O17, these two Mn5+O4 layers are sandwiched by two single octahedral NaO6 layers that connected by two successive octahedral NbO6 layers, forming alternative 2:1-ordered (Ba3NaM2O9)- and (Ba3NaMn2O8)+ perovskite-like units along the stacking direction. The Mn5+O4 tetrahedral units act as a turquoise chromophore in Ba6Na2M2Mn2O17, making these two compounds potential turquoise-coloring materials for the cool pigments.

  11. (La1-xSrx)0.98MnO3 perovskite with A-site deficiencies toward oxygen reduction reaction in aluminum-air batteries

    NASA Astrophysics Data System (ADS)

    Xue, Yejian; Miao, He; Sun, Shanshan; Wang, Qin; Li, Shihua; Liu, Zhaoping

    2017-02-01

    The strontium doped Mn-based perovskites have been proposed as one of the best oxygen reduction reaction catalysts (ORRCs) to substitute the noble metal. However, few studies have investigated the catalytic activities of LSM with the A-site deficiencies. Here, the (La1-xSrx)0.98MnO3 (LSM) perovskites with A-site deficiencies are prepared by a modified solid-liquid method. The structure, morphology, valence state and oxygen adsorption behaviors of these LSM samples are characterized, and their catalytic activities toward ORR are studied by the rotating ring-disk electrode (RRDE) and aluminum-air battery technologies. The results show that the appropriate doping with Sr and introducing A-site stoichiometry can effectively tailor the Mn valence and increase the oxygen adsorption capacity of LSM. Among all the LSM samples in this work, the (La0.7Sr0.3)0.98MnO3 perovskite composited with 50% carbon (50%LSM30) exhibits the best ORR catalytic activity due to the excellent oxygen adsorption capacity. Also, this catalyst has much higher durability than that of commercial 20%Pt/C. Moreover, the maximum power density of the aluminum-air battery using 50%LSM30 as the ORRC can reach 191.3 mW cm-2. Our work indicates that the LSM/C composite catalysts with A-site deficiencies can be used as a promising ORRC in the metal-air batteries.

  12. Origin of OER catalytic activity difference of oxygen-deficient perovskites A2Mn2O5 (A = Ca, Sr): A theoretical study

    NASA Astrophysics Data System (ADS)

    Yao, Xiaolong; Liu, Jieyu; Wang, Weihua; Lu, Feng; Wang, Weichao

    2017-06-01

    Mn-based oxygen-deficient perovskite catalysts A2Mn2O5 (A = Ca, Sr) have been experimentally proved high oxygen evolution reaction (OER) activities for replacing Pt in oxygen electrocatalysis. Nevertheless, the correlation between the fundamental electronic structure at room temperature and the corresponding electrocatalysis is not fully accessible. In this paper, we combine the ground state density functional theory (DFT) method and dynamic mean-field theory (DFT+DMFT) at room temperature to investigate the origin of the OER difference for electrocatalysts A2Mn2O5 (A = Ca, Sr). We find that at room temperature the highest occupied Mn dz2 orbital in the square pyramidal crystal field of oxygen-deficient perovskites A2Mn2O5 with insulating properties can provide a moderate bonding strength with intermediate hydroxyl OH*, leading to a high OER catalytic activity. According to the electronic structure analysis, we observe that replacing the A-site element Ca by Sr with the larger ionic radii would result in a higher OER activity due to the weakened hybridization between the Mn dz2 orbital and the O pσ orbital of OH*. This insight could provide hints for the screening metal oxide electrocatalysts in the applications of the energy storage and conversion.

  13. Layered oxygen-deficient double perovskite as an efficient and stable anode for direct hydrocarbon solid oxide fuel cells.

    PubMed

    Sengodan, Sivaprakash; Choi, Sihyuk; Jun, Areum; Shin, Tae Ho; Ju, Young-Wan; Jeong, Hu Young; Shin, Jeeyoung; Irvine, John T S; Kim, Guntae

    2015-02-01

    Different layered perovskite-related oxides are known to exhibit important electronic, magnetic and electrochemical properties. Owing to their excellent mixed-ionic and electronic conductivity and fast oxygen kinetics, cation layered double perovskite oxides such as PrBaCo2O5 in particular have exhibited excellent properties as solid oxide fuel cell oxygen electrodes. Here, we show for the first time that related layered materials can be used as high-performance fuel electrodes. Good redox stability with tolerance to coking and sulphur contamination from hydrocarbon fuels is demonstrated for the layered perovskite anode PrBaMn2O5+δ (PBMO). The PBMO anode is fabricated by in situ annealing of Pr0.5Ba0.5MnO3-δ in fuel conditions and actual fuel cell operation is demonstrated. At 800 °C, layered PBMO shows high electrical conductivity of 8.16 S cm(-1) in 5% H2 and demonstrates peak power densities of 1.7 and 1.3 W cm(-2) at 850 °C using humidified hydrogen and propane fuels, respectively.

  14. Spin glass behavior in a highly oxygen deficient Perovskite BaBiO.28Co0.72O2.2

    SciTech Connect

    Klimczuk, Thomasz W; Zandbergen, H; Huang, Q; Mcqueen, T

    2008-01-01

    A highly oxygen deficient perovskite, BaBio.28Coo.n02.2, was synthesized by solid state reaction. The crystal structure was determined by neutron and x-ray powder diffraction. The material exhlbits semiconducting behavior with an energy gap of 1.8 eV. Magnetic susceptibility studies reveal spin-glass ordering, which may have its origin in the frustration caused by the presence of competing antiferromagnetic and ferromagnetic interactions. The electron diffraction study shows the existence of short range ordering in thls phase.

  15. Oxygen deficient layered double perovskite as an active cathode for CO2 electrolysis using a solid oxide conductor.

    PubMed

    Shin, Tae Ho; Myung, Jae-Ha; Verbraeken, Maarten; Kim, Guntae; Irvine, John T S

    2015-01-01

    A-site ordered PrBaMn2O(5+δ) was investigated as a potential cathode for CO2 electrolysis using a La(0.9)Sr(0.1)Ga(0.8)Mg(0.2)O3 (LSGM) electrolyte. The A-site ordered layered double perovskite, PrBaMn2O(5+δ), was found to enhance electrocatalytic activity for CO2 reduction on the cathode side since it supports mixed valent transition metal cations such as Mn, which could provide high electrical conductivity and maintain a large oxygen vacancy content, contributing to fast oxygen ion diffusion. It was found that during the oxidation of the reduced PrBaMn2O(5+δ) (O5 phase) to PrBaMn2O(6-δ) (O6 phase), a reversible oxygen switchover in the lattice takes place. In addition, here the successful CO2 electrolysis was measured in LSGM electrolyte with this novel oxide electrode. It was found that this PrBaMn2O(5+δ), layered perovskite cathode exhibits a performance with a current density of 0.85 A cm(-2) at 1.5 V and 850 °C and the electrochemical properties were also evaluated by impedance spectroscopy.

  16. β-Sr 10Ga 6O 19: an oxygen deficient perovskite containing [Ga 6O 19]-polyanions

    NASA Astrophysics Data System (ADS)

    Kahlenberg, Volker

    2002-02-01

    A novel modification of hexagallium decastrontium oxide, β-Sr 10Ga 6O 19, has been prepared from a non-stoichiometric melt of composition 4SrO : Ga 2O 3 in the temperature range between 1490 to 1600 °C. The crystal structure was determined at 25 °C from single crystal X-ray diffraction data (orthorhombic, space group Pbcn, a=34.3163(21) Å, b=7.8918(4) Å, c=15.9558(7) Å, V=4321.1(4) Å 3, Z=8, R1=0.036, wR2=0.076 for 1839 observed reflections with I>2 σ( I)). It contains highly puckered unbranched six-membered oligogroups of composition [Ga 6O 19] 20-. The oligomers are located in 6.5 Å wide slabs oriented perpendicular to [0 0 1] and are connected via Sr-ions residing within as well as in between the slabs. Alternatively, the structure can be described as a 8×2×4 superstructure of perovskite ABO 3, with 20.8% vacancies in the oxygen sublattice. From the 64 B-sites in the unit cell of β-Sr 10Ga 6O 19, 25% are occupied by Sr- and 75% by Ga-cations, whereas the corresponding A-sites are exclusively occupied by Sr. Therefore, the relationship with perovskite can be expressed in the following crystal chemical formula: Sr(Ga 3/4Sr 1/4)(O 19/8□ 5/8).

  17. Oxygen-deficient and ordered perovskite-type solid-solution system Ba1+xBi1-xOy(0 <= x <= 0.5, 3.00 >= y >= 2.75)

    NASA Astrophysics Data System (ADS)

    Itoh, Mitsuru; Sawada, Tohru; Liang, Ruixing; Kawaji, Hitoshi; Nakamura, Tetsurō

    1990-07-01

    A new oxygen-deficient and ordered perovskite-type solid-solution system Ba1+xBi1-xOy(0 ≦ x ≦ 0.5, 3.00 ≧ y ≧ 2.75) was synthesized, with the estimated ionic configuration Ba(Ba 2+xBi 3+3.5-1.5 x-yBi 5+-3+0.5 x+y)(Bi 5+0.5)O y. The lattice parameters and mean valence of bismuth in the samples annealed in one atmosphere of oxygen at 773 K were determined by the powder X-ray diffraction method and iodometric titration method, respectively. Samples with the compositions 0 ≦ x ≦ 0.05, 0.10 ≦ x ≦ 0.15, 0.20 ≦ x ≦ 0.425, 0.45 ≦ x ≦ 0.475, and 0.475 < x ≦ 0.50 were found to be monoclinic, rhombohedral, cubic, tetragonal, and cubic, respectively. Oxygen deficiency was observed in the entire range of the composition; the ordering of the oxygen vacancies was confirmed in the range X ≧ 0.45.

  18. Strain effects on oxygen migration in perovskites.

    PubMed

    Mayeshiba, Tam; Morgan, Dane

    2015-01-28

    Fast oxygen transport materials are necessary for a range of technologies, including efficient and cost-effective solid oxide fuel cells, gas separation membranes, oxygen sensors, chemical looping devices, and memristors. Strain is often proposed as a method to enhance the performance of oxygen transport materials, but the magnitude of its effect and its underlying mechanisms are not well-understood, particularly in the widely-used perovskite-structured oxygen conductors. This work reports on an ab initio prediction of strain effects on migration energetics for nine perovskite systems of the form LaBO3, where B = [Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Ga]. Biaxial strain, as might be easily produced in epitaxial systems, is predicted to lead to approximately linear changes in migration energy. We find that tensile biaxial strain reduces the oxygen vacancy migration barrier across the systems studied by an average of 66 meV per percent strain for a single selected hop, with a low of 36 and a high of 89 meV decrease in migration barrier per percent strain across all systems. The estimated range for the change in migration barrier within each system is ±25 meV per percent strain when considering all hops. These results suggest that strain can significantly impact transport in these materials, e.g., a 2% tensile strain can increase the diffusion coefficient by about three orders of magnitude at 300 K (one order of magnitude at 500 °C or 773 K) for one of the most strain-responsive materials calculated here (LaCrO3). We show that a simple elasticity model, which assumes only dilative or compressive strain in a cubic environment and a fixed migration volume, can qualitatively but not quantitatively model the strain dependence of the migration energy, suggesting that factors not captured by continuum elasticity play a significant role in the strain response.

  19. Perovskite/Carbon Composites: Applications in Oxygen Electrocatalysis.

    PubMed

    Zhu, Yinlong; Zhou, Wei; Shao, Zongping

    2017-03-01

    Oxygen electrocatalysis, i.e., oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), plays an extremely important role in oxygen-based renewable-energy technologies such as rechargeable metal-air batteries, regenerative fuel cells and water splitting. Perovskite oxides have recently attracted increasing interest and hold great promise as efficient ORR and OER catalysts to replace noble-metal-based catalysts, owing to their high intrinsic catalytic activity, abundant variety, low cost, and rich resources. The introduction of perovskite-carbon interfaces by forming perovskite/carbon composites may bring a synergistic effect between the two phases, thus benefiting the oxygen electrocatalysis. This review provides a comprehensive overview of recent advances in perovskite/carbon composites for oxygen electrocatalysis in alkaline media, aiming to provide insights into the key parameters that influence the ORR/OER performance of the composites, including the physical/chemical properties and morphologies of the perovskites, the multiple roles of carbon, the synthetic method and the synergistic effect. A special emphasis is placed on the origin of the synergistic effect associated with the interfacial interaction between the perovskite and the carbon phases for enhanced ORR/OER performance. Finally, the existing challenges and the future directions for the synthesis and development of more efficient oxygen catalysts based on perovskite/carbon composites are proposed.

  20. Perovskite oxides: Oxygen electrocatalysis and bulk structure

    NASA Technical Reports Server (NTRS)

    Carbonio, R. E.; Fierro, C.; Tryk, D.; Scherson, D.; Yeager, Ernest

    1987-01-01

    Perovskite type oxides were considered for use as oxygen reduction and generation electrocatalysts in alkaline electrolytes. Perovskite stability and electrocatalytic activity are studied along with possible relationships of the latter with the bulk solid state properties. A series of compounds of the type LaFe(x)Ni1(-x)O3 was used as a model system to gain information on the possible relationships between surface catalytic activity and bulk structure. Hydrogen peroxide decomposition rate constants were measured for these compounds. Ex situ Mossbauer effect spectroscopy (MES), and magnetic susceptibility measurements were used to study the solid state properties. X ray photoelectron spectroscopy (XPS) was used to examine the surface. MES has indicated the presence of a paramagnetic to magnetically ordered phase transition for values of x between 0.4 and 0.5. A correlation was found between the values of the MES isomer shift and the catalytic activity for peroxide decomposition. Thus, the catalytic activity can be correlated to the d-electron density for the transition metal cations.

  1. Influence of iron addition on the oxygen-deficient Sr{sub 0.85}Bi{sub 0.15}Co{sub 1-x}Fe{sub x}O{sub 3-{delta}} (0.0{<=}x{<=}1.0) perovskites

    SciTech Connect

    Eriksson, Annika K.; Lindberg, Fredrik; Svensson, Gunnar; Svedlindh, Peter; Henry, Paul F.; Eriksson, Sten-G.; Knee, Christopher S.

    2008-08-15

    A series of oxygen-deficient Sr{sub 0.85}Bi{sub 0.15}Co{sub 1-x}Fe{sub x}O{sub 3-{delta}} (0.0{<=}x{<=}1.0) perovskite phases were prepared using solid-state reaction. Results of neutron powder diffraction analyses show that the introduction of Fe onto the B-site severely effects the long range coherence of the oxygen vacancy ordered, I4/mmm supercell, observed for the x=0.0 sample. For x=0.1 a smaller, a=b{approx}a{sub p}, c{approx}2a{sub p}, P4/mmm supercell gives the best agreement to the diffraction data, whilst phases in the range 0.2{<=}x{<=}0.6 adopt disordered cubic perovskite structures. Pseudo-cubic, a=b{approx}a{sub p}, c{approx}a{sub p}, structures are found for x{>=}0.8. Evidence of weak superstructures, reflecting local oxygen ordering, is also obtained from electron diffraction. For all oxygen-annealed phases the average structure reverts to cubic Pm3-bar m. The as-prepared samples show G-type antiferromagnetic order at room temperature. The oxygen annealed x=0.10, 0.25 and 1.0 samples display low-temperature spin-glass transitions. - Graphical abstract: Evolving crystal structures of the as-prepared Sr{sub 0.85}Bi{sub 0.15}Co{sub 1-x}Fe{sub x}O{sub 3-{delta}} perovskites as a function of iron content for the compositional range 0.1{<=}x{<=}1.0.

  2. 30 CFR 57.5015 - Oxygen deficiency.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 30 Mineral Resources 1 2013-07-01 2013-07-01 false Oxygen deficiency. 57.5015 Section 57.5015..., Physical Agents, and Diesel Particulate Matter Air Quality-Underground Only § 57.5015 Oxygen deficiency. Air in all active workings shall contain at least 19.5 volume percent oxygen....

  3. 30 CFR 57.5015 - Oxygen deficiency.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 30 Mineral Resources 1 2012-07-01 2012-07-01 false Oxygen deficiency. 57.5015 Section 57.5015..., Physical Agents, and Diesel Particulate Matter Air Quality-Underground Only § 57.5015 Oxygen deficiency. Air in all active workings shall contain at least 19.5 volume percent oxygen....

  4. 30 CFR 57.5015 - Oxygen deficiency.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 30 Mineral Resources 1 2010-07-01 2010-07-01 false Oxygen deficiency. 57.5015 Section 57.5015..., Physical Agents, and Diesel Particulate Matter Air Quality-Underground Only § 57.5015 Oxygen deficiency. Air in all active workings shall contain at least 19.5 volume percent oxygen....

  5. 30 CFR 57.5015 - Oxygen deficiency.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 30 Mineral Resources 1 2011-07-01 2011-07-01 false Oxygen deficiency. 57.5015 Section 57.5015..., Physical Agents, and Diesel Particulate Matter Air Quality-Underground Only § 57.5015 Oxygen deficiency. Air in all active workings shall contain at least 19.5 volume percent oxygen....

  6. 30 CFR 57.5015 - Oxygen deficiency.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 30 Mineral Resources 1 2014-07-01 2014-07-01 false Oxygen deficiency. 57.5015 Section 57.5015..., Physical Agents, and Diesel Particulate Matter Air Quality-Underground Only § 57.5015 Oxygen deficiency. Air in all active workings shall contain at least 19.5 volume percent oxygen....

  7. Oxygen Vacancy Linear Clustering in a Perovskite Oxide

    DOE PAGES

    Eom, Kitae; Choi, Euiyoung; Choi, Minsu; ...

    2017-07-14

    Oxygen vacancies have been implicitly assumed isolated ones, and understanding oxide materials possibly containing oxygen vacancies remains elusive within the scheme of the isolated vacancies, although the oxygen vacancies have been playing a decisive role in oxide materials. We report the presence of oxygen vacancy linear clusters and their orientation along a specific crystallographic direction in SrTiO3, a representative of a perovskite oxide. The presence of the linear clusters and associated electron localization was revealed by an electronic structure represented in the increase in the Ti2+ valence state or corresponding Ti 3d2 electronic configuration along with divacancy cluster model analysismore » and transport measurement. The orientation of the linear clusters along the [001] direction in perovskite SrTiO3 was verified by further X-ray diffuse scattering analysis. And because SrTiO3 is an archetypical perovskite oxide, the vacancy linear clustering with the specific aligned direction and electron localization can be extended to a wide variety of the perovskite oxides.« less

  8. Evaluation of perovskites as electrocatalysts for the oxygen evolution reaction.

    PubMed

    Rincón, Rosalba A; Ventosa, Edgar; Tietz, Frank; Masa, Justus; Seisel, Sabine; Kuznetsov, Volodymyr; Schuhmann, Wolfgang

    2014-09-15

    The oxygen evolution reaction (OER) is an enabling process for technologies in the area of energy conversion and storage, but its slow kinetics limits its efficiency. We performed an electrochemical evaluation of 14 different perovskites of variable composition and stoichiometry as OER electrocatalysts in alkaline media. We particularly focused on improved methods for a reliable comparison of catalyst activity. From initial electrochemical results we selected the most active samples for further optimization of electrode preparation and testing. An inverted cell configuration facilitated gas bubble detachment and thus minimized blockage of the active surface area. We describe parameters, such as the presence of specific cations, stoichiometry, and conductivity, that are important for obtaining electroactive perovskites for OER. Conductive additives enhanced the current and decreased the apparent overpotential of OER for one of the most active samples (La(0.58)Sr(0.4)Fe(0.8)Co(0.2)O(3)).

  9. Fast oxygen diffusion and iodide defects mediate oxygen-induced degradation of perovskite solar cells

    PubMed Central

    Aristidou, Nicholas; Eames, Christopher; Sanchez-Molina, Irene; Bu, Xiangnan; Kosco, Jan; Islam, M. Saiful; Haque, Saif A.

    2017-01-01

    Methylammonium lead halide perovskites are attracting intense interest as promising materials for next-generation solar cells, but serious issues related to long-term stability need to be addressed. Perovskite films based on CH3NH3PbI3 undergo rapid degradation when exposed to oxygen and light. Here, we report mechanistic insights into this oxygen-induced photodegradation from a range of experimental and computational techniques. We find fast oxygen diffusion into CH3NH3PbI3 films is accompanied by photo-induced formation of highly reactive superoxide species. Perovskite films composed of small crystallites show higher yields of superoxide and lower stability. Ab initio simulations indicate that iodide vacancies are the preferred sites in mediating the photo-induced formation of superoxide species from oxygen. Thin-film passivation with iodide salts is shown to enhance film and device stability. The understanding of degradation phenomena gained from this study is important for the future design and optimization of stable perovskite solar cells. PMID:28492235

  10. Fast oxygen diffusion and iodide defects mediate oxygen-induced degradation of perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Aristidou, Nicholas; Eames, Christopher; Sanchez-Molina, Irene; Bu, Xiangnan; Kosco, Jan; Islam, M. Saiful; Haque, Saif A.

    2017-05-01

    Methylammonium lead halide perovskites are attracting intense interest as promising materials for next-generation solar cells, but serious issues related to long-term stability need to be addressed. Perovskite films based on CH3NH3PbI3 undergo rapid degradation when exposed to oxygen and light. Here, we report mechanistic insights into this oxygen-induced photodegradation from a range of experimental and computational techniques. We find fast oxygen diffusion into CH3NH3PbI3 films is accompanied by photo-induced formation of highly reactive superoxide species. Perovskite films composed of small crystallites show higher yields of superoxide and lower stability. Ab initio simulations indicate that iodide vacancies are the preferred sites in mediating the photo-induced formation of superoxide species from oxygen. Thin-film passivation with iodide salts is shown to enhance film and device stability. The understanding of degradation phenomena gained from this study is important for the future design and optimization of stable perovskite solar cells.

  11. Design Principles of Perovskites for Thermochemical Oxygen Separation.

    PubMed

    Ezbiri, Miriam; Allen, Kyle M; Gàlvez, Maria E; Michalsky, Ronald; Steinfeld, Aldo

    2015-06-08

    Separation and concentration of O2 from gas mixtures is central to several sustainable energy technologies, such as solar-driven synthesis of liquid hydrocarbon fuels from CO2 , H2 O, and concentrated sunlight. We introduce a rationale for designing metal oxide redox materials for oxygen separation through "thermochemical pumping" of O2 against a pO2 gradient with low-grade process heat. Electronic structure calculations show that the activity of O vacancies in metal oxides pinpoints the ideal oxygen exchange capacity of perovskites. Thermogravimetric analysis and high-temperature X-ray diffraction for SrCoO3-δ , BaCoO3-δ and BaMnO3-δ perovskites and Ag2 O and Cu2 O references confirm the predicted performance of SrCoO3-δ , which surpasses the performance of state-of-the-art Cu2 O at these conditions with an oxygen exchange capacity of 44 mmol O 2 mol SrCoO 3-δ(-1) exchanged at 12.1 μmol O 2 min(-1)  g(-1) at 600-900 K. The redox trends are understood due to lattice expansion and electronic charge transfer. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Design Principles of Perovskites for Thermochemical Oxygen Separation

    PubMed Central

    Ezbiri, Miriam; Allen, Kyle M.; Gàlvez, Maria E.; Steinfeld, Aldo

    2015-01-01

    Abstract Separation and concentration of O2 from gas mixtures is central to several sustainable energy technologies, such as solar‐driven synthesis of liquid hydrocarbon fuels from CO2, H2O, and concentrated sunlight. We introduce a rationale for designing metal oxide redox materials for oxygen separation through “thermochemical pumping” of O2 against a pO2 gradient with low‐grade process heat. Electronic structure calculations show that the activity of O vacancies in metal oxides pinpoints the ideal oxygen exchange capacity of perovskites. Thermogravimetric analysis and high‐temperature X‐ray diffraction for SrCoO3−δ, BaCoO3−δ and BaMnO3−δ perovskites and Ag2O and Cu2O references confirm the predicted performance of SrCoO3−δ, which surpasses the performance of state‐of‐the‐art Cu2O at these conditions with an oxygen exchange capacity of 44 mmol O 2 mol SrCoO 3−δ −1 exchanged at 12.1 μmol O 2 min−1 g−1 at 600–900 K. The redox trends are understood due to lattice expansion and electronic charge transfer. PMID:25925955

  13. Bifunctional Oxygen Reaction Catalysis of Quadruple Manganese Perovskites.

    PubMed

    Yamada, Ikuya; Fujii, Hiroshi; Takamatsu, Akihiko; Ikeno, Hidekazu; Wada, Kouhei; Tsukasaki, Hirofumi; Kawaguchi, Shogo; Mori, Shigeo; Yagi, Shunsuke

    2017-01-01

    Bifunctional electrocatalysts for oxygen evolution/reduction reaction (OER/ORR) are desirable for the development of energy conversion technologies. It is discovered that the manganese quadruple perovskites CaMn7 O12 and LaMn7 O12 show bifunctional catalysis in the OER/ORR. A possible origin of the high OER activity is the unique surface structure through corner-shared planar MnO4 and octahedral MnO6 units to promote direct OO bond formations. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Dynamic Octahedral Breathing in Oxygen-Deficient Ba(0.9)Co(0.7)Fe(0.2)Nb(0.1)O(3-δ) Perovskite Performing as a Cathode in Intermediate-Temperature SOFC.

    PubMed

    Gong, Yudong; Sun, Chunwen; Huang, Qiu-an; Alonso, Jose Antonio; Fernández-Díaz, Maria Teresa; Chen, Liquan

    2016-03-21

    Ba(0.9)Co(0.7)Fe(0.2)Nb(0.1)O(3-δ) outperforms as a cathode in solid-oxide fuel cells (SOFC), at temperatures as low as 700-750 °C. The microscopical reason for this performance was investigated by temperature-dependent neutron powder diffraction (NPD) experiments. In the temperature range of 25-800 °C, Ba(0.9)Co(0.7)Fe(0.2)Nb(0.1)O(3-δ) shows a perfectly cubic structure (a = a0), with a significant oxygen deficiency in a single oxygen site, that substantially increases at the working temperatures of a SOFC. The anisotropic thermal motion of oxygen atoms considerably rises with T, reaching B(eq) ≈ 5 Å(2) at 800 °C, with prolate cigar-shaped, anisotropic vibration ellipsoids that suggest a dynamic breathing of the octahedra as oxygen ions diffuse across the structure by a vacancies mechanism, thus implying a significant ionic mobility that could be described as a molten oxygen sublattice. The test cell with a La(0.8)Sr(0.2)Ga(0.83)Mg(0.17)O(3-δ) electrolyte (∼300 μm in thickness)-supported configuration yields a peak power density of 0.20 and 0.40 W cm(-2) at temperatures of 700 and 750 °C, respectively, with pure H2 as fuel and ambient air as oxidant. The electrochemical impedance spectra (EIS) evolution with time of the symmetric cathode fuel cell measured at 750 °C shows that the Ba(0.9)Co(0.7)Fe(0.2)Nb(0.1)O(3-δ) cathode possesses a superior ORR catalytic activity and long-term stability. The mixed electronic-ionic conduction properties of Ba(0.9)Co(0.7)Fe(0.2)Nb(0.1)O(3-δ) account for its good performance as an oxygen-reduction catalyst.

  15. Perovskite-type oxides - Oxygen electrocatalysis and bulk structure

    NASA Technical Reports Server (NTRS)

    Carbonio, R. E.; Fierro, C.; Tryk, D.; Scherson, D.; Yeager, E.

    1988-01-01

    Perovskite type oxides were considered for use as oxygen reduction and generation electrocatalysts in alkaline electrolytes. Perovskite stability and electrocatalytic activity are studied along with possible relationships of the latter with the bulk solid state properties. A series of compounds of the type LaFe(x)Ni1(-x)O3 was used as a model system to gain information on the possible relationships between surface catalytic activity and bulk structure. Hydrogen peroxide decomposition rate constants were measured for these compounds. Ex situ Mossbauer effect spectroscopy (MES), and magnetic susceptibility measurements were used to study the solid state properties. X ray photoelectron spectroscopy (XPS) was used to examine the surface. MES has indicated the presence of a paramagnetic to magnetically ordered phase transition for values of x between 0.4 and 0.5. A correlation was found between the values of the MES isomer shift and the catalytic activity for peroxide decomposition. Thus, the catalytic activity can be correlated to the d-electron density for the transition metal cations.

  16. Perovskite-type oxides - Oxygen electrocatalysis and bulk structure

    NASA Technical Reports Server (NTRS)

    Carbonio, R. E.; Fierro, C.; Tryk, D.; Scherson, D.; Yeager, E.

    1988-01-01

    Perovskite type oxides were considered for use as oxygen reduction and generation electrocatalysts in alkaline electrolytes. Perovskite stability and electrocatalytic activity are studied along with possible relationships of the latter with the bulk solid state properties. A series of compounds of the type LaFe(x)Ni1(-x)O3 was used as a model system to gain information on the possible relationships between surface catalytic activity and bulk structure. Hydrogen peroxide decomposition rate constants were measured for these compounds. Ex situ Mossbauer effect spectroscopy (MES), and magnetic susceptibility measurements were used to study the solid state properties. X ray photoelectron spectroscopy (XPS) was used to examine the surface. MES has indicated the presence of a paramagnetic to magnetically ordered phase transition for values of x between 0.4 and 0.5. A correlation was found between the values of the MES isomer shift and the catalytic activity for peroxide decomposition. Thus, the catalytic activity can be correlated to the d-electron density for the transition metal cations.

  17. Effect of A-site deficiency in LaMn{sub 0.9}Co{sub 0.1}O{sub 3} perovskites on their catalytic performance for soot combustion

    SciTech Connect

    Dinamarca, Robinson; Garcia, Ximena; Jimenez, Romel; Fierro, J.L.G.; Pecchi, Gina

    2016-09-15

    Highlights: • A-site defective perovskites increases the oxidation state of the B-cation. • Not always non-stoichiometric perovskites exhibit higher catalytic activity in soot combustion. • The highly symmetric cubic crystalline structure diminishes the redox properties of perovskites. - Abstract: The influence of lanthanum stoichiometry in Ag-doped (La{sub 1-x}Ag{sub x}Mn{sub 0.9}Co{sub 0.1}O{sub 3}) and A-site deficient (La{sub 1-x}Mn{sub 0.9}Co{sub 0.1}O{sub 3-δ}) perovskites with x equal to 10, 20 and 30 at.% has been investigated in catalysts for soot combustion. The catalysts were prepared by the amorphous citrate method and characterized by XRD, nitrogen adsorption, XPS, O{sub 2}-TPD and TPR. The formation of a rhombohedral excess-oxygen perovskite for Ag-doped and a cubic perovskite structure for an A-site deficient series is confirmed. The efficient catalytic performance of the larger Ag-doped perovskite structure is attributed to the rhombohedral crystalline structure, Ag{sub 2}O segregated phases and the redox pair Mn{sup 4+}/Mn{sup 3+}. A poor catalytic activity for soot combustion was observed with A-site deficient perovskites, despite the increase in the redox pair Mn{sup 4+}/Mn{sup 3+}, which is attributed to the cubic crystalline structure.

  18. Activation of oxygen evolving perovskites for oxygen reduction by functionalization with Fe-N(x)/C groups.

    PubMed

    Rincón, Rosalba A; Masa, Justus; Mehrpour, Sara; Tietz, Frank; Schuhmann, Wolfgang

    2014-12-07

    The incorporation of Fe-Nx/C moieties into perovskites remarkably activates them for the oxygen reduction reaction (ORR) and also leads to notable improvement of their activity towards the oxygen evolution reaction (OER) thus presenting a new route for realizing high performance, low cost bifunctional catalysts for reversible oxygen electrodes.

  19. A tailored double perovskite nanofiber catalyst enables ultrafast oxygen evolution.

    PubMed

    Zhao, Bote; Zhang, Lei; Zhen, Dongxing; Yoo, Seonyoung; Ding, Yong; Chen, Dongchang; Chen, Yu; Zhang, Qiaobao; Doyle, Brian; Xiong, Xunhui; Liu, Meilin

    2017-02-27

    Rechargeable metal-air batteries and water splitting are highly competitive options for a sustainable energy future, but their commercialization is hindered by the absence of cost-effective, highly efficient and stable catalysts for the oxygen evolution reaction. Here we report the rational design and synthesis of a double perovskite PrBa0.5Sr0.5Co1.5Fe0.5O5+δ nanofiber as a highly efficient and robust catalyst for the oxygen evolution reaction. Co-doping of strontium and iron into PrBaCo2O5+δ is found to be very effective in enhancing intrinsic activity (normalized by the geometrical surface area, ∼4.7 times), as validated by electrochemical measurements and first-principles calculations. Further, the nanofiber morphology enhances its mass activity remarkably (by ∼20 times) as the diameter is reduced to ∼20 nm, attributed to the increased surface area and an unexpected intrinsic activity enhancement due possibly to a favourable eg electron filling associated with partial surface reduction, as unravelled from chemical titration and electron energy-loss spectroscopy.

  20. A tailored double perovskite nanofiber catalyst enables ultrafast oxygen evolution

    NASA Astrophysics Data System (ADS)

    Zhao, Bote; Zhang, Lei; Zhen, Dongxing; Yoo, Seonyoung; Ding, Yong; Chen, Dongchang; Chen, Yu; Zhang, Qiaobao; Doyle, Brian; Xiong, Xunhui; Liu, Meilin

    2017-02-01

    Rechargeable metal-air batteries and water splitting are highly competitive options for a sustainable energy future, but their commercialization is hindered by the absence of cost-effective, highly efficient and stable catalysts for the oxygen evolution reaction. Here we report the rational design and synthesis of a double perovskite PrBa0.5Sr0.5Co1.5Fe0.5O5+δ nanofiber as a highly efficient and robust catalyst for the oxygen evolution reaction. Co-doping of strontium and iron into PrBaCo2O5+δ is found to be very effective in enhancing intrinsic activity (normalized by the geometrical surface area, ~4.7 times), as validated by electrochemical measurements and first-principles calculations. Further, the nanofiber morphology enhances its mass activity remarkably (by ~20 times) as the diameter is reduced to ~20 nm, attributed to the increased surface area and an unexpected intrinsic activity enhancement due possibly to a favourable eg electron filling associated with partial surface reduction, as unravelled from chemical titration and electron energy-loss spectroscopy.

  1. A tailored double perovskite nanofiber catalyst enables ultrafast oxygen evolution

    PubMed Central

    Zhao, Bote; Zhang, Lei; Zhen, Dongxing; Yoo, Seonyoung; Ding, Yong; Chen, Dongchang; Chen, Yu; Zhang, Qiaobao; Doyle, Brian; Xiong, Xunhui; Liu, Meilin

    2017-01-01

    Rechargeable metal–air batteries and water splitting are highly competitive options for a sustainable energy future, but their commercialization is hindered by the absence of cost-effective, highly efficient and stable catalysts for the oxygen evolution reaction. Here we report the rational design and synthesis of a double perovskite PrBa0.5Sr0.5Co1.5Fe0.5O5+δ nanofiber as a highly efficient and robust catalyst for the oxygen evolution reaction. Co-doping of strontium and iron into PrBaCo2O5+δ is found to be very effective in enhancing intrinsic activity (normalized by the geometrical surface area, ∼4.7 times), as validated by electrochemical measurements and first-principles calculations. Further, the nanofiber morphology enhances its mass activity remarkably (by ∼20 times) as the diameter is reduced to ∼20 nm, attributed to the increased surface area and an unexpected intrinsic activity enhancement due possibly to a favourable eg electron filling associated with partial surface reduction, as unravelled from chemical titration and electron energy-loss spectroscopy. PMID:28240282

  2. 30 CFR 57.8527 - Oxygen-deficiency testing.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 30 Mineral Resources 1 2011-07-01 2011-07-01 false Oxygen-deficiency testing. 57.8527 Section 57... Underground Only § 57.8527 Oxygen-deficiency testing. Flame safety lamps or other suitable devices shall be used to test for acute oxygen deficiency....

  3. 30 CFR 57.8527 - Oxygen-deficiency testing.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 30 Mineral Resources 1 2013-07-01 2013-07-01 false Oxygen-deficiency testing. 57.8527 Section 57... Underground Only § 57.8527 Oxygen-deficiency testing. Flame safety lamps or other suitable devices shall be used to test for acute oxygen deficiency....

  4. 30 CFR 57.8527 - Oxygen-deficiency testing.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 30 Mineral Resources 1 2010-07-01 2010-07-01 false Oxygen-deficiency testing. 57.8527 Section 57... Underground Only § 57.8527 Oxygen-deficiency testing. Flame safety lamps or other suitable devices shall be used to test for acute oxygen deficiency....

  5. 30 CFR 57.8527 - Oxygen-deficiency testing.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 30 Mineral Resources 1 2014-07-01 2014-07-01 false Oxygen-deficiency testing. 57.8527 Section 57... Underground Only § 57.8527 Oxygen-deficiency testing. Flame safety lamps or other suitable devices shall be used to test for acute oxygen deficiency....

  6. 30 CFR 57.8527 - Oxygen-deficiency testing.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 30 Mineral Resources 1 2012-07-01 2012-07-01 false Oxygen-deficiency testing. 57.8527 Section 57... Underground Only § 57.8527 Oxygen-deficiency testing. Flame safety lamps or other suitable devices shall be used to test for acute oxygen deficiency....

  7. Antiferromagnetism and superconductivity in oxygen-deficient YBa2Cu3O(x)

    NASA Technical Reports Server (NTRS)

    Brewer, J. H.; Carolan, J. F.; Chaklader, A. C. D.; Hardy, W. N.; Ansaldo, E. J.

    1988-01-01

    Positive-muon spin-rotation and -relaxation measurements of the oxygen-deficient perovskite YBa2Cu3O(x) have revealed local antiferromagnetic order for x = 6.0-6.4 with a Neel temperature TN that decreases rapidly with increasing oxygen content x. For slowly annealed samples with x = 6.35-6.5 the superconducting transition temperature Tc increases smoothly with x from 25 K at x = 6.348 to 60 K at x = 6.507. Two such samples with x = 6.348 and x = 6.400 appear to 'switch' from superconductivity to antiferromagnetic order at lower temperatures.

  8. Reversible, Fast, and Wide-Range Oxygen Sensor Based on Nanostructured Organometal Halide Perovskite.

    PubMed

    Stoeckel, Marc-Antoine; Gobbi, Marco; Bonacchi, Sara; Liscio, Fabiola; Ferlauto, Laura; Orgiu, Emanuele; Samorì, Paolo

    2017-10-01

    Nanostructured materials characterized by high surface-volume ratio hold the promise to constitute the active materials for next-generation sensors. Solution-processed hybrid organohalide perovskites, which have been extensively used in the last few years for optoelectronic applications, are characterized by a self-assembled nanostructured morphology, which makes them an ideal candidate for gas sensing. Hitherto, detailed studies of the dependence of their electrical characteristics on the environmental atmosphere have not been performed, and even the effect of a ubiquitous gas such as O2 has been widely overlooked. Here, the electrical response of organohalide perovskites to oxygen is studied. Surprisingly, a colossal increase (3000-fold) in the resistance of perovskite-based lateral devices is found when measured in a full oxygen atmosphere, which is ascribed to a trap healing mechanism originating from an O2 -mediated iodine vacancies filling. A variation as small as 70 ppm in the oxygen concentration can be detected. The effect is fast (<400 ms) and fully reversible, making organohalide perovskites ideal active materials for oxygen sensing. The effect of oxygen on the electrical characteristics of organohalide perovskites must be taken into deep consideration for the design and optimization of any other perovskite-based (opto-) electronic device working in ambient conditions. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Systematic Study of Compositional and Synthetic Control of Vacancy and Magnetic Ordering in Oxygen-Deficient Perovskites Ca2Fe2 xMnxO5+yand CaSrFe2 xMnxO5+y (x = 1/2, 2/3, and 1; y = 0 1/2)

    SciTech Connect

    Ramezanipour, Farshid; Greedan, John E; Cranswick, Lachlan M.D.; Donaberger, R. L.; Garlea, Vasile O; Siewenie, Joan

    2012-01-01

    Ten compounds belonging to the series of oxygen-deficient perovskite oxides Ca2Fe2 xMnxO5 and CaSrFe2 xMnxO5+y, where x = 1/2, 2/3, and 1 and y 0 0.5, were synthesized and investigated with respect to the ordering of oxygen vacancies on both local and long-range length scales and the effect on crystal structure and magnetic properties. For the set with y 0 the oxygen vacancies always order in the long-range sense to form the brownmillerite structure containing alternating layers of octahedrally and tetrahedrally coordinated cations. However, there is a change in symmetry from Pnma to Icmm upon substitution of Sr for one Ca for all x, indicating local Td chain (vacancy) disorder. In the special case of CaSrFeMnO5 the neutron diffraction peaks broaden, indicating only short-range structural order on a length scale of 160 . This reveals a systematic progression from Ca2FeMnO5 (Pnma, well-ordered tetrahedral chains) to CaSrFeMnO5 (Icmm, disordered tetrahedral chains, overall short-range order) to Sr2FeMnO5 (Pm3m, destruction of tetrahedral chains in a long-range sense). Systematic changes occur in the magnetic properties as well. While long-range antiferromagnetic order is preserved, the magnetic transition temperature, Tc, decreases for the same x when Sr substitutes for one Ca. A review of the changes in Tc for the series Ca2Fe2 xMxO5, taking into account the tetrahedral/octahedral site preferences for the various M3+ ions, leads to a partial understanding of the origin of magnetic order in these materials in terms of a layered antiferromagnetic model. While in all cases the preferred magnetic moment direction is (010) at low temperatures, there is a cross over for x = 0.5 to (100) with increasing temperature for both the Ca2Fe2 xMnxO5 and the CaSrFe2 xMnxO5 series. For the y > 0 phases, while a brownmillerite ordering of oxygen vacancies is preserved for the Ca2 phases, a disordered Pm3m cubic perovskite structure is always found when Sr is substituted for one Ca

  10. Systematic study of compositional and synthetic control of vacancy and magnetic ordering in oxygen-deficient perovskites Ca2Fe(2-x)Mn(x)O(5+y)and CaSrFe(2-x)Mn(x)O(5+y) (x = 1/2, 2/3, and 1; y = 0-1/2).

    PubMed

    Ramezanipour, Farshid; Greedan, John E; Cranswick, Lachlan M D; Garlea, V Ovidiu; Donaberger, Ronald L; Siewenie, Joan

    2012-02-15

    Ten compounds belonging to the series of oxygen-deficient perovskite oxides Ca(2)Fe(2-x)Mn(x)O(5) and CaSrFe(2-x)Mn(x)O(5+y), where x = 1/2, 2/3, and 1 and y ≈ 0-0.5, were synthesized and investigated with respect to the ordering of oxygen vacancies on both local and long-range length scales and the effect on crystal structure and magnetic properties. For the set with y ≈ 0 the oxygen vacancies always order in the long-range sense to form the brownmillerite structure containing alternating layers of octahedrally and tetrahedrally coordinated cations. However, there is a change in symmetry from Pnma to Icmm upon substitution of Sr for one Ca for all x, indicating local T(d) chain (vacancy) disorder. In the special case of CaSrFeMnO(5) the neutron diffraction peaks broaden, indicating only short-range structural order on a length scale of ~160 Å. This reveals a systematic progression from Ca(2)FeMnO(5) (Pnma, well-ordered tetrahedral chains) to CaSrFeMnO(5) (Icmm, disordered tetrahedral chains, overall short-range order) to Sr(2)FeMnO(5) (Pm3m, destruction of tetrahedral chains in a long-range sense). Systematic changes occur in the magnetic properties as well. While long-range antiferromagnetic order is preserved, the magnetic transition temperature, T(c), decreases for the same x when Sr substitutes for one Ca. A review of the changes in T(c) for the series Ca(2)Fe(2-x)M(x)O(5), taking into account the tetrahedral/octahedral site preferences for the various M(3+) ions, leads to a partial understanding of the origin of magnetic order in these materials in terms of a layered antiferromagnetic model. While in all cases the preferred magnetic moment direction is (010) at low temperatures, there is a cross over for x = 0.5 to (100) with increasing temperature for both the Ca(2)Fe(2-x)Mn(x)O(5) and the CaSrFe(2-x)Mn(x)O(5) series. For the y > 0 phases, while a brownmillerite ordering of oxygen vacancies is preserved for the Ca(2) phases, a disordered Pm3m cubic

  11. Effect of cation ordering on oxygen vacancy diffusion pathways in double perovskites

    SciTech Connect

    Uberuaga, Blas Pedro; Pilania, Ghanshyam

    2015-07-08

    Perovskite structured oxides (ABO3) are attractive for a number of technological applications, including as superionics because of the high oxygen conductivities they exhibit. Double perovskites (AA’BB’O6) provide even more flexibility for tailoring properties. Using accelerated molecular dynamics, we examine the role of cation ordering on oxygen vacancy mobility in one model double perovskite SrLaTiAlO6. We find that the mobility of the vacancy is very sensitive to the cation ordering, with a migration energy that varies from 0.6 to 2.7 eV. In the extreme cases, the mobility is both higher and lower than either of the two end member single perovskites. Further, the nature of oxygen vacancy diffusion, whether one-dimensional, two-dimensional, or three-dimensional, also varies with cation ordering. We correlate the dependence of oxygen mobility on cation structure to the distribution of Ti4+ cations, which provide unfavorable environments for the positively charged oxygen vacancy. The results demonstrate the potential of using tailored double perovskite structures to precisely control the behavior of oxygen vacancies in these materials.

  12. Effect of cation ordering on oxygen vacancy diffusion pathways in double perovskites

    DOE PAGES

    Uberuaga, Blas Pedro; Pilania, Ghanshyam

    2015-07-08

    Perovskite structured oxides (ABO3) are attractive for a number of technological applications, including as superionics because of the high oxygen conductivities they exhibit. Double perovskites (AA’BB’O6) provide even more flexibility for tailoring properties. Using accelerated molecular dynamics, we examine the role of cation ordering on oxygen vacancy mobility in one model double perovskite SrLaTiAlO6. We find that the mobility of the vacancy is very sensitive to the cation ordering, with a migration energy that varies from 0.6 to 2.7 eV. In the extreme cases, the mobility is both higher and lower than either of the two end member single perovskites.more » Further, the nature of oxygen vacancy diffusion, whether one-dimensional, two-dimensional, or three-dimensional, also varies with cation ordering. We correlate the dependence of oxygen mobility on cation structure to the distribution of Ti4+ cations, which provide unfavorable environments for the positively charged oxygen vacancy. The results demonstrate the potential of using tailored double perovskite structures to precisely control the behavior of oxygen vacancies in these materials.« less

  13. A high reliability oxygen deficiency monitoring system

    SciTech Connect

    Parry, R.; Claborn, G.; Haas, A.; Landis, R.; Page, W.; Smith, J.

    1993-05-01

    The escalating use of cryogens at national laboratories in general and accelerators in particular, along with the increased emphasis placed on personnel safety, mandates the development and installation of oxygen monitoring systems to insure personnel safety in the event of a cryogenic leak. Numerous vendors offer oxygen deficiency monitoring systems but fail to provide important features and/or flexibility. This paper describes a unique oxygen monitoring system developed for the Magnet Test Laboratory (MTL) at the Superconducting Super Collider Laboratory (SSCL). Features include: high reliability, oxygen cell redundancy, sensor longevity, simple calibration, multiple trip points, offending sensor audio and visual indication, global alarms for building evacuation, local and remote analog readout, event and analog data logging, EMAIL event notification, phone line voice status system, and multi-drop communications network capability for reduced cable runs. Of particular importance is the distributed topology of the system which allows it to operate in a stand-alone configuration or to communicate with a host computer. This flexibility makes it ideal for small applications such as a small room containing a cryogenic dewar, as well as larger systems which monitor many offices and labs in several buildings.

  14. Enhanced Bifunctional Oxygen Catalysis in Strained LaNiO3 Perovskites

    SciTech Connect

    Petrie, Jonathan R.; Cooper, Valentino R.; Freeland, John W.; Meyer, Tricia L.; Zhang, Zhiyong; Lutterman, Daniel A.; Lee, Ho Nyung

    2016-03-02

    Strain is known to greatly influence low temperature oxygen electro catalysis on noble metal films, leading to significant enhancements in bifunctional activity essential for fuel cells and Metal-air batteries. However, its catalytic impact on transition-metal oxide thin films, such as perovskites, is not widely understood. Here, we epitaxially strain the conducting perovskite LaNiO3 to systematically determine its influence on both the oxygen reduction and oxygen evolution reaction. Uniquely, we found that compressive strain could significantly enhance both reactions, yielding a bifunctional catalyst that surpasses the performance of noble metals' such as Pt. We attribute the improved bifunctionality to strain induced splitting of the e(g) Orbitals, which can customize orbital asymmetry at the surface. Analogous to strain induced shifts in the d-band center of noble metals relative to the Fermi level, :such splitting can dramatically affect catalytic activity in this perovskite and other potentially more active Oxides.

  15. Electrocatalytic oxygen reduction reaction on perovskite oxides: series versus direct pathway.

    PubMed

    Poux, Tiphaine; Bonnefont, Antoine; Kéranguéven, Gwénaëlle; Tsirlina, Galina A; Savinova, Elena R

    2014-07-21

    The mechanism of the oxygen reduction reaction (ORR) on LaCoO(3) and La(0.8)Sr(0.2)MnO(3) perovskite oxides is studied in 1 M NaOH by using the rotating ring disc electrode (RRDE) method. By combining experimental studies with kinetic modeling, it was demonstrated that on perovskite, as well as on perovskite/carbon electrodes, the ORR follows a series pathway through the intermediate formation of hydrogen peroxide. The escape of this intermediate from the electrode strongly depends on: 1) The loading of perovskite; high loadings lead to an overall 4 e(-) oxygen reduction due to efficient hydrogen peroxide re-adsorption on the active sites and its further reduction. 2) The addition of carbon to the catalytic layer, which affects both the utilization of the perovskite surface and the production of hydrogen peroxide. 3) The type of oxide; La(0.8)Sr(0.2)MnO(3) displays higher (compared to LaCoO(3)) activity in the reduction of oxygen to hydrogen peroxide and in the reduction/oxidation of the latter.

  16. Chemically Driven Enhancement of Oxygen Reduction Electrocatalysis in Supported Perovskite Oxides.

    PubMed

    Lee, Daehee; Tan, Jeiwan; Chae, Keun Hwa; Jeong, Beomgyun; Soon, Aloysius; Ahn, Sung-Jin; Kim, Joosun; Moon, Jooho

    2017-01-05

    Perovskite oxides have the capacity to efficiently catalyze the oxygen reduction reaction (ORR), which is of fundamental importance for electrochemical energy conversion. While the perovskite catalysts have been generally utilized with a support, the role of the supports, regarded as inert toward the ORR, has been emphasized mostly in terms of the thermal stability of the catalyst system and as an ancillary transport channel for oxygen ions during the ORR. We demonstrate a novel approach to improving the catalytic activity of perovskite oxides for solid oxide fuel cells by controlling the oxygen-ion conducting oxide supports. Catalytic activities of (La0.8Sr0.2)0.95MnO3 perovskite thin-film placed on different oxide supports are characterized by electrochemical impedance spectroscopy and X-ray absorption spectroscopy. These analyses confirm that the strong atomic orbital interactions between the support and the perovskite catalyst enhance the surface exchange kinetics by ∼2.4 times, in turn, improving the overall ORR activity.

  17. Oxygen-deficient metabolism and corneal edema.

    PubMed

    Leung, B K; Bonanno, J A; Radke, C J

    2011-11-01

    Wear of low-oxygen-transmissible soft contact lenses swells the cornea significantly, even during open eye. Although oxygen-deficient corneal edema is well-documented, a self-consistent quantitative prediction based on the underlying metabolic reactions is not available. We present a biochemical description of the human cornea that quantifies hypoxic swelling through the coupled transport of water, salt, and respiratory metabolites. Aerobic and anaerobic consumption of glucose, as well as acidosis and pH buffering, are incorporated in a seven-layer corneal model (anterior chamber, endothelium, stroma, epithelium, postlens tear film, contact lens, and prelens tear film). Corneal swelling is predicted from coupled transport of water, dissolved salts, and especially metabolites, along with membrane-transport resistances at the endothelium and epithelium. At the endothelium, the Na+/K+ - ATPase electrogenic channel actively transports bicarbonate ion from the stroma into the anterior chamber. As captured by the Kedem-Katchalsky membrane-transport formalism, the active bicarbonate-ion flux provides the driving force for corneal fluid pump-out needed to match the leak-in tendency of the stroma. Increased lactate-ion production during hypoxia osmotically lowers the pump-out rate requiring the stroma to swell to higher water content. Concentration profiles are predicted for glucose, water, oxygen, carbon dioxide, and hydronium, lactate, bicarbonate, sodium, and chloride ions, along with electrostatic potential and pressure profiles. Although the active bicarbonate-ion pump at the endothelium drives bicarbonate into the aqueous humor, we find a net flux of bicarbonate ion into the cornea that safeguards against acidosis. For the first time, we predict corneal swelling upon soft-contact-lens wear from fundamental biophysico-chemical principles. We also successfully predict that hypertonic tear alleviates contact-lens-induced edema.

  18. Oxygen-deficient metabolism and corneal edema

    PubMed Central

    Leung, B.K.; Bonanno, J.A.; Radke, C.J.

    2014-01-01

    Wear of low-oxygen-transmissible soft contact lenses swells the cornea significantly, even during open eye. Although oxygen-deficient corneal edema is well-documented, a self-consistent quantitative prediction based on the underlying metabolic reactions is not available. We present a biochemical description of the human cornea that quantifies hypoxic swelling through the coupled transport of water, salt, and respiratory metabolites. Aerobic and anaerobic consumption of glucose, as well as acidosis and pH buffering, are incorporated in a seven-layer corneal model (anterior chamber, endothelium, stroma, epithelium, postlens tear film, contact lens, and prelens tear film). Corneal swelling is predicted from coupled transport of water, dissolved salts, and especially metabolites, along with membrane-transport resistances at the endothelium and epithelium. At the endothelium, the Na+/K+ - ATPase electrogenic channel actively transports bicarbonate ion from the stroma into the anterior chamber. As captured by the Kedem–Katchalsky membrane-transport formalism, the active bicarbonate-ion flux provides the driving force for corneal fluid pump-out needed to match the leak-in tendency of the stroma. Increased lactate-ion production during hypoxia osmotically lowers the pump-out rate requiring the stroma to swell to higher water content. Concentration profiles are predicted for glucose, water, oxygen, carbon dioxide, and hydronium, lactate, bicarbonate, sodium, and chloride ions, along with electrostatic potential and pressure profiles. Although the active bicarbonate-ion pump at the endothelium drives bicarbonate into the aqueous humor, we find a net flux of bicarbonate ion into the cornea that safeguards against acidosis. For the first time, we predict corneal swelling upon soft-contact-lens wear from fundamental biophysico-chemical principles. We also successfully predict that hypertonic tear alleviates contact-lens-induced edema. PMID:21820076

  19. Influence of transition metal electronegativity on the oxygen storage capacity of perovskite oxides.

    PubMed

    Liu, Lu; Taylor, Daniel D; Rodriguez, Efrain E; Zachariah, Michael R

    2016-08-16

    The selection of highly efficient oxygen carriers (OCs) is a key step necessary for the practical development of chemical looping combustion (CLC). In this study, a series of ABO3 perovskites, where A = La, Ba, Sr, Ca and B = Cr, Mn, Fe, Co, Ni, Cu, are synthesized and tested in a fixed bed reactor for reactivity and stability as OCs with CH4 as the fuel. We find that the electronegativity of the transition metal on the B-site (λB), is a convenient descriptor for oxygen storage capacity (OSC) of our perovskite samples. By plotting OSC for total methane oxidation against λB, we observe an inverted volcano plot relationship. These results could provide useful guidelines for perovskite OC design and their other energy related applications.

  20. Relaxation behavior of oxygen deficient strontium manganite

    SciTech Connect

    Pandey, Namita Thakur, Awalendra Kumar

    2014-04-24

    Conduction behavior of nanocrystalline oxygen deficient ceramic-SrMnO{sub 3–δ}(δ∼0.14) has been studied. The structural analysis of nano-SrMnO{sub 2.86} follows hexagonal unit cell structure with P6{sub 3}/mmc (194) space group belonging to 6/mmm point group with 4H – layered type hexagonal-cubic layers. The system have lattice parameters; a = 5.437(92) Å, c = 9.072(92) Å, c/a∼1.66 (85) with α =90° γ= 120° and cell volume, V= 232.35(18). The relaxation times estimated from complex impedance and modulus relaxation spectrum, show the thermally activated system with corresponding activation energies as 0.66 eV and 0.51 eV The stretching factor ‘β’ from the scaled modulus spectrum shows the poly-dispersive non-Debye nature of the system. The hopping number ‘n’ shows the influence of ionic charge carriers which controls the conduction mechanism of nano-SrMnO{sub 2.86}.

  1. Oxygen content tailored magnetic and electronic properties in cobaltite double perovskite thin films

    NASA Astrophysics Data System (ADS)

    Harrell, Zach; Enriquez, Erik; Chen, Aiping; Dowden, Paul; Mace, Brennan; Lü, Xujie; Jia, Quanxi; Chen, Chonglin

    2017-02-01

    Oxygen content in transition metal oxides is one of the most important parameters to control for the desired physical properties. Recently, we have systematically studied the oxygen content and property relationship of the double perovskite PrBaCo2O5.5+δ (PBCO) thin films deposited on the LaAlO3 substrates. The oxygen content in the films was varied by in-situ annealing in a nitrogen, oxygen, or ozone environment. Associated with the oxygen content, the out-of-plane lattice parameter progressively decreases with increasing oxygen content in the films. The saturated magnetization shows a drastic increase and resistivity is significantly reduced in the ozone annealed samples, indicating the strong coupling between physical properties and oxygen content. These results demonstrate that the magnetic properties of PBCO films are highly dependent on the oxygen contents, or the film with higher oxygen uptake has the largest magnetization.

  2. Co-doping Strategy for Developing Perovskite Oxides as Highly Efficient Electrocatalysts for Oxygen Evolution Reaction.

    PubMed

    Xu, Xiaomin; Su, Chao; Zhou, Wei; Zhu, Yinlong; Chen, Yubo; Shao, Zongping

    2016-02-01

    A synergistic co-doping strategy is proposed to identify a series of BaCo0.9-x Fe x Sn0.1O3-δ perovskites with tunable electrocatalytic activity for the oxygen evolution reaction (OER). Simply through tailoring the relative concentrations of less OER-active tin and iron dopants, a cubic perovskite structure (BaCo0.7Fe0.2Sn0.1O3-δ) is stabilized, showing intrinsic OER activity >1 order of magnitude larger than IrO2 and a Tafel slope of 69 mV dec(-1).

  3. Compositional engineering of perovskite oxides for highly efficient oxygen reduction reactions.

    PubMed

    Chen, Dengjie; Chen, Chi; Zhang, Zhenbao; Baiyee, Zarah Medina; Ciucci, Francesco; Shao, Zongping

    2015-04-29

    Mixed conducting perovskite oxides are promising catalysts for high-temperature oxygen reduction reaction. Pristine SrCoO(3-δ) is a widely used parent oxide for the development of highly active mixed conductors. Doping a small amount of redox-inactive cation into the B site (Co site) of SrCoO(3-δ) has been applied as an effective way to improve physicochemical properties and electrochemical performance. Most findings however are obtained only from experimental observations, and no universal guidelines have been proposed. In this article, combined experimental and theoretical studies are conducted to obtain fundamental understanding of the effect of B-site doping concentration with redox-inactive cation (Sc) on the properties and performance of the perovskite oxides. The phase structure, electronic conductivity, defect chemistry, oxygen reduction kinetics, oxygen ion transport, and electrochemical reactivity are experimentally characterized. In-depth analysis of doping level effect is also undertaken by first-principles calculations. Among the compositions, SrCo0.95Sc0.05O(3-δ) shows the best oxygen kinetics and corresponds to the minimum fraction of Sc for stabilization of the oxygen-vacancy-disordered structure. The results strongly support that B-site doping of SrCoO(3-δ) with a small amount of redox-inactive cation is an effective strategy toward the development of highly active mixed conducting perovskites for efficient solid oxide fuel cells and oxygen transport membranes.

  4. Strong excitonic interactions in the oxygen K-edge of perovskite oxides.

    PubMed

    Tomita, Kota; Miyata, Tomohiro; Olovsson, Weine; Mizoguchi, Teruyasu

    2017-07-01

    Excitonic interactions of the oxygen K-edge electron energy-loss near-edge structure (ELNES) of perovskite oxides, CaTiO3, SrTiO3, and BaTiO3, together with reference oxides, MgO, CaO, SrO, BaO, and TiO2, were investigated using a first-principles Bethe-Salpeter equation calculation. Although the transition energy of oxygen K-edge is high, strong excitonic interactions were present in the oxygen K-edge ELNES of the perovskite oxides, whereas the excitonic interactions were negligible in the oxygen K-edge ELNES of the reference compounds. Detailed investigation of the electronic structure suggests that the strong excitonic interaction in the oxygen K-edge ELNES of the perovskite oxides is caused by the directionally confined, low-dimensional electronic structure at the Ti-O-Ti bonds. Copyright © 2016 Elsevier B.V. All rights reserved.

  5. Activity and stability trends of perovskite oxides for oxygen evolution catalysis at neutral pH.

    PubMed

    Han, Binghong; Risch, Marcel; Lee, Yueh-Lin; Ling, Chen; Jia, Hongfei; Shao-Horn, Yang

    2015-09-21

    Perovskite oxides (ABO3) have been studied extensively to promote the kinetics of the oxygen evolution reaction (OER) in alkaline electrolytes. However, developing highly active catalysts for OER at near-neutral pH is desirable for many photoelectrochemical/electrochemical devices. In this paper, we systematically studied the activity and stability of well-known perovskite oxides for OER at pH 7. Previous activity descriptors established for perovskite oxides at pH 13, such as having an eg occupancy close to unity or having an O p-band center close to Fermi level, were shown to scale with OER activity at pH 7. Stability was a greater challenge at pH 7 than at pH 13, where two different modes of instability were identified from combined transmission electron microscopy and density functional theory analyses. Perovskites with O p-band close to Fermi level showed leaching of A-site atoms and surface amorphization under all overpotentials examined at pH 7, while those with O p-band far from Fermi level were stable under low OER current/potential but became unstable at high current/potential accompanied by leaching of B-site atoms. Therefore, efforts are needed to enhance the activity and stability of perovskites against A-site or B-site loss if used at neutral pH.

  6. Oxygen nonstoichiometry, defect structure and oxygen diffusion in the double perovskite GdBaCo2O6-δ.

    PubMed

    Tsvetkov, D S; Ananjev, M V; Eremin, V A; Zuev, A Yu; Kurumchin, E Kh

    2014-11-14

    Oxygen nonstoichiometry of GdBaCo2O6-δ was studied by means of the thermogravimetric technique in the temperature range 600-1000 °C. The defect structure model based on the simple cubic perovskite GdCoO3-δ was shown to be valid for GdBaCo2O6-δ up to temperatures as low as 600 °C. Two independent methods, namely dc-polarization with the YSZ microelectrode and (18)O-isotope exchange with gas phase analysis, were used to determine the oxygen self-diffusion coefficient in the double perovskite GdBaCo2O6-δ. All measurements were carried out using ceramic samples identically prepared from the same single phase powder of GdBaCo2O6-δ. The experimental data on oxygen nonstoichiometry of GdBaCo2O6-δ allowed a precise calculation of the oxygen interphase exchange rate and the oxygen tracer diffusion coefficient on the basis of the isotope exchange measurements. The values of the oxygen self-diffusion coefficient measured by the dc-polarization technique were found to be in very good agreement with the ones of the oxygen tracer diffusion coefficient.

  7. Effect of A-Site Cation Ordering on Chemical Stability, Oxygen Stoichiometry and Electrical Conductivity in Layered LaBaCo2O5+δ Double Perovskite

    PubMed Central

    Bernuy-Lopez, Carlos; Høydalsvik, Kristin; Einarsrud, Mari-Ann; Grande, Tor

    2016-01-01

    The effect of the A-site cation ordering on the chemical stability, oxygen stoichiometry and electrical conductivity in layered LaBaCo2O5+δ double perovskite was studied as a function of temperature and partial pressure of oxygen. Tetragonal A-site cation ordered layered LaBaCo2O5+δ double perovskite was obtained by annealing cubic A-site cation disordered La0.5Ba0.5CoO3-δ perovskite at 1100 °C in N2. High temperature X-ray diffraction between room temperature (RT) and 800 °C revealed that LaBaCo2O5+δ remains tetragonal during heating in oxidizing atmosphere, but goes through two phase transitions in N2 and between 450 °C and 675 °C from tetragonal P4/mmm to orthorhombic Pmmm and back to P4/mmm due to oxygen vacancy ordering followed by disordering of the oxygen vacancies. An anisotropic chemical and thermal expansion of LaBaCo2O5+δ was demonstrated. La0.5Ba0.5CoO3-δ remained cubic at the studied temperature irrespective of partial pressure of oxygen. LaBaCo2O5+δ is metastable with respect to La0.5Ba0.5CoO3-δ at oxidizing conditions inferred from the thermal evolution of the oxygen deficiency and oxidation state of Co in the two materials. The oxidation state of Co is higher in La0.5Ba0.5CoO3-δ resulting in a higher electrical conductivity relative to LaBaCo2O5+δ. The conductivity in both materials was reduced with decreasing partial pressure of oxygen pointing to a p-type semiconducting behavior. PMID:28773279

  8. Mineralogy and Oxygen Isotope Compositions of an Unusual Hibonite-Perovskite Refractory Inclusion from Allende

    NASA Technical Reports Server (NTRS)

    Keller, L. P.; Snead, C.; Rahman, Z.; McKeegan, K. D.

    2012-01-01

    Hibonite-rich Ca- and Al-rich inclusions (CAIs) are among the earliest formed solids that condensed in the early nebula. We discovered an unusual refractory inclusion from the Allende CV3 chondrite (SHAL) containing an approx 500 micron long single crystal of hibonite and co-existing coarse-grained perovskite. The mineralogy and petrography of SHAL show strong similarities to some FUN inclusions, especially HAL. Here we report on the mineralogy, petrography, mineral chemistry and oxygen isotopic compositions in SHAL.

  9. Direct measurement of oxygen stoichiometry in perovskite films

    NASA Astrophysics Data System (ADS)

    Scola, J.; Benamar, A.; Berini, B.; Jomard, F.; Dumont, Y.

    2017-02-01

    We present a direct method to measure the oxygen stoichiometry in an oxide film with an accuracy of about 2%. It is based on a combination of 18O annealing and high mass resolution secondary ion mass spectroscopy. Calibration has been done on a LaNiO3 film whose electrical properties dependence on oxygen stoichiometry are well documented. The method is illustrated with a series of LaNiO3 films grown on SrTiO3 substrates prepared with different oxygen stoichiometries. The large influence of the surface state on oxygen exchange is evidenced in films grown on different substrate orientations or coated with a thin layer of LaAlO3. Oxygen surface exchange and bulk diffusion is then discussed for both LaNiO3 and SrVO3 films.

  10. Enhanced Bifunctional Oxygen Catalysis in Strained LaNiO3 Perovskites

    DOE PAGES

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

    2016-02-11

    Strain is known to greatly influence low-temperature oxygen electrocatalysis on noble metal films, leading to significant enhancements in bifunctional activity essential for fuel cells and metal-air batteries. Still, its catalytic impact on transition-metal oxide thin films, such as perovskites, is not widely understood. Here, we epitaxially strain the conducting perovskite LaNiO3 to systematically determine its influence on both the oxygen reduction and oxygen evolution reaction. Uniquely, we found that compressive strain could significantly enhance both reactions, yielding a bifunctional catalyst that surpasses the performance of noble metals such as Pt. We attribute the improved bifunctionality to strain-induced splitting of themore » eg orbitals, which can customize orbital asymmetry at the surface. Lastly, analogous to strain-induced shifts in the d-band center of noble metals relative to the Fermi level, such splitting can dramatically affect catalytic activity in this perovskite and other potentially more active oxides.« less

  11. Enhanced Bifunctional Oxygen Catalysis in Strained LaNiO3 Perovskites

    SciTech Connect

    Petrie, Jonathan R.; Cooper, Valentino R.; Freeland, John W.; Meyer, Tricia L.; Zhang, Zhiyong; Lutterman, Daniel A.; Lee, Ho Nyung

    2016-02-11

    Strain is known to greatly influence low-temperature oxygen electrocatalysis on noble metal films, leading to significant enhancements in bifunctional activity essential for fuel cells and metal-air batteries. Still, its catalytic impact on transition-metal oxide thin films, such as perovskites, is not widely understood. Here, we epitaxially strain the conducting perovskite LaNiO3 to systematically determine its influence on both the oxygen reduction and oxygen evolution reaction. Uniquely, we found that compressive strain could significantly enhance both reactions, yielding a bifunctional catalyst that surpasses the performance of noble metals such as Pt. We attribute the improved bifunctionality to strain-induced splitting of the eg orbitals, which can customize orbital asymmetry at the surface. Lastly, analogous to strain-induced shifts in the d-band center of noble metals relative to the Fermi level, such splitting can dramatically affect catalytic activity in this perovskite and other potentially more active oxides.

  12. Equation of state of Ca2AlSiO5.5 oxygen defect perovskite

    NASA Astrophysics Data System (ADS)

    Xu, Chaowen; Zhai, Shuangmeng; Ye, Lijin; Higo, Yuji

    2015-04-01

    The elastic properties of synthetic low-pressure and high-pressure Ca2AlSiO5.5 oxygen defect perovskites were investigated by in situ X-ray diffraction in a large-volume high-pressure apparatus. The P- V- T data were collected up to 22.75 GPa at room temperature, up to 12.88 GPa and 1,300 K for low-pressure phase and up to 25.76 GPa at room temperature for high-pressure phase. The P- V data at room temperature were fitted using a third-order Birch-Murnaghan equation of state to obtain K 0 = 146.1(9) GPa and = 3.64(9) for the monoclinic low-pressure phase, and K 0 = 150.4(19) GPa and = 3.16(23) for the rhombohedral high-pressure phase. If was fixed at 4.0, the isothermal bulk moduli were obtained as 142.6(3) and 144.0(8) GPa for low-pressure and high-pressure phase, respectively. Both the low-pressure and high-pressure Ca2AlSiO5.5 oxygen defect perovskites are much softer than pure CaSiO3 perovskite. The P- V- T data of low-pressure phase were fitted by the high-temperature Birch-Murnaghan equation of state to get thermoelastic properties as V 0 = 827.0(3) Å3, K T = 146.8(22) GPa, = 3.55(21), (∂ K T /∂ T)P = -0.037(2) GPa/K and α T = 7.67(20) × 10-5 - 3.20(30) × 10-8 T. Based on the results, the density profiles of low-pressure and high-pressure Ca2AlSiO5.5 oxygen defect perovskites were calculated and compared with those of some mantle silicate minerals to discuss the potential occurrence of Ca2AlSiO5.5 oxygen defect perovskite in the Earth's interior.

  13. Probing metastability in oxygen deficient YMn2O5

    NASA Astrophysics Data System (ADS)

    Pal, Sudip; Kumar, Kranti; Banerjee, A.

    2017-05-01

    In this article magnetic properties of YMn2O5-δ (δ=0.062) has been investigated through DC magnetization and ac susceptibility measurements. Sample has been prepared through chemical route. Iodometric titration has been used to determine oxygen deficiency and average Mn valance. Significant changes in magnetic properties have been found due to oxygen deficiency in the sample. It is observed that at low field, oxygen deficient sample undergoes only one phase transition around 42K but at higher applied field it shows three magnetic phase transitions while cooling those can be related to phase transitions found in stoichiometric sample. Frequency dependence of ac susceptibility indicates towards metastable nature of low temperature phase observed at low field. This is further buttressed by magnetic relaxation measurements.

  14. Hypoxia, Color Vision Deficiencies, and Blood Oxygen Saturation

    DTIC Science & Technology

    2013-11-01

    only a few subjects with congenital color vision defects and dichromats were excluded, we were interested in obtaining additional data from individuals...Hypoxia, Color Vision Deficiencies, and Blood Oxygen Saturation Jeffery K. Hovis1 Nelda J. Milburn2 Thomas E. Nesthus2 1University of Waterloo...2. Government Accession No. 3. Recipient’s Catalog No. DOT/FAA/AM-13/20 4. Title and Subtitle 5. Report Date Hypoxia, Color Vision Deficiencies

  15. Toward Switchable Photovoltaic Effect via Tailoring Mobile Oxygen Vacancies in Perovskite Oxide Films.

    PubMed

    Ge, Chen; Jin, Kui-Juan; Zhang, Qing-Hua; Du, Jian-Yu; Gu, Lin; Guo, Hai-Zhong; Yang, Jing-Ting; Gu, Jun-Xing; He, Meng; Xing, Jie; Wang, Can; Lu, Hui-Bin; Yang, Guo-Zhen

    2016-12-21

    The defect chemistry of perovskite oxides involves the cause to most of their abundant functional properties, including interface magnetism, charge transport, ionic exchange, and catalytic activity. The possibility to achieve dynamic control over oxygen anion vacancies offers a unique opportunity for the development of appealing switchable devices, which at present are commonly based on ferroelectric materials. Herein, we report the discovery of a switchable photovoltaic effect, that the sign of the open voltage and the short circuit current can be reversed by inverting the polarity of the applied field, upon electrically tailoring the distribution of oxygen vacancies in perovskite oxide films. This phenomenon is demonstrated in lateral photovoltaic devices based on both ferroelectric BiFeO3 and paraelectric SrTiO3 films, under a reversed applied field whose magnitude is much smaller than the coercivity value of BiFeO3. The migration of oxygen vacancies was directly observed by employing an advanced annular bright-field scanning transmission electron microscopy technique with in situ biasing equipment. We conclude that the band bending induced by the motion of oxygen vacancies is the driving force for the reversible switching between two photovoltaic states. The present work can provide an active path for the design of novel switchable photovoltaic devices with a wide range of transition metal oxides in terms of the ionic degrees of freedom.

  16. Enhanced CO2 Resistance for Robust Oxygen Separation Through Tantalum-doped Perovskite Membranes.

    PubMed

    Zhang, Chi; Tian, Hao; Yang, Dong; Sunarso, Jaka; Liu, Jian; Liu, Shaomin

    2016-03-08

    Oxygen selective membranes with enhanced oxygen permeability and CO2 resistance are highly required in sustainable clean energy generation technologies. Here, we present novel, cobalt-free, SrFe1-x Tax O3-δ (x=0, 0.025, 0.05, 0.1, 0.2) perovskite membranes. Ta-doping induced lattice structure progression from orthorhombic (x=0) to cubic (x=0.05). SrFe0.95 Ta0.05 O3-δ (SFT0.05) showed the highest oxygen flux rates reaching 0.85 mL min(-1) cm(-2) at 950 °C on a 1.0 mm-thick membrane. Surface decoration can increase the permeation rate further. Ta inclusion within the perovskite lattice of SrFeO3-δ (SF) enhanced the CO2 resistance of the membranes significantly as evidenced by the absence of the carbonate functional groups on the FTIR spectrum when exposed to CO2 atmosphere at 850 °C. The CO2 resistance of Ta-doped SF compounds correlates with the lower basicity and the higher binding energy for the lattice oxygen. SFT0.05 demonstrated high stability during long-term permeation tests under 10% CO2 atmosphere. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  17. An A-site-deficient perovskite offers high activity and stability for low-temperature solid-oxide fuel cells.

    PubMed

    Zhu, Yinlong; Chen, Zhi-Gang; Zhou, Wei; Jiang, Shanshan; Zou, Jin; Shao, Zongping

    2013-12-01

    Solid oxide fuel cells (SOFCs) directly convert fossil and/or renewable fuels into electricity and/or high-quality heat in an environmentally friendly way. However, high operating temperatures result in high cost and material issues, which have limited the commercialization of SOFCs. To lower their operating temperatures, highly active and stable cathodes are required to maintain a reasonable power output. Here, we report a layer-structured A-site deficient perovskite Sr0.95 Nb0.1 Co0.9 O3-δ (SNC0.95) prepared by solid-state reactions that shows not only high activity towards the oxygen reduction reaction (ORR) at operating temperatures below 600 °C, but also offers excellent structural stability and compatibility, and improved CO2 resistivity. An anode-supported fuel cell with SNC0.95 cathode delivers a peak power density as high as 1016 mW cm(-2) with an electrode-area-specific resistance of 0.052 Ω cm(2) at 500 °C.

  18. D0 Detector Collision Hall Oxygen Deficiancy Hazard Analysis

    SciTech Connect

    Wu, J.; /Fermilab

    1992-08-06

    EN-258, D0 Platform ODH Analysts. provided the oxygen deficiency hazard analysts for the D0 detector in the Assembly Hall. This note covers the same analysis. but revised for the Collision Hall. Liquid cryogens. released and warming to atmosphere conditions, expand to, on average, seven hundred times their liquid volume, and displace vital atmospheric oxygen. An oxygen deficiency hazard analysis assesses the increased risk to personnel in areas containing cryogenic systems. The D0 detector Collision Hall ODH analysis has been approached five different ways using established methods. If the low beta quad magnets are powered, and the exhaust rate is below 4220 scfm, the area is ODH class 1. In any other case, the analysis shows the area to be ODH class 0 as equipped (with ventilation fans) and requiring no special safety provisions. System designers have provided for a reduced oxygen level detection and warning system as well as emergency procedures to address fault conditions.

  19. Oxygen content determination in perovskite-type cobaltates

    SciTech Connect

    Conder, K. . E-mail: kazimierz.conder@psi.ch; Pomjakushina, E.; Soldatov, A.; Mitberg, E.

    2005-02-15

    Three oxygen content determination methods (iodometric titration, gas volumetric analysis and thermogravimetric hydrogen reduction) have been evaluated for the case of rare earth cobaltates LnBCo{sub 2}O{sub 5+{delta}} (were Ln-rare earth, B-alkali earth elements). All the methods are based on oxidation properties of both Co{sup 4+} and Co{sup 3+} cations but different instrumentation was used for each of the method. We have obtained good agreement within {+-}0.02 in {delta} for both the iodometric titration and the gas volumetric analysis, whereas the thermogravimetric hydrogen reduction was found to be less credible.

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

    NASA Astrophysics Data System (ADS)

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

    2017-01-01

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

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

    SciTech Connect

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

    2016-10-03

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

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

    DOE PAGES

    Han, Binghong; Stoerzinger, Kelsey A.; Tileli, Vasiliki; ...

    2016-10-03

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

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

    PubMed

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

    2017-01-01

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

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

    SciTech Connect

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

    2016-10-03

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

  5. B-site Cation Ordered Double Perovskites as Efficient and Stable Electrocatalysts for Oxygen Evolution Reaction.

    PubMed

    Sun, Hainan; Chen, Gao; Zhu, Yinlong; Liu, Bo; Zhou, Wei; Shao, Zongping

    2017-03-02

    Simple disordered perovskite oxides have been intensively exploited as promising electrocatalysts for catalysing the oxygen evolution reaction (OER) towards its application in water splitting, reversible fuel cells, and rechargeable metal-air batteries. Here, we demonstrated that B-site cation-ordered double perovskite Ba2BixSc0.2Co1.8-xO6-δ with two types of cobalt local environments are superior electrocatalysts for OER in alkaline solutions, demonstrating ultrahigh catalytic activity. In addition, no obvious performance degradation was observed for the Ba2Bi0.1Sc0.2Co1.7O6-δ sample after a continuous chronopotentiometry test. The critical role of the ordered [Co2+] and [Sc3+, Bi5+, Co3+] dual environments in improving OER activity was exhibited. The aforementioned results indicate that B-site cation-ordered double perovskite oxides may represent a new class of promising electrocatalysts for the OER in sustainable energy storage and conversion systems.

  6. Oxygen ion conduction in barium doped LaInO3 perovskite oxides

    NASA Astrophysics Data System (ADS)

    Kim, Hye-Lim; Kim, Shin; Lee, Kyu-Hyung; Lee, Hong-Lim; Lee, Ki-Tae

    2014-12-01

    Oxygen ion conduction behaviors of the 0-5 mol% excess Ba-doped La0.6Ba0.4InO3-δ cubic perovskite oxides have been investigated to elucidate their potential as electrolyte materials. The highest conductivity, 5.6 × 10-2 S cm-1 at 800 °C, is obtained at the 3 mol% excess Ba-doped composition benefiting from a supplementation of Ba2+ ions on the vacant A-site generated by the volatilization during the heat-treatment processes. Interestingly, all the samples except the undoped composition show curved electrical conductivity behavior in the Arrhenius plot. The activation energy is 0.50-0.52 eV in the high-temperature region above 900 °C, which is slightly lower than that of the doped LaGaO3 system. Moreover, all the samples show significantly lower activation energy values of both the high- and low-temperature regions compared with yttria-stabilized zirconia. The 3 mol% excess Ba-doped La1-xBaxInO3-δ (0.4 ≤ x ≤ 0.8) sample has also been studied. All of the compositions show a cubic perovskite structure and a nearly pure oxygen ion conduction behavior in a dry atmosphere even when p(O2) = 1atm. The composition of x = 0.4 exhibits the highest oxygen ion conductivities.

  7. Oxygen transport in perovskite-type solid oxide fuel cell materials: insights from quantum mechanics.

    PubMed

    Muñoz-García, Ana B; Ritzmann, Andrew M; Pavone, Michele; Keith, John A; Carter, Emily A

    2014-11-18

    CONSPECTUS: Global advances in industrialization are precipitating increasingly rapid consumption of fossil fuel resources and heightened levels of atmospheric CO2. World sustainability requires viable sources of renewable energy and its efficient use. First-principles quantum mechanics (QM) studies can help guide developments in energy technologies by characterizing complex material properties and predicting reaction mechanisms at the atomic scale. QM can provide unbiased, qualitative guidelines for experimentally tailoring materials for energy applications. This Account primarily reviews our recent QM studies of electrode materials for solid oxide fuel cells (SOFCs), a promising technology for clean, efficient power generation. SOFCs presently must operate at very high temperatures to allow transport of oxygen ions and electrons through solid-state electrolytes and electrodes. High temperatures, however, engender slow startup times and accelerate material degradation. SOFC technologies need cathode and anode materials that function well at lower temperatures, which have been realized with mixed ion-electron conductor (MIEC) materials. Unfortunately, the complexity of MIECs has inhibited the rational tailoring of improved SOFC materials. Here, we gather theoretically obtained insights into oxygen ion conductivity in two classes of perovskite-type materials for SOFC applications: the conventional La1-xSrxMO3 family (M = Cr, Mn, Fe, Co) and the new, promising class of Sr2Fe2-xMoxO6 materials. Using density functional theory + U (DFT+U) with U-J values obtained from ab initio theory, we have characterized the accompanying electronic structures for the two processes that govern ionic diffusion in these materials: (i) oxygen vacancy formation and (ii) vacancy-mediated oxygen migration. We show how the corresponding macroscopic oxygen diffusion coefficient can be accurately obtained in terms of microscopic quantities calculated with first-principles QM. We find that the

  8. Thermal conductivity reduction in oxygen-deficient strontium titanates

    NASA Astrophysics Data System (ADS)

    Yu, Choongho; Scullin, Matthew L.; Huijben, Mark; Ramesh, Ramamoorthy; Majumdar, Arun

    2008-05-01

    We report significant thermal conductivity reduction in oxygen-deficient lanthanum-doped strontium titanate (Sr1-xLaxTiO3-δ) films as compared to unreduced strontium titanates. Our experimental results suggest that the oxygen vacancies could have played an important role in the reduction. This could be due to the nature of randomly distributed and clustered vacancies, which would be very effective to scatter phonons. Our results could provide a pathway for tailoring the thermal conductivity of complex oxides, which is very beneficial to various applications including thermoelectrics.

  9. 30 CFR 77.1901-1 - Methane and oxygen deficiency tests; approved devices.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 30 Mineral Resources 1 2012-07-01 2012-07-01 false Methane and oxygen deficiency tests; approved... AREAS OF UNDERGROUND COAL MINES Slope and Shaft Sinking § 77.1901-1 Methane and oxygen deficiency tests; approved devices. Tests for oxygen deficiency shall be made with a permissible flame safety lamp or...

  10. 30 CFR 77.101 - Tests for methane and for oxygen deficiency; qualified person.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 30 Mineral Resources 1 2013-07-01 2013-07-01 false Tests for methane and for oxygen deficiency... oxygen deficiency; qualified person. (a) The provisions of Subparts C, P, R, and T of this Part 77 require that tests for methane and for oxygen deficiency be made by a qualified person. A person is...

  11. 30 CFR 77.102 - Tests for methane; oxygen deficiency; qualified person, additional requirement.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 30 Mineral Resources 1 2013-07-01 2013-07-01 false Tests for methane; oxygen deficiency; qualified... methane; oxygen deficiency; qualified person, additional requirement. Notwithstanding the provisions of... and oxygen deficiency unless he has demonstrated to the satisfaction of an authorized...

  12. 30 CFR 77.1901-1 - Methane and oxygen deficiency tests; approved devices.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 30 Mineral Resources 1 2011-07-01 2011-07-01 false Methane and oxygen deficiency tests; approved... AREAS OF UNDERGROUND COAL MINES Slope and Shaft Sinking § 77.1901-1 Methane and oxygen deficiency tests; approved devices. Tests for oxygen deficiency shall be made with a permissible flame safety lamp or...

  13. 30 CFR 77.101 - Tests for methane and for oxygen deficiency; qualified person.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 30 Mineral Resources 1 2010-07-01 2010-07-01 false Tests for methane and for oxygen deficiency... oxygen deficiency; qualified person. (a) The provisions of Subparts C, P, R, and T of this Part 77 require that tests for methane and for oxygen deficiency be made by a qualified person. A person is...

  14. 30 CFR 77.101 - Tests for methane and for oxygen deficiency; qualified person.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 30 Mineral Resources 1 2011-07-01 2011-07-01 false Tests for methane and for oxygen deficiency... oxygen deficiency; qualified person. (a) The provisions of Subparts C, P, R, and T of this Part 77 require that tests for methane and for oxygen deficiency be made by a qualified person. A person is...

  15. 30 CFR 77.101 - Tests for methane and for oxygen deficiency; qualified person.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 30 Mineral Resources 1 2012-07-01 2012-07-01 false Tests for methane and for oxygen deficiency... oxygen deficiency; qualified person. (a) The provisions of Subparts C, P, R, and T of this Part 77 require that tests for methane and for oxygen deficiency be made by a qualified person. A person is...

  16. 30 CFR 77.1901-1 - Methane and oxygen deficiency tests; approved devices.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 30 Mineral Resources 1 2010-07-01 2010-07-01 false Methane and oxygen deficiency tests; approved... AREAS OF UNDERGROUND COAL MINES Slope and Shaft Sinking § 77.1901-1 Methane and oxygen deficiency tests; approved devices. Tests for oxygen deficiency shall be made with a permissible flame safety lamp or...

  17. 30 CFR 77.102 - Tests for methane; oxygen deficiency; qualified person, additional requirement.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 30 Mineral Resources 1 2014-07-01 2014-07-01 false Tests for methane; oxygen deficiency; qualified... methane; oxygen deficiency; qualified person, additional requirement. Notwithstanding the provisions of... and oxygen deficiency unless he has demonstrated to the satisfaction of an authorized...

  18. 30 CFR 77.1901-1 - Methane and oxygen deficiency tests; approved devices.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 30 Mineral Resources 1 2014-07-01 2014-07-01 false Methane and oxygen deficiency tests; approved... AREAS OF UNDERGROUND COAL MINES Slope and Shaft Sinking § 77.1901-1 Methane and oxygen deficiency tests; approved devices. Tests for oxygen deficiency shall be made with a permissible flame safety lamp or...

  19. 30 CFR 77.102 - Tests for methane; oxygen deficiency; qualified person, additional requirement.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 30 Mineral Resources 1 2011-07-01 2011-07-01 false Tests for methane; oxygen deficiency; qualified... methane; oxygen deficiency; qualified person, additional requirement. Notwithstanding the provisions of... and oxygen deficiency unless he has demonstrated to the satisfaction of an authorized...

  20. 30 CFR 77.1901-1 - Methane and oxygen deficiency tests; approved devices.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 30 Mineral Resources 1 2013-07-01 2013-07-01 false Methane and oxygen deficiency tests; approved... AREAS OF UNDERGROUND COAL MINES Slope and Shaft Sinking § 77.1901-1 Methane and oxygen deficiency tests; approved devices. Tests for oxygen deficiency shall be made with a permissible flame safety lamp or...

  1. 30 CFR 77.102 - Tests for methane; oxygen deficiency; qualified person, additional requirement.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 30 Mineral Resources 1 2010-07-01 2010-07-01 false Tests for methane; oxygen deficiency; qualified... methane; oxygen deficiency; qualified person, additional requirement. Notwithstanding the provisions of... and oxygen deficiency unless he has demonstrated to the satisfaction of an authorized...

  2. 30 CFR 77.101 - Tests for methane and for oxygen deficiency; qualified person.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 30 Mineral Resources 1 2014-07-01 2014-07-01 false Tests for methane and for oxygen deficiency... oxygen deficiency; qualified person. (a) The provisions of Subparts C, P, R, and T of this Part 77 require that tests for methane and for oxygen deficiency be made by a qualified person. A person is...

  3. 30 CFR 77.102 - Tests for methane; oxygen deficiency; qualified person, additional requirement.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 30 Mineral Resources 1 2012-07-01 2012-07-01 false Tests for methane; oxygen deficiency; qualified... methane; oxygen deficiency; qualified person, additional requirement. Notwithstanding the provisions of... and oxygen deficiency unless he has demonstrated to the satisfaction of an authorized...

  4. Research Update: Interface-engineered oxygen octahedral tilts in perovskite oxide heterostructures

    SciTech Connect

    Kan, Daisuke Aso, Ryotaro; Kurata, Hiroki; Shimakawa, Yuichi

    2015-06-01

    Interface engineering of structural distortions is a key for exploring the functional properties of oxide heterostructures and superlattices. In this paper, we report on our comprehensive investigations of oxygen octahedral distortions at the heterointerface between perovskite oxides SrRuO{sub 3} and BaTiO{sub 3} on GdScO{sub 3} substrates and of the influences of the interfacially engineered distortions on the magneto-transport properties of the SrRuO{sub 3} layer. Our state-of-the-art annular bright-field imaging in aberration-corrected scanning transmission electron microscopy revealed that the RuO{sub 6} octahedral distortions in the SrRuO{sub 3} layer have strong dependence on the stacking order of the SrRuO{sub 3} and BaTiO{sub 3} layers on the substrate. This can be attributed to the difference in the interfacial octahedral connections. We also found that the stacking order of the oxide layers has a strong impact on the magneto-transport properties, allowing for control of the magnetic anisotropy of the SrRuO{sub 3} layer through interface engineering. Our results demonstrate the significance of the interface engineering of the octahedral distortions on the structural and physical properties of perovskite oxides.

  5. Remarkable effect of Pt nanoparticles on visible light-induced oxygen generation from water catalysed by perovskite oxides.

    PubMed

    Gupta, Uttam; Naidu, B S; Rao, C N R

    2015-01-14

    Oxidation of water is a challenging process with a positive free energy change and it is purposeful to find good catalysts to facilitate the process. While the perovskite oxides, LaCoO3 and LaMnO3, are good electron transfer catalysts in artificial photosynthesis to produce oxygen by the oxidation of water, the electron transfer is further favoured by the presence of platinum nanoparticles, causing a substantial increase in oxygen evolution.

  6. Ethanol flame synthesis of carbon nanotubes in deficient oxygen environments

    NASA Astrophysics Data System (ADS)

    Hu, Wei-Chieh; Lin, Ta-Hui

    2016-04-01

    In this study, carbon nanotubes (CNTs) were synthesized using ethanol diffusion flames in a stagnation-flow system composed of an upper oxidizer duct and a lower liquid pool. In the experiments, a gaseous mixture of oxygen and nitrogen flowed from the upper oxidizer duct, and then impinged onto the vertically aligned ethanol pool to generate a planar and steady diffusion flame in a deficient oxygen environment. A nascent nickel mesh was used as the catalytic metal substrate to collect deposited materials. The effect of low oxygen concentration on the formation of CNTs was explored. The oxygen concentration significantly influenced the flame environment and thus the synthesized carbon products. Lowering the oxygen concentration increased the yield, diameter, and uniformity of CNTs. The optimal operating conditions for CNT synthesis were an oxygen concentration in the range of 15%-19%, a flame temperature in the range of 460 °C-870 °C, and a sampling position of 0.5-1 mm below the upper edge of the blue flame front. It is noteworthy that the concentration gradient of C2 species and CO governed the CNT growth directly. CNTs were successfully fabricated in regions with uniform C2 species and CO distributions.

  7. Ethanol flame synthesis of carbon nanotubes in deficient oxygen environments.

    PubMed

    Hu, Wei-Chieh; Lin, Ta-Hui

    2016-04-22

    In this study, carbon nanotubes (CNTs) were synthesized using ethanol diffusion flames in a stagnation-flow system composed of an upper oxidizer duct and a lower liquid pool. In the experiments, a gaseous mixture of oxygen and nitrogen flowed from the upper oxidizer duct, and then impinged onto the vertically aligned ethanol pool to generate a planar and steady diffusion flame in a deficient oxygen environment. A nascent nickel mesh was used as the catalytic metal substrate to collect deposited materials. The effect of low oxygen concentration on the formation of CNTs was explored. The oxygen concentration significantly influenced the flame environment and thus the synthesized carbon products. Lowering the oxygen concentration increased the yield, diameter, and uniformity of CNTs. The optimal operating conditions for CNT synthesis were an oxygen concentration in the range of 15%-19%, a flame temperature in the range of 460 °C-870 °C, and a sampling position of 0.5-1 mm below the upper edge of the blue flame front. It is noteworthy that the concentration gradient of C2 species and CO governed the CNT growth directly. CNTs were successfully fabricated in regions with uniform C2 species and CO distributions.

  8. D0 Detector Assemble Hall Platform Oxygen Deficiency Hazard Analysis

    SciTech Connect

    Clark, D.; Michael, J.; /Fermilab

    1991-01-29

    Liquid cryogens, released and warming to atmosphere conditions, expand to, on average, seven hundred times their liquid volume, and displace vital atmospheric oxygen. An oxygen deficiency hazard analysis assesses the increased risk to personnel in areas containing cryogenic systems. The D0 detector platform area ODH analysis has been approached four different ways using established methods. In each case, the analysis shows the platform area to be ODH class 0 as equipped (with ventilation fans) and requiring no special safety provisions. System designers have provided for a reduced oxygen level detection and warning system as well as emergency procedures to address fault conditions. The Oxygen Deficiency Hazard of any particular area is defined by these parameters: the nature of the accidental supply of inert gas (probability of occurrence and quantity then released), the area's volume, the area's ventilation rate, and to a small degree the elevation of the area. Once this information is assembled, the ODH classification can be determined through standardized calculations. The platform area under the D0 detector contains much of the cryogenic and gas system piping necessary for the D0 experiment. Prior to moving the detector into the Collision Hall, the liquid argon calorimeters are cooled down and operated in the Assembly Hall. The first phase of this operation involved the cooldown of the Central Calorimeter, which was done in February 1991. This engineering note assesses the increased risk to personnel in the platform level to a reduced oxygen atmosphere during the cool down and subsequent operation of the calorimeters in the Assembly Hall. In addition, it outlines the steps taken to warn personnel of an emergency and to direct the subsequent evacuation. This note analyses only the Assembly Hall area. A similar engineering note, EN-332, covers the analysis of the Collision Hall area.

  9. Gas diffusion-type oxygen electrode using perovskite-type oxides for metal-air batteries

    SciTech Connect

    Hyodo, Takeo; Miura, Norio; Yamazoe, Noboru

    1995-12-31

    In order to develop an air cathode of metal-air batteries, oxygen reduction behavior of gas diffusion-type carbon electrodes loaded with perovskite-type oxides, La{sub 1{minus}x}A{prime}{sub x}FeO{sub 3} (A{prime} = Ca, Sr, Ba, 0 {le} x {le} 1.0), was examined in 8 M KOH at 60 C. Among the oxide catalysts tested, La{sub 0.5}Sr{sub 0.5}FeO{sub 3} (specific surface area: 21.5 m{sup 2}{center_dot}g{sup {minus}1}) gave the highest electrode performance. On the basis of electrode reaction kinetics, H{sub 2}O{sub 2} decomposition rates, and temperature programmed desorption of oxygen, it was concluded that such a performance was attributable to the active sites of the oxide for the direct 4-electron reduction of oxygen. Moreover, the electrode using La{sub 0.5}Sr{sub 0.5}FeO{sub 3} was found to be rather stable in a short-term operation for 90 h at 300 mA{center_dot}cm{sup {minus}2}.

  10. Thermodynamic stability of perovskites and related compounds in some alkaline earth-transition metal-oxygen systems

    NASA Astrophysics Data System (ADS)

    Yokokawa, Harumi; Sakai, Natsuko; Kawada, Tatsuya; Dokiya, Masayuki

    1991-09-01

    The thermodynamic properties of some alkaline earth ( A)-transition metal ( M) perovskites and K 2NiF 4 compounds have been collected, analyzed, and utilized to examine their stabilities by constructing the chemical potential diagrams of a log [ {a(A)}/{a(M)}] vs log P(O 2) plot. A thermodynamic analysis was performed on the dissociation reaction of K 2NiF 4 compounds ( A2MO 4) into perovskites ( AMO 3) and alkaline earth oxides ( AO) using empirical correlations between stabilization energy and tolerance factor. It has been found that the softness of calcium ions, which shrink markedly with decreasing coordination number from 12 to 9, makes the calcium K 2NiF 4 compounds (Ca 2MO 4) relatively less stable with increasing radius of the transition metal ions, r( M4+). This destabilization related to the coordination-number-dependent radii implies that when compared with the strontium perovskites, the calcium analogous perovskites may have a smaller number of oxygen vacancies, because the formation of oxygen vacancies should be accompanied with a decrease in coordination number of A-site ions.

  11. Oxygen Vacancy-Tuned Physical Properties in Perovskite Thin Films with Multiple B-site Valance States

    NASA Astrophysics Data System (ADS)

    Enriquez, Erik; Chen, Aiping; Harrell, Zach; Dowden, Paul; Koskelo, Nicholas; Roback, Joseph; Janoschek, Marc; Chen, Chonglin; Jia, Quanxi

    2017-04-01

    Controlling oxygen content in perovskite oxides with ABO3 structure is one of most critical steps for tuning their functionality. Notably, there have been tremendous efforts to understand the effect of changes in oxygen content on the properties of perovskite thin films that are not composed of cations with multiple valance states. Here, we study the effect of oxygen vacancies on structural and electrical properties in epitaxial thin films of SrFeO3-δ (SFO), where SFO is a compound with multiple valance states at the B site. Various annealing treatments are used to produce different oxygen contents in the films, which has resulted in significant structural changes in the fully strained SFO films. The out-of-plane lattice parameter and tetragonality increase with decreasing oxygen concentration, indicating the crystal structure is closely related to the oxygen content. Importantly, variation of the oxygen content in the films significantly affects the dielectric properties, leakage conduction mechanisms, and the resistive hysteresis of the materials. These results establish the relationship between oxygen content and structural and functional properties for a range of multivalent transition metal oxides.

  12. Oxygen Vacancy-Tuned Physical Properties in Perovskite Thin Films with Multiple B-site Valance States

    PubMed Central

    Enriquez, Erik; Chen, Aiping; Harrell, Zach; Dowden, Paul; Koskelo, Nicholas; Roback, Joseph; Janoschek, Marc; Chen, Chonglin; Jia, Quanxi

    2017-01-01

    Controlling oxygen content in perovskite oxides with ABO3 structure is one of most critical steps for tuning their functionality. Notably, there have been tremendous efforts to understand the effect of changes in oxygen content on the properties of perovskite thin films that are not composed of cations with multiple valance states. Here, we study the effect of oxygen vacancies on structural and electrical properties in epitaxial thin films of SrFeO3−δ (SFO), where SFO is a compound with multiple valance states at the B site. Various annealing treatments are used to produce different oxygen contents in the films, which has resulted in significant structural changes in the fully strained SFO films. The out-of-plane lattice parameter and tetragonality increase with decreasing oxygen concentration, indicating the crystal structure is closely related to the oxygen content. Importantly, variation of the oxygen content in the films significantly affects the dielectric properties, leakage conduction mechanisms, and the resistive hysteresis of the materials. These results establish the relationship between oxygen content and structural and functional properties for a range of multivalent transition metal oxides. PMID:28417954

  13. Oxygen Vacancy-Tuned Physical Properties in Perovskite Thin Films with Multiple B-site Valance States

    DOE PAGES

    Enriquez, Erik; Chen, Aiping; Harrell, Zach; ...

    2017-04-18

    Controlling oxygen content in perovskite oxides with ABO3 structure is one of most critical steps for tuning their functionality. Notably, there have been tremendous efforts to understand the effect of changes in oxygen content on the properties of perovskite thin films that are not composed of cations with multiple valance states. Here, we study the effect of oxygen vacancies on structural and electrical properties in epitaxial thin films of SrFeO3-δ (SFO), where SFO is a compound with multiple valance states at the B site. Various annealing treatments are used to produce different oxygen contents in the films, which has resultedmore » in significant structural changes in the fully strained SFO films. The out-of-plane lattice parameter and tetragonality increase with decreasing oxygen concentration, indicating the crystal structure is closely related to the oxygen content. Importantly, variation of the oxygen content in the films significantly affects the dielectric properties, leakage conduction mechanisms, and the resistive hysteresis of the materials. These results establish the relationship between oxygen content and structural and functional properties for a range of multivalent transition metal oxides.« less

  14. Magnetic properties of defect-free and oxygen-deficient cubic SrCoO3 -δ

    NASA Astrophysics Data System (ADS)

    Hoffmann, Martin; Borisov, Vladislav S.; Ostanin, Sergey; Mertig, Ingrid; Hergert, Wolfram; Ernst, Arthur

    2015-09-01

    We investigated theoretically electronic and magnetic properties of the perovskite material SrCoO3 -δ with δ ≤0.15 using a projector-augmented plane-wave method and a Green's function method. This material is known from various experiments to be ferromagnetic with a Curie temperature of 260 K to 305 K and a magnetic moment of 1.5 μB to 3.0 μB . Applying the magnetic force theorem as it is formulated within the Green's function method, we calculated for SrCoO3 -δ the magnetic exchange interactions and estimated the Curie temperature. Including correlation effects by an effective U parameter within the GGA +U approach and verifying this by hybrid functional calculations, we obtained the Curie temperatures in dependence of the oxygen deficiency close to the experimental values.

  15. Copper-substituted perovskite compositions for solid oxide fuel cell cathodes and oxygen reduction electrodes in other electrochemical devices

    DOEpatents

    Rieke, Peter C [Pasco, WA; Coffey, Gregory W [Richland, WA; Pederson, Larry R [Kennewick, WA; Marina, Olga A [Richland, WA; Hardy, John S [Richland, WA; Singh, Prabhaker [Richland, WA; Thomsen, Edwin C [Richland, WA

    2010-07-20

    The present invention provides novel compositions that find advantageous use in making electrodes for electrochemical cells. Also provided are electrochemical devices that include active oxygen reduction electrodes, such as solid oxide fuel cells, sensors, pumps and the like. The compositions comprises a copper-substituted ferrite perovskite material. The invention also provides novel methods for making and using the electrode compositions and solid oxide fuel cells and solid oxide fuel cell assemblies having cathodes comprising the compositions.

  16. Neutron Diffraction Study of Silicate Perovskites

    NASA Astrophysics Data System (ADS)

    Mao, H. K.; van Orman, J.; Fei, Y.; Hemley, R. J.; Loveday, J.; Nelmes, R.; Smith, R. I.

    2002-12-01

    The oxygen deficiency and cation-site distribution of silicate perovskite control its physical and chemical properties, including density, bulk modulus, defect mobility, ionic transport, flow behavior, oxidation states, hydration, and minor-element solubility. These properties of perovskite, in turn control the geophysical and geochemical processes of the Earth. The possibility of oxygen deficiency was first recognized in perovskite with minor amounts of Al replacing Mg and Si [1, 2], and its significance is compared to the analogous defect perovskite in ceramics [3]. Basic crystallographic characteristics of the silicate perovskite, including the lattice parameters of the orthorhombic unit cell, the Pbmn space group, and atomic positions, were previously determined by x-ray diffraction [4]. The defect crystallography of silicate perovskite, however, cannot be measured by x-rays because the relevant ions (Mg2+, Al3+, Si4+ and O2-) are isoelectronic. These ions have very different neutron cross-section and can be readily resolved by neutron diffraction. Using multianvil apparatus, we synthesized perovskite samples at 1700°C and 25-28 GPa. We perform multiple runs to accumulate 3 mm3 sample each for the MgSiO3 end member and MgSiO3 plus 5 weight %\\ Al2O3 in perovskite structure. Excellent powder diffraction data were collected at the POLARIS Beamline of ISIS, Rutherford Appleton Lab, and were subjected to Rietveld analysis. Neutron derived information sheds light on the unusual effects found for Al3+ substitution on the compressibility of the silicate perovskite [1]. 1. J. Zhang and D. J. Weidner, Science 284, 782 (1999). 2. J. P. Brodholt, Nature 407, 620 (2000). 3. A. Navrotsky, Science 284, 1788 (1999). 4. N. L. Ross and R. M. Hazen, Phys. Chem. Minerals 17, 228 (1990).

  17. Conducting Membranes: Unprecedented Perovskite Oxyfluoride Membranes with High-Efficiency Oxygen Ion Transport Paths for Low-Temperature Oxygen Permeation (Adv. Mater. 18/2016).

    PubMed

    Zhu, Jiawei; Liu, Gongping; Liu, Zhengkun; Chu, Zhenyu; Jin, Wanqin; Xu, Nanping

    2016-05-01

    Perovskite oxyfluoride (ABO3-δ Fγ ) membranes for low-temperature oxygen permeation are reported by W. Jin and co-workers. As described on page 3511, using mixed ionic and electronic conducting (MIEC) oxides, this new type of membrane outperforms current state-of-the-art MIEC membranes and satisfies commercial requirements at low temperatures (<923 K). © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Tuning bipolar resistive switching by forming defect dipoles in A-site-deficient perovskite calcium titanate thin films

    NASA Astrophysics Data System (ADS)

    Xie, Wei; Hu, Wei; Zou, Lilan; Chen, Ruqi; Li, Baojun; Bao, Dinghua

    2015-04-01

    If we intentionally make the A-site in an ABO3 perovskite structure deficient, it is possible to tune the resistive switching effect by forming defect dipoles. In this study, an A-site-deficient calcium titanate (Ca0.95TiO3, CTO) thin film was fabricated on a Pt/Ti/SiO2/Si substrate as an active layer for resistive random-access memory. The Pt/CTO/Pt device exhibited stable bipolar resistive switching performance with good endurance and long retention. The resistive switching may be attributable to the formation and rupture of the conduction filaments due to the O vacancies and defect dipoles resulting from the interaction between the Ca and O vacancies.

  19. Electrical properties and water incorporation in A-site deficient perovskite La1-xBaxNb3O9-0.5x

    NASA Astrophysics Data System (ADS)

    Animitsa, I.; Iakovleva, A.; Belova, K.

    2016-06-01

    Barium doped A-site deficient perovskites La1-xBaxNb3O9-0.5x (x=0-0.05) were synthesized by the solid state method, their structure, electrical properties and state of oxygen-hydrogen groups have been investigated. These phases were found to be able to incorporate water from the gas phase and to exhibit proton transport. Hydration is accompanied by the formation of different forms of oxygen-hydrogen groups: OH- - groups and H3O+ - ions. The total conductivities of doped samples increased in a wet atmosphere due to the appearance of proton current carriers (at the temperatures below 700 °C), but the conductivity increased insignificantly (~0.25 order of magnitude) because of a low doping level and, consequently, small concentration of protons. TG-measurements confirmed relatively low water content (below 0.2%). The total conductivity depends substantially on x and exhibits a minimum on σ-f(x) dependencies. It has been suggested that such behavior is a manifestation of a mixed cation effect.

  20. Promotion on electrochemical performance of a cation deficient SrCo0.7Nb0.1Fe0.2O3-δ perovskite cathode for intermediate-temperature solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Ding, Liming; Wang, Lixi; Ding, Dong; Zhang, Shihua; Ding, Xifeng; Yuan, Guoliang

    2017-06-01

    Solid oxide fuel cells (SOFCs) offer great promise for the most efficient and cost-effective conversion to electricity of a wide variety of fuels. The cathode materials with high electro-catalytic activity for oxygen reduction reaction is vital to the development of commercially-viable SOFCs to be operated at reduced temperatures. In present study, cobalt-based perovskite oxides SrxCo0.7Nb0.1Fe0.2O3-δ (SCNF, x = 0.95 and 1) were comparatively investigated as promising cathode materials for intermediate-temperature SOFCs. The SCNF compounds with a slight Sr deficiency (S0.95CNF) exhibited single phase of primitive cubic structure with Pm-3m symmetry. A small Sr deficiency is demonstrated to greatly enhance the electrochemical performance of stoichiometric SCNF cathode due to significantly increased oxygen vacancy. The polarization resistance of S0.95CNF at 700 °C was 0.11 Ω cm2, only about 61% of SCNF. The rate limiting step for oxygen reduction reaction (ORR) is demonstrated to be oxygen ion transfer within the bulk electrode and/or from electrode to electrolyte through the triple phase boundary. Full cells with the SCNF cathode present good performance and stable output at reduced temperatures, indicating the great potential for enhanced performance of Co-based cathodes with A-site deficiency.

  1. Persistent optically induced magnetism in oxygen-deficient strontium titanate.

    PubMed

    Rice, W D; Ambwani, P; Bombeck, M; Thompson, J D; Haugstad, G; Leighton, C; Crooker, S A

    2014-05-01

    Strontium titanate (SrTiO3) is a foundational material in the emerging field of complex oxide electronics. Although its bulk electronic and optical properties are rich and have been studied for decades, SrTiO3 has recently become a renewed focus of materials research catalysed in part by the discovery of superconductivity and magnetism at interfaces between SrTiO3 and other non-magnetic oxides. Here we illustrate a new aspect to the phenomenology of magnetism in SrTiO3 by reporting the observation of an optically induced and persistent magnetization in slightly oxygen-deficient bulk SrTiO3-δ crystals using magnetic circular dichroism (MCD) spectroscopy and SQUID magnetometry. This zero-field magnetization appears below ~18 K, persists for hours below 10 K, and is tunable by means of the polarization and wavelength of sub-bandgap (400-500 nm) light. These effects occur only in crystals containing oxygen vacancies, revealing a detailed interplay between magnetism, lattice defects, and light in an archetypal complex oxide material.

  2. 30 CFR 75.150 - Tests for methane and for oxygen deficiency; qualified person.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 30 Mineral Resources 1 2010-07-01 2010-07-01 false Tests for methane and for oxygen deficiency... Certified Persons § 75.150 Tests for methane and for oxygen deficiency; qualified person. (a) The provisions of Subpart D—Ventilation of this part and § 75.1106 require that tests for methane and for...

  3. 30 CFR 75.150 - Tests for methane and for oxygen deficiency; qualified person.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 30 Mineral Resources 1 2013-07-01 2013-07-01 false Tests for methane and for oxygen deficiency... Certified Persons § 75.150 Tests for methane and for oxygen deficiency; qualified person. (a) The provisions of Subpart D—Ventilation of this part and § 75.1106 require that tests for methane and for...

  4. 30 CFR 75.150 - Tests for methane and for oxygen deficiency; qualified person.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 30 Mineral Resources 1 2012-07-01 2012-07-01 false Tests for methane and for oxygen deficiency... Certified Persons § 75.150 Tests for methane and for oxygen deficiency; qualified person. (a) The provisions of Subpart D—Ventilation of this part and § 75.1106 require that tests for methane and for...

  5. 30 CFR 75.150 - Tests for methane and for oxygen deficiency; qualified person.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 30 Mineral Resources 1 2011-07-01 2011-07-01 false Tests for methane and for oxygen deficiency... Certified Persons § 75.150 Tests for methane and for oxygen deficiency; qualified person. (a) The provisions of Subpart D—Ventilation of this part and § 75.1106 require that tests for methane and for...

  6. 30 CFR 75.150 - Tests for methane and for oxygen deficiency; qualified person.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 30 Mineral Resources 1 2014-07-01 2014-07-01 false Tests for methane and for oxygen deficiency... Certified Persons § 75.150 Tests for methane and for oxygen deficiency; qualified person. (a) The provisions of Subpart D—Ventilation of this part and § 75.1106 require that tests for methane and for...

  7. Physical Properties of Oxygen Deficient YTTRIUM(1) BARIUM(2) COPPER(3) OXYGEN(7-DELTA) Superconductors.

    NASA Astrophysics Data System (ADS)

    Sun, He Bi.

    The physical properties of oxygen deficient polycrystalline rm YBa_2Cu_3O_{7 -delta} superconducting materials have been systematically investigated. These properties include magnetic susceptibility, electrical transport, thermoelectric power and infrared reflectivity. A great deal of this study has concentrated on the magnetic and transport properties of these materials when they are in the mixed state. The polycrystalline specimens used in this work were prepared through a solid state reaction. The oxygen content of the specimens was controlled using several annealing methods and the oxygen deficiency delta was determined by X-ray diffraction, gas evolution, iodometric titration and neutron diffraction techniques. A new method has been developed for the investigation of magnetic relaxation in these materials using the conventional a.c. susceptibility technique after modification. This thesis represents the first detailed and systematic study of the thermal activation energy for high Tc superconductors using many different methods, including a.c. susceptibility, magnetic relaxation, electric resistivity and thermoelectric power. All the results obtained, including their numerical values and field dependence are consistent with and comparable to previously reported data. A modified critical state model has been successfully used to interpret the magnetic field dependence of the isothermal a.c. susceptibility data, including field dependent a.c. losses and the chi^' -chi^{'' } interrelationship. This study highlights the strong influence that delta exerts on the superconducting and normal state properties of polycrystalline rm YBa_2Cu_3O_{7-delta } material. In particular, for transport properties, delta affects the carrier doping in the CuO_2 planes, which determines the carrier concentration. Therefore increasing delta reduces the superconducting transition temperature. For the magnetic property, delta has a negative influence on the pinning energy in

  8. Praseodymium-deficiency Pr0.94BaCo2O6-δ double perovskite: A promising high performance cathode material for intermediate-temperature solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Meng, Fuchang; Xia, Tian; Wang, Jingping; Shi, Zhan; Zhao, Hui

    2015-10-01

    Praseodymium-deficiency Pr0.94BaCo2O6-δ (P0.94BCO) double perovskite has been evaluated as a cathode material for intermediate-temperature solid oxide fuel cells. X-ray diffraction pattern shows the orthorhombic structure with double lattice parameters from the primitive perovskite cell in Pmmm space group. P0.94BCO has a good chemical compatibility with Ce0.9Gd0.1O1.95 (CGO) electrolyte even at 1000 °C for 24 h. It is observed that the Pr-deficiency can introduce the extra oxygen vacancies in P0.94BCO, further enhancing its electrocatalytic activity for oxygen reduction reaction. P0.94BCO demonstrates the promising cathode performance as evidenced by low polarization are-specific resistance (ASR), e. g. 0.11 Ω cm2 and low cathodic overpotential e. g. -56 mV at a current density of -78 mA cm-2 at 600 °C in air. These features are comparable to those of the benchmark cathode Ba0.5Sr0.5Co0.8Fe0.2O3-δ. The fuel cell CGO-Ni|CGO|P0.94BCO presents the attractive peak power density of 1.05 W cm-2 at 600 °C. Furthermore, the oxygen reduction kinetics of P0.94BCO material is also investigated, and the rate-limiting steps for oxygen reduction reaction are determined.

  9. Room temperature magnetocaloric effect of La-deficient bulk perovskite manganite La 0.7MnO 3- δ

    NASA Astrophysics Data System (ADS)

    Wang, Zhiming; Xu, Qingyu; Sun, Jingzhi; Pan, Jian; Zhang, He

    2011-04-01

    Room temperature magnetocaloric effect in La-deficient bulk perovskite manganite La 0.7MnO 3- δ prepared by conventional solid-state reaction has been reported. The maximum value of the magnetic entropy change (about-1.32 J/kg K) and the refrigerant capacity (approximately close to 37 J/kg) had been obtained at 290 K corresponding to a magnetic field variation of 1 T for La 0.7MnO 3- δ. It is the strong Jahn-Teller coupling that changes Mn-O bond length and Mn-O-Mn bond angles and then the canted spin arrangement and induces the strong double-exchange coupling to a comparatively high magnetic transition temperature. This Curie temperature near room temperature with easy fabrication and higher chemical stability makes La 0.7MnO 3- δ a potential candidate as a working substance in magnetic refrigeration technology.

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

    PubMed

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

    2015-07-15

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

  11. Transition metal substituted SrTiO3 perovskite oxides as promising functional materials for oxygen sensor

    NASA Astrophysics Data System (ADS)

    Misra, Sunasira

    2012-07-01

    Modern industries employ several gases as process fluids. Leakage of these gases in the operating area could lead to undesirable consequences. Even in chemical industries, which use large quantities of inert gases in confined areas, accidental leakage of these process gases would result in the reduction of oxygen partial pressure in atmospheric air. For instance, large amounts of gaseous nitrogen and argon are used in pharmaceutical industries, gas filling/bottling plants, operating area of Fast Breeder reactors, etc. Fall of concentration of oxygen in air below 17% could lead to life risk (Asphyxiation) of the working personnel that has to be checked well in advance. Further, when the leaking gas is of explosive nature, its damage potential would be very high if its concentration level in air increases beyond its lower explosive limit. Surveillance of the ambient within these industries at the critical areas and also in the environment around them for oxygen therefore becomes highly essential. Sensitive and selective gas sensors made of advanced materials are required to meet this demand of monitoring environmental pollution. The perovskite class of oxides (ABO3) is chemically stable even at high temperatures and can tolerate large levels of dopants without phase transformations. The electronic properties of this parent functional material can be tailored by adding appropriate dopants that exhibit different valence states. Aliovalent transition metal substituted SrTiO3 perovskites are good mixed ionic and electronic conductors and potential candidates for sensing oxygen at percentage level exploiting their oxygen pressure dependent electrical conductivity. This paper presents the preparation, study of electrical conductivity and oxygen-sensing characteristics of iron and cobalt substituted SrTiO3.

  12. Enhanced Microwave Absorption Properties by Tuning Cation Deficiency of Perovskite Oxides of Two-Dimensional LaFeO3/C Composite in X-Band.

    PubMed

    Liu, Xiang; Wang, Lai-Sen; Ma, Yating; Zheng, Hongfei; Lin, Liang; Zhang, Qinfu; Chen, Yuanzhi; Qiu, Yulong; Peng, Dong-Liang

    2017-03-01

    Development of microwave absorption materials with tunable thickness and bandwidth is particularly urgent for practical applications but remains a great challenge. Here, two-dimensional nanocomposites consisting of perovskite oxides (LaFeO3) and amorphous carbon were successfully obtained through a one pot with heating treatment using sodium chloride as a hard template. The tunable absorption properties were realized by introducing A-site cation deficiency in LaFeO3 perovskite. Among the A-site cation-deficient perovskites, La0.62FeO3/C (L0.62FOC) has the best microwave absorption properties in which the maximum absorption is -26.6 dB at 9.8 GHz with a thickness of 2.94 mm and the bandwidth range almost covers all X-band. The main reason affecting the microwave absorption performance was derived from the A-site cation deficiency which induced more dipoles polarization loss. This work proposes a promising method to tune the microwave absorption performance via introducing deficiency in a crystal lattice.

  13. First-principles study of band gap engineering via oxygen vacancy doping in perovskite ABB'O₃ solid solutions

    SciTech Connect

    Qi, Tingting; Curnan, Matthew T.; Kim, Seungchul; Bennett, Joseph W.; Grinberg, Ilya; Rappe, Andrew M.

    2011-12-15

    Oxygen vacancies in perovskite oxide solid solutions are fundamentally interesting and technologically important. However, experimental characterization of the vacancy locations and their impact on electronic structure is challenging. We have carried out first-principles calculations on two Zr-modified solid solutions, Pb(Zn1/3Nb2/3)O₃ and Pb(Mg1/3Nb2/3)O₃, in which vacancies are present. We find that the vacancies are more likely to reside between low-valent cation-cation pairs than high-valent cation-cation pairs. Based on the analysis of our results, we formulate guidelines that can be used to predict the location of oxygen vacancies in perovskite solid solutions. Our results show that vacancies can have a significant impact on both the conduction and valence band energies, in some cases lowering the band gap by ≈0.5 eV. The effects of vacancies on the electronic band structure can be understood within the framework of crystal field theory.

  14. First-principles study of band gap engineering via oxygen vacancy doping in perovskite ABB'O₃ solid solutions

    DOE PAGES

    Qi, Tingting; Curnan, Matthew T.; Kim, Seungchul; ...

    2011-12-15

    Oxygen vacancies in perovskite oxide solid solutions are fundamentally interesting and technologically important. However, experimental characterization of the vacancy locations and their impact on electronic structure is challenging. We have carried out first-principles calculations on two Zr-modified solid solutions, Pb(Zn1/3Nb2/3)O₃ and Pb(Mg1/3Nb2/3)O₃, in which vacancies are present. We find that the vacancies are more likely to reside between low-valent cation-cation pairs than high-valent cation-cation pairs. Based on the analysis of our results, we formulate guidelines that can be used to predict the location of oxygen vacancies in perovskite solid solutions. Our results show that vacancies can have a significant impactmore » on both the conduction and valence band energies, in some cases lowering the band gap by ≈0.5 eV. The effects of vacancies on the electronic band structure can be understood within the framework of crystal field theory.« less

  15. First-principles study of ionic oxygen mobility of Sr-containing LaAlO(3) perovskite.

    PubMed

    Hernández, Norge Cruz; Fernández Sanz, Javier; Alvarez, Luis Javier

    2009-07-29

    The fundamental phenomena underlying the electrical conduction properties of Sr-containing LaAlO(3) perovskites are studied through DFT simulations. The most energetically favourable substitution sites for Sr in the LaAlO(3) lattice and the energetic barriers for oxygen diffusion were calculated. Ab initio molecular dynamics was used to investigate the onset of oxygen transport. Experimental characterization of this material has suggested the existence of undercoordinated Al atoms upon substitution of La with Sr. Our results confirm the existence of four-  (Al(IV)) and fivefold (Al(V))-coordinated Al at the expense of the amount of sixfold-coordinated ones (Al(VI)), and explain the appearance of a small peak at 66 ppm in the (27)Al NMR spectrum.

  16. Oxygen-deficiency hazard induced by helium release in accelerator tunnel

    SciTech Connect

    Brown, D.P.; Sondericker, J.H.

    1983-01-01

    Tests to investigate oxygen deficiency levels due to release of helium into the CBA tunnel are described. Results of the tests indicate that the helium stratifies and spreads quickly in the horizontal plane. This demonstrates that adequate warning of possible asphyxiation hazards can be achieved. When oxygen deficiency monitors are located at ceiling level they may be spaced at intervals of 60 m. or more and still achieve acceptable results.

  17. Structure and magnetic properties of a new anion-deficient perovskite Pb{sub 2}Ba{sub 2}BiFe{sub 4}ScO{sub 13} with crystallographic shear structure

    SciTech Connect

    Batuk, Maria; Tyablikov, Oleg A.; Tsirlin, Alexander A.; Kazakov, Sergey M.; Rozova, Marina G.; Pokholok, Konstantin V.; Filimonov, Dmitry S.; Antipov, Evgeny V.; Abakumov, Artem M.; Hadermann, Joke

    2013-09-01

    Graphical abstract: - Highlights: • Pb{sub 2}Ba{sub 2}BiFe{sub 4}ScO{sub 13} was obtained by solid state synthesis. • Its structure was refined from combination of XPD and TEM. • It is a new member of the perovskite-related homologous series A{sub n}B{sub n}O{sub 3n−2} with n = 5. • Pb{sub 2}Ba{sub 2}BiFe{sub 4}ScO{sub 13} is antiferromagnetically ordered below T{sub N} ≈350 K. - Abstract: Pb{sub 2}Ba{sub 2}BiFe{sub 4}ScO{sub 13}, a new n = 5 member of the oxygen-deficient perovskite-based A{sub n}B{sub n}O{sub 3n−2} homologous series, was synthesized using a solid-state method. The crystal structure of Pb{sub 2}Ba{sub 2}BiFe{sub 4}ScO{sub 13} was investigated by a combination of synchrotron X-ray powder diffraction, electron diffraction, high-angle annular dark-field scanning transmission electron microscopy and Mössbauer spectroscopy. At 900 K, it crystallizes in the Ammm space group with the unit cell parameters a = 5.8459(1) Å, b = 4.0426(1) Å, and c = 27.3435(1) Å. In the Pb{sub 2}Ba{sub 2}BiFe{sub 4}ScO{sub 13} structure, quasi-two-dimensional perovskite blocks are periodically interleaved with ½[1 1 0] (1{sup ¯}01){sub p} crystallographic shear (CS) planes. At the CS planes, the corner-sharing FeO{sub 6} octahedra are transformed into chains of edge-sharing FeO{sub 5} distorted tetragonal pyramids. B-positions of the perovskite blocks between the CS planes are jointly occupied by Fe{sup 3+} and Sc{sup 3+}. The chains of the FeO{sub 5} pyramids and (Fe,Sc)O{sub 6} octahedra delimit six-sided tunnels that are occupied by double columns of cations with a lone electron pair (Pb{sup 2+}). The remaining A-cations (Bi{sup 3+}, Ba{sup 2+}) occupy positions in the perovskite block. According to the magnetic susceptibility measurements, Pb{sub 2}Ba{sub 2}BiFe{sub 4}ScO{sub 13} is antiferromagnetically ordered below T{sub N} ≈350 K.

  18. Evolution of Oxygen-Vacancy Ordered Crystal Structures in the Perovskite Series Sr nFe nO 3 n-1 ( n=2, 4, 8, and ∞), and the Relationship to Electronic and Magnetic Properties

    NASA Astrophysics Data System (ADS)

    Hodges, J. P.; Short, S.; Jorgensen, J. D.; Xiong, X.; Dabrowski, B.; Mini, S. M.; Kimball, C. W.

    2000-05-01

    Over the oxygen composition range 2.5≤x≤3.0, the SrFeOx system exists as four distinct compounds with the nominal composition SrnFenO3n-1 (n=2, 4, 8, and ∞). The end member SrFeO3 (n=∞) possesses a simple cubic perovskite crystal structure, whereas the oxygen-deficient (n=2, 4, and 8) members each adopt a different vacancy-ordered perovskite crystal structure. Using time-of-flight neutron powder diffraction, we show that previously proposed structures for the Sr4Fe4O11 (n=4) and Sr8Fe8O23 (n=8) compounds are incorrect. We determine the correct crystal structures for Sr4Fe4O11 (orthorhombic, space group Cmmm, a=10.974(1) Å, b=7.702(1) Å, and c=5.473(1) Å) and Sr8Fe8O23 (tetragonal, space group I4/mmm, a=10.929(1) Å and c=7.698(1) Å) through comparisons of the goodness of fit for Rietveld refinements of candidate models and bond-length distributions for each model. Using the correct crystal structures, we are able to assign valence states to the Fe crystallographic sites and to achieve consistency with published Mössbauer results for the same compounds.

  19. Characterization of Ordering in A-Site Deficient Perovskite Ca1-xLa2x/3TiO3 Using STEM/EELS.

    PubMed

    Danaie, Mohsen; Kepaptsoglou, Demie; Ramasse, Quentin M; Ophus, Colin; Whittle, Karl R; Lawson, Sebastian M; Pedrazzini, Stella; Young, Neil P; Bagot, Paul A J; Edmondson, Philip D

    2016-10-03

    The vacancy ordering behavior of an A-site deficient perovskite system, Ca1-xLa2x/3TiO3, was studied using atomic resolution scanning transmission electron microscopy (STEM) in conjunction with electron energy-loss spectroscopy (EELS), with the aim of determining the role of A-site composition changes. At low La content (x = 0.2), adopting Pbnm symmetry, there was no indication of long-range ordering. Domains, with clear boundaries, were observed in bright-field (BF) imaging, but were not immediately visible in the corresponding high-angle annular dark-field (HAADF) image. These boundaries, with the aid of displacement maps from A-site cations in the HAADF signal, are shown to be tilt boundaries. At the La-rich end of the composition (x = 0.9), adopting Cmmm symmetry, long-range ordering of vacancies and La(3+) ions was observed, with alternating La-rich and La-poor layers on (001)p planes, creating a double perovskite lattice along the c axis. These highly ordered domains can be found isolated within a random distribution of vacancies/La(3+), or within a large population, encompassing a large volume. In regions with a high number density of double perovskite domains, these highly ordered domains were separated by twin boundaries, with 90° or 180° lattice rotations across boundaries. The occurrence and characteristics of these ordered structures are discussed and compared with similar perovskite systems.

  20. Oxygen vacancy effects on double perovskite Bi2FeMnO6: A first-principles study

    NASA Astrophysics Data System (ADS)

    Ghosh, Ayana; Ahmed, Towfiq; Yarotski, Dzmitry A.; Nakhmanson, Serge M.; Zhu, Jian-Xin

    2016-12-01

    Double perovskite Bi2FeMnO6 (BFMO) is a potential candidate for the highly sought single-phase multiferroic system. The large orbital radius of the Bi 6s2 lone pairs is responsible for BFMO to exhibit low symmetries and spontaneous polarization, whereas B-site ordering of Mn and Fe contributes to its magnetic properties. In this work, we study both electronic correlation and oxygen vacancy effects on magnetic, electronic and optical properties of BFMO by performing first-principles simulations using density functional theory within the local spin-density approximation (LSDA) and the LSDA+U method. We have numerically demonstrated that a strong on-site Hubbard interaction is critical for the gap opening in a pristine BFMO. We have performed calculations on a supercell constructed with eight chemical formula units of BFMO, from which oxygen atoms were removed incrementally. We showed that the average magnetization decreases with the increase of oxygen vacancy concentration. From the calculated band structure and optical conductivity, an insulator-metal transition or crossover was identified with oxygen in BFMO.

  1. Oxygen-deficient metal oxide nanostructures for photoelectrochemical water oxidation and other applications.

    PubMed

    Wang, Gongming; Ling, Yichuan; Li, Yat

    2012-11-07

    This review presents highlights of the latest results of studies directed at developing oxygen-deficient metal oxides, including TiO(2), WO(3), and α-Fe(2)O(3), nanostructures as electrode materials, which show significantly enhanced performance in applications for photoelectrochemical water oxidation. The enhanced photoelectrochemical performance is attributed to improved electrical conductivities by controlled incorporation of oxygen vacancies as shallow donors for metal oxides. We also discuss the potential of these oxygen-deficient metal oxides for other energy conversion and storage applications, such as photocatalytic reactions and charge storage.

  2. Oxygen Evolution at Manganite Perovskite Ruddlesden-Popper Type Particles: Trends of Activity on Structure, Valence and Covalence.

    PubMed

    Ebrahimizadeh Abrishami, Majid; Risch, Marcel; Scholz, Julius; Roddatis, Vladimir; Osterthun, Norbert; Jooss, Christian

    2016-11-14

    An improved understanding of the correlation between the electronic properties of Mn-O bonds, activity and stability of electro-catalysts for the oxygen evolution reaction (OER) is of great importance for an improved catalyst design. Here, an in-depth study of the relation between lattice structure, electronic properties and catalyst performance of the perovskite Ca1-xPrxMnO₃ and the first-order RP-system Ca2-xPrxMnO₄ at doping levels of x = 0, 0.25 and 0.5 is presented. Lattice structure is determined by X-ray powder diffraction and Rietveld refinement. X-ray absorption spectroscopy of Mn-L and O-K edges gives access to Mn valence and covalency of the Mn-O bond. Oxygen evolution activity and stability is measured by rotating ring disc electrode studies. We demonstrate that the highest activity and stability coincidences for systems with a Mn-valence state of +3.7, though also requiring that the covalency of the Mn-O bond has a relative minimum. This observation points to an oxygen evolution mechanism with high redox activity of Mn. Covalency should be large enough for facile electron transfer from adsorbed oxygen species to the MnO₆ network; however, it should not be hampered by oxidation of the lattice oxygen, which might cause a crossover to material degradation. Since valence and covalency changes are not entirely independent, the introduction of the energy position of the eg(↑) pre-edge peak in the O-K spectra as a new descriptor for oxygen evolution is suggested, leading to a volcano-like representation of the OER activity.

  3. Promotion of Oxygen Reduction by Exsolved Silver Nanoparticles on a Perovskite Scaffold for Low-Temperature Solid Oxide Fuel Cells.

    PubMed

    Zhu, Yinlong; Zhou, Wei; Ran, Ran; Chen, Yubo; Shao, Zongping; Liu, Meilin

    2016-01-13

    Solid oxide fuel cells (SOFCs) have potential to be the cleanest and most efficient electrochemical energy conversion devices with excellent fuel flexibility. To make SOFC systems more durable and economically competitive, however, the operation temperature must be significantly reduced, which depends sensitively on the development of highly active electrocatalysts for oxygen reduction reaction (ORR) at low temperatures. Here we report a novel silver nanoparticle-decorated perovskite oxide, prepared via a facile exsolution process from a Sr0.95Ag0.05Nb0.1Co0.9O3-δ (SANC) perovskite precursor, as a highly active and robust ORR electrocatalyst for low-temperature SOFCs. The exsolved Sr0.95Ag0.05Nb0.1Co0.9O3-δ (denoted as e-SANC) electrode is very active for ORR, achieving a very low area specific resistance (∼0.214 Ω cm(2) at 500 °C). An anode-supported cell with the new heterostructured cathode demonstrates very high peak power density (1116 mW cm(-2) at 500 °C) and stable operation for 140 h at a current density of 625 mA cm(-2). The superior ORR activity and stability are attributed to the fast oxygen surface exchange kinetics and the firm adhesion of the Ag nanoparticles to the Sr0.95Nb0.1Co0.9O3-δ (SNC0.95) support. Moreover, the e-SANC cathode displays improved tolerance to CO2. These unique features make the new heterostructured material a highly promising cathode for low-temperature SOFCs.

  4. Origin of photoactivity of oxygen-deficient TiO{sub 2} under visible light

    SciTech Connect

    Lo, H.-H.; Gopal, Neeruganti O.; Ke, S.-C.

    2009-08-24

    As it is now well established that oxygen vacancies are spontaneously introduced during nitrogen doping of anatase TiO{sub 2}, there is a lively debate on whether nitrogen dopant or oxygen vacancy contributes to the visible light photoactivity of the doped catalyst. We showed that the coordinately unsaturated Ti site is integral to the visible light photoactivity in anatase oxygen-deficient TiO{sub 2} catalyst. Accordingly, oxygen vacancies may contribute to the visible light photoactivities in N-doped TiO{sub 2} and other nonmetallic ion-doped TiO{sub 2} as well. A redox active visible light photocatalyst has been developed based on oxygen-deficient structure in anatase TiO{sub 2}.

  5. Origin of photoactivity of oxygen-deficient TiO2 under visible light

    NASA Astrophysics Data System (ADS)

    Lo, Hsin-Hsi; Gopal, Neeruganti O.; Ke, Shyue-Chu

    2009-08-01

    As it is now well established that oxygen vacancies are spontaneously introduced during nitrogen doping of anatase TiO2, there is a lively debate on whether nitrogen dopant or oxygen vacancy contributes to the visible light photoactivity of the doped catalyst. We showed that the coordinately unsaturated Ti site is integral to the visible light photoactivity in anatase oxygen-deficient TiO2 catalyst. Accordingly, oxygen vacancies may contribute to the visible light photoactivities in N-doped TiO2 and other nonmetallic ion-doped TiO2 as well. A redox active visible light photocatalyst has been developed based on oxygen-deficient structure in anatase TiO2.

  6. Raman study of oxygen deficient YVO{sub 4} single crystals

    SciTech Connect

    Jin, B.M.; Erdei, S.; Bhalla, A.S.; Ainger, F.W.

    1995-10-01

    Oxygen deficiency which is an inherent problem in melt grown YVO{sub 4} single crystals was investigated by Micro-Probe Raman Spectroscopy (MPRS). External vibrational modes at 157 cm{sup {minus}1}, 162 cm{sup {minus}1} and selected internal vibrational modes at 379 cm{sup {minus}1}, 840 cm{sup {minus}1} of full Raman spectra were compared with different YVO{sub 4} crystals grown by the Czochralski (CZ) technique both with and without annealing in an O{sub 2} atmosphere as well as by top seeded solution growth technique (TSSG) in directly produced oxygen deficiency-free form. Special differences of above mentioned frequencies and over 1,000 cm{sup {minus}1} were observed in the Raman spectra, which could prove that the growth technologies generated different rates of oxygen deficiency in addition to critical intrinsic segregation effects in YVO{sub 4} which significantly determine the crystal quality.

  7. Effect of oxygen deficiency on electronic properties and local structure of amorphous tantalum oxide thin films

    SciTech Connect

    Denny, Yus Rama; Firmansyah, Teguh; Oh, Suhk Kun; Kang, Hee Jae; Yang, Dong-Seok; Heo, Sung; Chung, JaeGwan; Lee, Jae Cheol

    2016-10-15

    Highlights: • The effect of oxygen flow rate on electronic properties and local structure of tantalum oxide thin films was studied. • The oxygen deficiency induced the nonstoichiometric state a-TaOx. • A small peak at 1.97 eV above the valence band side appeared on nonstoichiometric Ta{sub 2}O{sub 5} thin films. • The oxygen flow rate can change the local electronic structure of tantalum oxide thin films. - Abstract: The dependence of electronic properties and local structure of tantalum oxide thin film on oxygen deficiency have been investigated by means of X-ray photoelectron spectroscopy (XPS), Reflection Electron Energy Loss Spectroscopy (REELS), and X-ray absorption spectroscopy (XAS). The XPS results showed that the oxygen flow rate change results in the appearance of features in the Ta 4f at the binding energies of 23.2 eV, 24.4 eV, 25.8, and 27.3 eV whose peaks are attributed to Ta{sup 1+}, Ta{sup 2+}, Ta{sup 3+}/Ta{sup 4+}, and Ta{sup 5+}, respectively. The presence of nonstoichiometric state from tantalum oxide (TaOx) thin films could be generated by the oxygen vacancies. In addition, XAS spectra manifested both the increase of coordination number of the first Ta-O shell and a considerable reduction of the Ta-O bond distance with the decrease of oxygen deficiency.

  8. Relation between oxygen stoichiometry and thermodynamic properties and the electronic structure of nonstoichiometric perovskite La0.6Sr0.4CoO3-δ.

    PubMed

    Bychkov, S F; Sokolov, A G; Popov, M P; Nemudry, A P

    2016-10-26

    Continuous phase diagram 3 - δ - log pO2 - T of the nonstoichiometric perovskite La0.6Sr0.4CoO3-δ was obtained in a gas flow reactor by means of the quasi-equilibrium oxygen release technique. The thermodynamic properties of oxides were determined as a function of oxygen nonstoichiometry. Within the framework of the itinerant electron model, the dependence of the oxide nonstoichiometry on the oxygen activity was related to the density of electronic states near the Fermi level.

  9. Electrical properties and water incorporation in A-site deficient perovskite La{sub 1−x}Ba{sub x}Nb{sub 3}O{sub 9−0.5x}

    SciTech Connect

    Animitsa, I.; Iakovleva, A.; Belova, K.

    2016-06-15

    Barium doped A-site deficient perovskites La{sub 1−x}Ba{sub x}Nb{sub 3}O{sub 9−0.5x} (x=0–0.05) were synthesized by the solid state method, their structure, electrical properties and state of oxygen-hydrogen groups have been investigated. These phases were found to be able to incorporate water from the gas phase and to exhibit proton transport. Hydration is accompanied by the formation of different forms of oxygen-hydrogen groups: OH{sup −} – groups and H{sub 3}O{sup +} – ions. The total conductivities of doped samples increased in a wet atmosphere due to the appearance of proton current carriers (at the temperatures below 700 °C), but the conductivity increased insignificantly (~0.25 order of magnitude) because of a low doping level and, consequently, small concentration of protons. TG-measurements confirmed relatively low water content (below 0.2%). The total conductivity depends substantially on x and exhibits a minimum on σ−f(x) dependencies. It has been suggested that such behavior is a manifestation of a mixed cation effect. - Highlights: • Barium doped perovskites La{sub 1−x}Ba{sub x}Nb{sub 3}O{sub 9−0.5x} (x=0–0.05) are capable to incorporate water from the gas phase and to exhibit proton transport. • The hydration is accompanied by the formation of OH{sup −} – groups and H{sub 3}O{sup +} – ions. • The total conductivity exhibits a minimum on σ−f(x) dependencies as a result of a mixed cation effect.

  10. Role of Nonradiative Defects and Environmental Oxygen on Exciton Recombination Processes in CsPbBr3 Perovskite Nanocrystals.

    PubMed

    Lorenzon, Monica; Sortino, Luca; Akkerman, Quinten; Accornero, Sara; Pedrini, Jacopo; Prato, Mirko; Pinchetti, Valerio; Meinardi, Francesco; Manna, Liberato; Brovelli, Sergio

    2017-06-14

    Lead halide perovskite nanocrystals (NCs) are emerging as optically active materials for solution-processed optoelectronic devices. Despite the technological relevance of tracing rational guidelines for optimizing their performances and stability beyond their intrinsic resilience to structural imperfections, no in-depth study of the role of selective carrier trapping and environmental conditions on their exciton dynamics has been reported to date. Here we conduct spectro-electrochemical (SEC) experiments, side-by-side to oxygen sensing measurements on CsPbBr3 NCs for the first time. We show that the application of EC potentials controls the emission intensity by altering the occupancy of defect states without degrading the NCs. Reductive potentials lead to strong (60%) emission quenching by trapping of photogenerated holes, whereas the concomitant suppression of electron trapping is nearly inconsequential to the emission efficiency. Consistently, oxidizing conditions result in minor (5%) brightening due to suppressed hole trapping, confirming that electron traps play a minor role in nonradiative decay. This behavior is rationalized through a model that links the occupancy of trap sites with the position of the NC Fermi level controlled by the EC potential. Photoluminescence measurements in controlled atmosphere reveal strong quenching by collisional interactions with O2, which is in contrast to the photobrightening effect observed in films and single crystals. This indicates that O2 acts as a scavenger of photoexcited electrons without mediation by structural defects and, together with the asymmetrical SEC response, suggests that electron-rich defects are likely less abundant in nanostructured perovskites than in the bulk, leading to an emission response dominated by direct interaction with the environment.

  11. Roles of Bulk and Surface Chemistry in the Oxygen Exchange Kinetics and Related Properties of Mixed Conducting Perovskite Oxide Electrodes

    PubMed Central

    Perry, Nicola H.; Ishihara, Tatsumi

    2016-01-01

    Mixed conducting perovskite oxides and related structures serving as electrodes for electrochemical oxygen incorporation and evolution in solid oxide fuel and electrolysis cells, respectively, play a significant role in determining the cell efficiency and lifetime. Desired improvements in catalytic activity for rapid surface oxygen exchange, fast bulk transport (electronic and ionic), and thermo-chemo-mechanical stability of oxygen electrodes will require increased understanding of the impact of both bulk and surface chemistry on these properties. This review highlights selected work at the International Institute for Carbon-Neutral Energy Research (I2CNER), Kyushu University, set in the context of work in the broader community, aiming to characterize and understand relationships between bulk and surface composition and oxygen electrode performance. Insights into aspects of bulk point defect chemistry, electronic structure, crystal structure, and cation choice that impact carrier concentrations and mobilities, surface exchange kinetics, and chemical expansion coefficients are emerging. At the same time, an understanding of the relationship between bulk and surface chemistry is being developed that may assist design of electrodes with more robust surface chemistries, e.g., impurity tolerance or limited surface segregation. Ion scattering techniques (e.g., secondary ion mass spectrometry, SIMS, or low energy ion scattering spectroscopy, LEIS) with high surface sensitivity and increasing lateral resolution are proving useful for measuring surface exchange kinetics, diffusivity, and corresponding outer monolayer chemistry of electrodes exposed to typical operating conditions. Beyond consideration of chemical composition, the use of strain and/or a high density of active interfaces also show promise for enhancing performance. PMID:28773978

  12. Responses of Sugar Beet Roots to Iron Deficiency. Changes in Carbon Assimilation and Oxygen Use1

    PubMed Central

    López-Millán, Ana Flor; Morales, Fermín; Andaluz, Sofía; Gogorcena, Yolanda; Abadía, Anunciación; Rivas, Javier De Las; Abadía, Javier

    2000-01-01

    Different root parts with or without increased iron-reducing activities have been studied in iron-deficient and iron-sufficient control sugar beet (Beta vulgaris L. Monohil hybrid). The distal root parts of iron-deficient plants, 0 to 5 mm from the root apex, were capable to reduce Fe(III)-chelates and contained concentrations of flavins near 700 μm, two characteristics absent in the 5 to 10 mm sections of iron-deficient plants and the whole root of iron-sufficient plants. Flavin-containing root tips had large pools of carboxylic acids and high activities of enzymes involved in organic acid metabolism. In iron-deficient yellow root tips there was a large increase in carbon fixation associated to an increase in phosphoenolpyruvate carboxylase activity. Part of this carbon was used, through an increase in mitochondrial activity, to increase the capacity to produce reducing power, whereas another part was exported via xylem. Root respiration was increased by iron deficiency. In sugar beet iron-deficient roots flavins would provide a suitable link between the increased capacity to produce reduced nucleotides and the plasma membrane associated ferric chelate reductase enzyme(s). Iron-deficient roots had a large oxygen consumption rate in the presence of cyanide and hydroxisalycilic acid, suggesting that the ferric chelate reductase enzyme is able to reduce oxygen in the absence of Fe(III)-chelates. PMID:11027736

  13. Effects of environmental oxygen deficiency on embryos and larvae of bay scallop, Argopecten irradians irradians

    NASA Astrophysics Data System (ADS)

    Chun-de, Wang; Fu-Sui, Zhang

    1995-12-01

    The experimental results showed that: 1) The embryonic development of bay scallop is inhibited at a dissolved oxygen range of 1.38-3.64×10-3 at 23°C, and completely blocked below the lower limit. 2) The tolerance of larvae to anoxia increased with larval sizes and was related to their oxygen debt. 3) The scallop larvae exhibited specific behavioral responses to oxygen deficiency, which finally led to velum disintegration and larval death. The possible relationship between environmental oxygen deficiency and the disease of disintegration of the larval velum is also discussed. In this study, considerable oxygen debt was found in bay scallop larvae, which was greater in small animals. Based on the works of previous authors, a new concept is proposed for the estimation of oxygen debt, namely, the compensatory rate of oxygen debt (CROD). This can be used in intra—or interspecific comparison of oxygen debt. The results can be helpful in the management of water quality and for the prevention of larval diseases encountered in scallop culture.

  14. Asphyxia due to oxygen deficiency by gaseous substances.

    PubMed

    Watanabe, T; Morita, M

    1998-08-31

    The determination of the cause of death in asphyxiation gas cases is very difficult because of the variation in circumstances surrounding such deaths. To clarify the cause of death and to identify the factors involved in asphyxia, the symptoms during asphyxia, the concentration of gases at the respiratory arrest, the time to death and the concentration of the gaseous substances in the tissues were studied using rats and six gases. Three inhalations were used: (1) rapid asphyxia (2-3 min) in the exposure chamber in which the oxygen was depleted completely, (2) prolonged asphyxia (20-25 min) by gradually depleted oxygen, and (3) asphyxia by the inhalation of gases saturated with a critical gas concentration, maintaining the O2 at 20% (60 min). In the rapid asphyxia groups, respiratory arrest occurred within 30 to 40 s, followed by cardiac arrest 2 or 3 min thereafter. Severe convulsions were observed only with the use of nitrogen. In the prolonged asphyxia groups, respiratory arrest occurred at the concentration of 4-5% O2 with non-toxic gases (N2, CH4, N2O, and propane). The toxic gases CO2 and Freon-22 produced respiratory arrest at the concentration of 6.6-8.0% O2 (60-67% CO2) and 13-14% of O2 (30-35% Freon-22), respectively. Variations in the concentrations of the gases among the tissues was observed according to the type of asphyxia, type of gas and the duration of exposure. The concentration of the fat-soluble gases in the adipose tissue showed marked variation according to the duration of the exposure. The distribution pattern of methane was different from those of the other gases, in which the variation of concentrations among the tissues except lung were little in both rapid and prolonged asphyxia. These phenomena were considered to be attributable to the solubility of the gaseous substances in blood and tissues. Atrophy in the alveoli was observed after the rapid asphyxia with CO2 and N2O. Local hemorrhaging in the lungs was also observed, especially in CO2

  15. Characterization of ordering in A-site deficient perovskite Ca1–xLa 2x/3TiO3 using STEM/EELS

    DOE PAGES

    Danaie, Mohsen; Kepaptsoglou, Demie; Ramasse, Quentin M.; ...

    2016-09-15

    The vacancy ordering behavior of an A-site deficient perovskite system, Ca1–xLa2x/3TiO3, was studied using atomic resolution scanning transmission electron microscopy (STEM) in conjunction with electron energy-loss spectroscopy (EELS), with the aim of determining the role of A-site composition changes. At low La content (x = 0.2), adopting Pbnm symmetry, there was no indication of long-range ordering. Domains, with clear boundaries, were observed in bright-field (BF) imaging, but were not immediately visible in the corresponding high-angle annular dark-field (HAADF) image. These boundaries, with the aid of displacement maps from A-site cations in the HAADF signal, are shown to be tilt boundaries.more » At the La-rich end of the composition (x = 0.9), adopting Cmmm symmetry, long-range ordering of vacancies and La3+ ions was observed, with alternating La-rich and La-poor layers on (001)p planes, creating a double perovskite lattice along the c axis. These highly ordered domains can be found isolated within a random distribution of vacancies/La3+, or within a large population, encompassing a large volume. In regions with a high number density of double perovskite domains, these highly ordered domains were separated by twin boundaries, with 90° or 180° lattice rotations across boundaries. In conclusion, the occurrence and characteristics of these ordered structures are discussed and compared with similar perovskite systems.« less

  16. Oxygen-deficient waters along the Japanese coast and their effects upon the estuarine ecosystem.

    PubMed

    Suzuki, T

    2001-01-01

    Development of hypoxia in Japan has been confirmed in the inner part of almost every major bay of Japan on the Pacific Coast from Tokyo southward. This paper presents multiple aspects (present condition, hydraulic mechanism, effect upon fisheries, historical progress and nutrient budget between sediment and water) using Mikawa Bay, where Japan's most serious hypoxia occurs, as an example. Although hypoxia basically results from the increase of nutrient load input from domestic and livestock sources, the intense reclamation of shallows (including tidal flats) and the large reduction in river flow due to farmland irrigation drastically accelerated dissolved oxygen deficiency. Oxygen-deficient waters in Mikawa Bay are large enough to strip the water purification capacity of the remaining shallows. Unfortunately, the shallows have turned from a purifier to a source of nutrient load. These conditions are more or less common in all bays where the dissolved oxygen-deficient waters have been reported. To break this cycle, dissolved oxygen deficiency must be contained to the extent that the purification capacity of the shallows can be restored to an efficient level. For this purpose, the first thing to do is to restore tidal flats over an extensive area and to recover sufficient water flow, which may be a more urgent imperative than reducing the nutrient load input.

  17. The oxygen defect perovskite Ca 3Mn 1.35Fe 1.65O 8.02: A highly frustrated antiferromagnet

    NASA Astrophysics Data System (ADS)

    Nguyen, N.; Calage, Y.; Varret, F.; Ferey, G.; Caignaert, V.; Hervieu, M.; Raveau, B.

    1984-07-01

    A new oxygen defect perovskite Ca 3Mn 1.35Fe 1.65O 8.02 has been isolated. It crystallizes in the orthorhombic system with the following parameters: a ⋍ a p√2; b ⋍ 3a p, and c ⋍ a p√2 . X-Ray diffraction shows that it corresponds to the second member of the structural series ( AMO 3) m( AMO 2□) and thus consists of double perovskite layers separated by tetrahedral layers. This phase, related to the brownmillerite structure, differs from the latter, in that it exhibits oxygen defects in the perovskite layer and an excess of oxygen in the tetrahedral layer. These results are explained by the ability of Mn III to adopt pyramidal coordination. Its magnetic properties have been investigated by susceptibility and magnetization measurements and Mössbauer spectroscopy in the temperature range 4-300 K. The dependence of the freezing temperature on the measuring technique (125 K with Mössbauer spectroscopy and 100 K from magnetization), the wide range of temperature where the freezing of the spins occurs, the sensitivity of χ on the cooling magnetic field and the drastic lowering of CM characterize a highly frustrated behavior due to cationic disorder in the structure.

  18. Layered perovskite oxide: a reversible air electrode for oxygen evolution/reduction in rechargeable metal-air batteries.

    PubMed

    Takeguchi, Tatsuya; Yamanaka, Toshiro; Takahashi, Hiroki; Watanabe, Hiroshi; Kuroki, Tomohiro; Nakanishi, Haruyuki; Orikasa, Yuki; Uchimoto, Yoshiharu; Takano, Hiroshi; Ohguri, Nobuaki; Matsuda, Motofumi; Murota, Tadatoshi; Uosaki, Kohei; Ueda, Wataru

    2013-07-31

    For the development of a rechargeable metal-air battery, which is expected to become one of the most widely used batteries in the future, slow kinetics of discharging and charging reactions at the air electrode, i.e., oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), respectively, are the most critical problems. Here we report that Ruddlesden-Popper-type layered perovskite, RP-LaSr3Fe3O10 (n = 3), functions as a reversible air electrode catalyst for both ORR and OER at an equilibrium potential of 1.23 V with almost no overpotentials. The function of RP-LaSr3Fe3O10 as an ORR catalyst was confirmed by using an alkaline fuel cell composed of Pd/LaSr3Fe3O10-2x(OH)2x·H2O/RP-LaSr3Fe3O10 as an open circuit voltage (OCV) of 1.23 V was obtained. RP-LaSr3Fe3O10 also catalyzed OER at an equilibrium potential of 1.23 V with almost no overpotentials. Reversible ORR and OER are achieved because of the easily removable oxygen present in RP-LaSr3Fe3O10. Thus, RP-LaSr3Fe3O10 minimizes efficiency losses caused by reactions during charging and discharging at the air electrode and can be considered to be the ORR/OER electrocatalyst for rechargeable metal-air batteries.

  19. Enhanced magnetoresistance induced by oxygen deficiency in La{sub 0.4}Ca{sub 0.6}MnO{sub 3-δ} oxides

    SciTech Connect

    Triki, M. Dhahri, E.; Hlil, E. K.; Garden, J. L.

    2014-03-14

    We report electrical features and magnetoresistance behavior of the oxygen deficient La{sub 0.4}Ca{sub 0.6}MnO{sub 3-δ} perovskites (δ = 0, 0.15, and 0.2). These samples will be referred to as S0, S15, and S20, respectively. The dependence of electrical transport on temperature and magnetic field is systematically investigated between 2 K and 400 K in magnetic field ranging up to 5 T. The parent compound shows a stable charge ordering/antiferromagnetic state with a semiconductor-like behavior in all considered temperature range. The variable range hopping and thermally activated hopping models are found to fit well with the electrical resistivity data at low and high temperatures, respectively. Oxygen deficiency tends to weaken the charge ordering and induce ferromagnetism and metallicity at low temperature. Metal insulator transition appears at higher fields for lower oxygen deficit (S15 sample) and without field for the S20 sample. The resistivity data for S15 sample are discussed in the framework of the variable-range hopping model. Abnormal transport properties were observed in the S20 sample, characterized by the double metal-insulator transitions and low minimum behavior. These results are discussed in terms of phenomenological percolation model, based on the phase segregation of ferromagnetic metallic clusters and paramagnetic insulating regions. While the parent compound shows no magnetoresistance, a large magnetoresistance is observed in the deficient samples at low temperature reaching 90% and 75% at 2 T for S15 and S20 samples, respectively. Noticeably, these values reached 98% and 91% at 5 T. The appearance of colossal magnetoresistance is attributed to the spin dependent hopping between spin clusters and/or ferromagnetic domains.

  20. Dinitrogen Fixation Within and Adjacent to Oxygen Deficient Waters of the Eastern Tropical South Pacific Ocean

    NASA Astrophysics Data System (ADS)

    Widner, B.; Mulholland, M. R.; Bernhardt, P. W.; Chang, B. X.; Jayakumar, A.

    2016-02-01

    Recent work suggests that planktonic diazotrophs are geographically more widely distributed than previously thought including relatively warm (14-23oC) aphotic oxygenated pelagic waters and in aphotic waters within oxygen deficient zones. Because the volume of aphotic water in the ocean is large and may increase in the future, if dinitrogen (N2) fixation is widely occurring at sub-euphotic depths, this could result in a dramatic upward revision of global nitrogen (N) inputs via this process. N2 fixation rates were measured during a cruise in the Eastern Tropical South Pacific using stable isotope tracer techniques that account for slow gas dissolution. Results are compared with light, nutrient, and oxygen gradients (and necessarily temperature gradients). In addition, rates of N2 fixation made in vertical profiles within and above oxygen deficient waters are compared with those measured in vertical profiles adjacent to oxygen deficient waters. Results suggest that while rates of N2 fixation were measurable in deeper anoxic waters, volumetric N2 fixation rates were higher in surface waters.

  1. Preparation and electrochemical properties of urchin-like La0.8Sr0.2MnO3 perovskite oxide as a bifunctional catalyst for oxygen reduction and oxygen evolution reaction

    NASA Astrophysics Data System (ADS)

    Jin, Chao; Cao, Xuecheng; Zhang, Liya; Zhang, Cong; Yang, Ruizhi

    2013-11-01

    An urchin-like La0.8Sr0.2MnO3 (LSM) perovskite oxide has been synthesized through a co-precipitation method with urea as a precipitator, and characterized by thermogravimetric analysis (TGA), X-ray diffraction (XRD), scanning electron microscopy (SEM) and BET analysis. SEM results show that a micro/nanocomposite with an urchin-like morphology has been obtained. The as-synthesized LSM perovskite oxide has a high specific surface area of 48 m2 g-1. The catalytic activity of the oxide for the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER) in 0.1 M KOH solution has been studied by using a rotating-ring-disk electrode (RRDE). In the ORR test, a maximum cathodic current density of 5.2 mA cm-2 at -1.0 V (vs. Ag/AgCl) with 2500 rpm was obtained, and the ORR mainly favors a direct four-electron pathway. The results of anodic linear scanning voltammograms indicate that the urchin-like LSM perovskite oxide exhibits an encouraging catalytic activity for the OER. All electrochemical measurements suggest that the urchin-like LSM perovskite oxide could be used as a bifunctional catalyst for the ORR and the OER.

  2. Effect of oxygen deficiency on the photoresponse and reactivity of mixed phase titania thin films

    SciTech Connect

    DeSario, Paul A.; Chen Le; Graham, Michael E.; Gray, Kimberly A.

    2011-05-15

    Nonstoichiometric mixed phased titania nanocomposites (TiO{sub 2-x}) were deposited by reactive direct current magnetron sputtering. The authors explored the role of nonstoichiometry (as defined by oxygen deficiency in synthesis) in mixed phase titania thin films and its effects on the photoresponse and photocatalytic performance for CO{sub 2} reduction to methane under UV and visible light. Oxygen partial pressure was varied during film deposition, yielding different levels of oxygen deficiency in the films. Optimized nonstoichiometric films showed a strong redshift. The authors have identified an optimum set of synthesis conditions for TiO{sub 2-x} films that produce a relative maximum in photocatalytically produced methane under both UV and visible light.

  3. Bacterial Activity and Organic Matter Turnover in Oxygen Deficient Waters of the Baltic Sea

    NASA Astrophysics Data System (ADS)

    Piontek, J.; Massmig, M.; Endres, S.; Le Moigne, F. A. C.; Bange, H. W.; Engel, A.

    2016-02-01

    The Baltic Sea is an enclosed marine system that suffers from expanding zones of oxygen deficiency due to limited ventilation by the episodic inflow of oxygenated North Sea water combined with high anthropogenic nutrient loads. In particular coastal areas are strongly influenced by eutrophication that leads to enhanced microbial oxygen consumption and sporadic anoxia even at shallow sites. It has been shown that oxygen availability is a powerful determinant of the taxonomic composition of prokaryotic communities in deep waters of the Baltic Sea. However, it remains unclear if community changes in response to low oxygen impact carbon remineralization or if functional redundancy prevents effects on major biogeochemical processes driven by bacterial activity. Our study includes monthly samplings at a coastal time series station over three annual cycles with recurring anoxic periods in late summer. Furthermore, sampling was accomplished in the deep Gotland Basin, where a permanent pycnocline prevents vertical mixing. We determined rates of extracellular glucosidase, aminopeptidase and phosphatase, as well as bacterial protein production using fluorescent and radioactive labelled substrate analogues, respectively. The rate measurements were combined with the analysis of organic matter concentration and composition by different analytical tools. Field data and experimental work show that enzymatic polymer hydrolysis, bacterial biomass production and growth rates in oxygen deficient waters of the Baltic Sea are not inherently lower than in oxic waters. Instead, results reveal that the reactivity of organic carbon and the availability of inorganic nutrients are more powerful constraints on organic matter turnover in oxygen deficient zones of the Baltic Sea. Our results imply that oxygen availability alone is not the decisive factor for heterotrophic bacterial activity in deep waters, instead it is part of a multiple environmental control of carbon remineralization.

  4. Thermal assisted oxygen annealing for high efficiency planar CH₃NH₃PbI₃ perovskite solar cells.

    PubMed

    Ren, Zhiwei; Ng, Annie; Shen, Qian; Gokkaya, Huseyin Cem; Wang, Jingchuan; Yang, Lijun; Yiu, Wai-Kin; Bai, Gongxun; Djurišić, Aleksandra B; Leung, Wallace Woon-fong; Hao, Jianhua; Chan, Wai Kin; Surya, Charles

    2014-10-24

    We report investigations on the influences of post-deposition treatments on the performance of solution-processed methylammonium lead triiodide (CH₃NH₃PbI₃)-based planar solar cells. The prepared films were stored in pure N₂ at room temperature or annealed in pure O₂ at room temperature, 45°C, 65°C and 85°C for 12 hours prior to the deposition of the metal electrodes. It is found that annealing in O₂ leads to substantial increase in the power conversion efficiencies (PCEs) of the devices. Furthermore, strong dependence on the annealing temperature for the PCEs of the devices suggests that a thermally activated process may underlie the observed phenomenon. It is believed that the annealing process may facilitate the diffusion of O₂ into the spiro-MeOTAD for inducing p-doping of the hole transport material. Furthermore, the process can result in lowering the localized state density at the grain boundaries as well as the bulk of perovskite. Utilizing thermal assisted O₂ annealing, high efficiency devices with good reproducibility were attained. A PCE of 15.4% with an open circuit voltage (VOC) 1.04 V, short circuit current density (JSC) 23 mA/cm(2), and fill factor 0.64 had been achieved for our champion device.

  5. Emergent Noncentrosymmetry and Piezoelectricity Driven by Oxygen Octahedral Rotations in n = 2 Dion-Jacobson Phase Layer Perovskites

    SciTech Connect

    Strayer, Megan E.; Gupta, Arnab Sen; Akamatsu, Hirofumi; Lei, Shiming; Benedek, Nicole A.; Gopalan, Venkatraman; Mallouk, Thomas E.

    2016-04-29

    We demonstrate the loss of centrosymmetry via oxygen octahedral rotations in the n = 2 Dion–Jacobson family of layered oxide perovskites, A'LaB2O7 (A' = Rb, Cs; B = Nb, Ta). Ab initio density functional theory calculations predict that all four materials should adopt polar space groups, in contrast to the results of previous experimental studies that have assigned these materials to the centrosymmetric P4/mmm space group. Optical second harmonic generation experiments confirm the presence of a noncentrosymmetric phase at ambient temperature. Piezoresponse force microscopy experiments also show that this phase is piezoelectric. Moreover, to elucidate the symmetry-breaking and assign the appropriate space groups, the crystal structure of CsLaNb2O7is refined as a function of temperature from synchrotron X-ray diffraction data. Above 550 K, CsLaNb2O7 adopts the previously determined centrosymmetric P4/mmm space group. Between 550 and 350 K, the symmetry is lowered to the noncentrosymmetric space group Amm2. Below 350 K, additional symmetry lowering is observed as peak splitting, but the space group cannot be unambiguously identified.

  6. Evolution of oxygen-vacancy ordered crystal structures in the perovskite series SrnFenO3n-1 (n=2, 4, 8, and {infinity}), and the relationship to electronic and magnetic properties.

    SciTech Connect

    Hodges, J. P.; Jorgensen, J. D.; Xiong, X.; Dabrowski, B.; Mini, S. M.; Kimball, C. W.; Materials Science Division; Northern Illinois Univ.

    2000-05-01

    Over the oxygen composition range 2.5{<=}x{<=}3.0, the SrFeO{sub x} system exists as four distinct compounds with the nominal composition Sr{sub n}Fe{sub n}O{sub 3n-1} (n=2, 4, 8, and {infinity}). The end member SrFeO{sub 3} (n={infinity}) possesses a simple cubic perovskite crystal structure, whereas the oxygen-deficient (n=2, 4, and 8) members each adopt a different vacancy-ordered perovskite crystal structure. Using time-of-flight neutron powder diffraction, we show that previously proposed structures for the Sr{sub 4}Fe{sub 4}O{sub 11} (n=4) and Sr{sub 8}Fe{sub 8}O{sub 23} (n=8) compounds are incorrect. We determine the correct crystal structures for Sr{sub 4}Fe{sub 4}O{sub 11} (orthorhombic, space group Cmmm, a=10.974(1) {angstrom}, b=7.702(1) {angstrom}, and c=5.473(1) {angstrom}) and Sr{sub 8}Fe{sub 8}O{sub 23} (tetragonal, space group I4/mmm, a=10.929(1) {angstrom} and c=7.698(1) {angstrom}) through comparisons of the goodness of fit for Rietveld refinements of candidate models and bond-length distributions for each model. Using the correct crystal structures, we are able to assign valence states to the Fe crystallographic sites and to achieve consistency with published Moessbauer results for the same compounds.

  7. Induced polarized state in intentionally grown oxygen deficient KTaO{sub 3} thin films

    SciTech Connect

    Mota, D. A.; Romaguera-Barcelay, Y.; Tkach, A.; Agostinho Moreira, J.; Almeida, A.; Perez de la Cruz, J.; Vilarinho, P. M.; Tavares, P. B.

    2013-07-21

    Deliberately oxygen deficient potassium tantalate thin films were grown by RF magnetron sputtering on Si/SiO{sub 2}/Ti/Pt substrates. Once they were structurally characterized, the effect of oxygen vacancies on their electric properties was addressed by measuring leakage currents, dielectric constant, electric polarization, and thermally stimulated depolarization currents. By using K{sub 2}O rich KTaO{sub 3} targets and specific deposition conditions, KTaO{sub 3-{delta}} oxygen deficient thin films with a K/Ta = 1 ratio were obtained. Room temperature X-ray diffraction patterns show that KTaO{sub 3-{delta}} thin films are under a compressive strain of 2.3% relative to KTaO{sub 3} crystals. Leakage current results reveal the presence of a conductive mechanism, following the Poole-Frenkel formalism. Furthermore, dielectric, polarization, and depolarization current measurements yield the existence of a polarized state below T{sub pol} {approx} 367 Degree-Sign C. A Cole-Cole dipolar relaxation was also ascertained apparently due to oxygen vacancies induced dipoles. After thermal annealing the films in an oxygen atmosphere at a temperature above T{sub pol}, the aforementioned polarized state is suppressed, associated with a drastic oxygen vacancies reduction emerging from annealing process.

  8. Magnetism and Metal-Insulator Transition in Oxygen Deficient SrTiO3

    DOE PAGES

    Lopez-Bezanilla, Alejandro; Ganesh, Panchapakesan; Littlewood, Peter B.

    2015-09-08

    First-principles calculations to study the electronic and magnetic properties of bulk, oxygen-deficient SrTiO3 (STO) under different doping conditions and densities have been conducted. The appearance of magnetism in oxygen-deficient STO is not determined solely by the presence of a single oxygen vacancy but by the density of free carriers and the relative proximity of the vacant sites. We find that while an isolated vacancy behaves as a nonmagnetic double donor, manipulation of the doping conditions allows the stability of a single-donor state, with emergent local moments coupled ferromagnetically by carriers in the conduction band. Strong local lattice distortions enhance themore » binding of this state. As a result, the energy of the in-gap local moment can be further tuned by orthorhombic strain. Consequently we find that the free-carrier density and strain are fundamental components to obtaining trapped spin-polarized electrons in oxygen-deficient STO, which may have important implications in the design of optical devices.« less

  9. Magnetism and Metal-Insulator Transition in Oxygen Deficient SrTiO3

    SciTech Connect

    Lopez-Bezanilla, Alejandro; Ganesh, Panchapakesan; Littlewood, Peter B.

    2015-09-08

    First-principles calculations to study the electronic and magnetic properties of bulk, oxygen-deficient SrTiO3 (STO) under different doping conditions and densities have been conducted. The appearance of magnetism in oxygen-deficient STO is not determined solely by the presence of a single oxygen vacancy but by the density of free carriers and the relative proximity of the vacant sites. We find that while an isolated vacancy behaves as a nonmagnetic double donor, manipulation of the doping conditions allows the stability of a single-donor state, with emergent local moments coupled ferromagnetically by carriers in the conduction band. Strong local lattice distortions enhance the binding of this state. As a result, the energy of the in-gap local moment can be further tuned by orthorhombic strain. Consequently we find that the free-carrier density and strain are fundamental components to obtaining trapped spin-polarized electrons in oxygen-deficient STO, which may have important implications in the design of optical devices.

  10. Transport properties and photo electrochemical characterization of oxygen-deficient ASnO 3- δ (A=Ca, Sr and Ba)

    NASA Astrophysics Data System (ADS)

    Zidi, N.; Omeiri, S.; Hadjarab, B.; Bouguelia, A.; Akroun, A.; Trari, M.

    2010-08-01

    The deficient stannate BaSnO 3- δ, prepared at 980 °C in sealed tube, crystallizes in an ideal perovskite structure. The oxide exhibits a blue color, the bandgap is found to be 2.65 eV and the transition is directly allowed. The non-stoichiometry could not be measured, indicating no appreciable oxygen deficiency. Nevertheless, the transport properties were found to change markedly with the heat treatment. BaSnO 3- δ behaves as degenerate SC with a conductivity σ300 K (=1.63 Ω -1 cm -1) and where the level Ef drops above mobility edge to delocalized states. The electric balance leads to a simultaneous reduction of Sn 4+ inducing n-type behavior. The thermal variation of the thermopower indicates an electron mobility μ300 K (=0.013 cm 2 V -1 s -1) thermally activated. The metal-insulating transition is considered of Anderson type due to the random potential to oxygen vacancies. A predominant variable range hopping is predicted from the non-linearity of Ln σ versus T-1 plot. The capacitance measurement ( C-2- V), measured in KOH media, shows a linear behavior from which a flat band potential Vfb (=-0.67 VSCE) and a density ND (=7.59×10 20 cm -3) are determined. The deficient stannates CaSnO 3 and SrSnO 3 are reported for a comparative purpose. The decrease of Eg is ascribed to the increase of the conduction band width when going from Ba to Ca.

  11. Generation of Oxygen Deficiency in Cell Culture Using a Two-Enzyme System to Evaluate Agents Targeting Hypoxic Tumor Cells

    PubMed Central

    Baumann, Raymond P.; Penketh, Philip G.; Seow, Helen A.; Shyam, Krishnamurthy; Sartorelli, Alan C.

    2008-01-01

    The poor and aberrant vascularization of solid tumors makes them susceptible to localized areas of oxygen deficiency that can be considered sites of tumor vulnerability to pro-drugs that are preferentially activated to cytotoxic species under conditions of low oxygenation. To readily facilitate the selection of agents targeted to oxygen-deficient cells in solid tumors, we have developed a simple and convenient two-enzyme system to generate oxygen deficiency in cell cultures. Glucose oxidase is employed to deplete oxygen from the medium by selectively oxidizing glucose and reducing molecular oxygen to hydrogen peroxide; an excess of catalase is also used to scavenge the peroxide molecules. Rapid and sustained depletion of oxygen occurs in medium or buffer, even in the presence of oxygen at the liquid/air interface. Studies using CHO/AA8 Chinese hamster cells, EMT6 murine mammary carcinoma cells, and U251 human glioma cells indicate that this system generates an oxygen deficiency that produces activation of the hypoxia-targeted prodrug KS119. This method of generating oxygen deficiency in cell culture is inexpensive, does not require cumbersome equipment, permits longer incubation times to be used without the loss of sample volume, and should be adaptable for high-throughput screening in 96-well plates. PMID:18959466

  12. Structure and ferromagnetic instability of the oxygen-deficient SrTiO3 surface

    NASA Astrophysics Data System (ADS)

    Ghosh, Soham S.; Manousakis, Efstratios

    2016-08-01

    SrTiO3 (STO) is the substrate of choice to grow oxide thin films and oxide heterojunctions, which can form quasi-two-dimensional electronic phases that exhibit a wealth of phenomena, and thus a workhorse in the emerging field of metal-oxide electronics. Hence, it is of great importance to know the exact character of the STO surface itself under various oxygen environments. Using density functional theory within the spin generalized gradient approximation we have investigated the structural, electronic, and magnetic properties of the oxygen-deficient STO surface. We find that the surface oxygen vacancies order in periodic arrays giving rise to surface magnetic moments and a quasi-two-dimensional electron gas in the occupied Ti 3 d orbitals. The surface confinement, the oxygen-vacancy ordering, and the octahedra distortions give rise to spin-polarized t2 g dispersive subbands; their energy split near the Brillouin zone center acts as an effective Zeeman term, which, when we turn on a Rashba interaction, produces bands with momentum-spin correlations similar to those recently discovered on oxygen-deficient STO surface.

  13. Synthesis and Redox Behavior of Oxygen Deficient Brannerite LiVWO6-δ for Lithium Batteries

    NASA Astrophysics Data System (ADS)

    Prabaharan, S. R. S.; Mumtaj Begam, K.; Fauzi, A.; Ramesh, S.; Michael, M. S.

    2002-12-01

    This paper describes the synthesis and electrochemical behavior of the oxygen deficient brannerite LiVWO6-δ Brannerite LiVWO6-δ has been synthesized by means of a simple aqueous solution reaction (ASR) technique namely soft-combustion process employing glycine as a soft combustion agent. The synthesized product has been subjected to thermal treatment in various stages in order to best understand the phase formation and study their redox behavior in lithium-containing cells. Electrochemical studies such as Cyclic voltammetry, Galvanostatic (constant current) charge-discharge curves and Galvanostatic Intermittent Titration Technique (GITT) on this oxygen deficient product show that this material could be regarded as 4-volt class category with specific capacities as high as ~ 95 mAh/g in the voltage regime 4.9 V to 2.8 V vs Li+/Li.

  14. Enhanced nonlinear optical properties of oxygen deficient lead-niobium-germanate film glasses

    NASA Astrophysics Data System (ADS)

    Gonzalo, J.; Fernandez, H.; Solis, J.; Munoz-Martin, D.; Fernandez-Navarro, J. M.; Afonso, C. N.; Fierro, J. L. G.

    2007-06-01

    The third order nonlinear optical properties of oxygen deficient lead-niobium-germanate film glasses with heavy metal contents beyond that of the bulk glass formation region have been investigated. Values of the nonlinear third order optical susceptibility up to /χ(3)/≈1.8×10-11esu have been measured by degenerate four wave mixing at 800nm in films having large heavy metal fractions (0.93). The fast buildup and decay times (≈130fs) of the nonlinear response confirm its nonresonant character. The partial reduction of Nb5+ to Nb4+ evidenced by x-ray photoelectron spectroscopy, which is associated with the oxygen deficiency, appears to be responsible for the strong enhancement of /χ(3)/.

  15. Nitrogen Doping in Oxygen-Deficient Ca2Fe2O5: A Strategy for Efficient Oxygen Reduction Oxide Catalysts.

    PubMed

    Jijil, Chamundi P; Lokanathan, Moorthi; Chithiravel, Sundaresan; Nayak, Chandrani; Bhattacharyya, Dibyendu; Jha, Shambhu Nath; Babu, P D; Kakade, Bhalchandra; Devi, R Nandini

    2016-12-21

    Oxygen reduction reaction (ORR) is increasingly being studied in oxide systems due to advantages ranging from cost effectiveness to desirable kinetics. Oxygen-deficient oxides like brownmillerites are known to enhance ORR activity by providing oxygen adsorption sites. In parallel, nitrogen and iron doping in carbon materials, and consequent presence of catalytically active complex species like C-Fe-N, is also suggested to be good strategies for designing ORR-active catalysts. A combination of these features in N-doped Fe containing brownmillerite can be envisaged to present synergistic effects to improve the activity. This is conceptualized in this report through enhanced activity of N-doped Ca2Fe2O5 brownmillerite when compared to its oxide parents. N doping is demonstrated by neutron diffraction, UV-vis spectroscopy, X-ray photoelectron spectroscopy, and X-ray absorption spectroscopy. Electrical conductivity is also found to be enhanced by N doping, which influences the activity. Electrochemical characterization by cyclic voltammetry, rotating disc electrode, and rotating ring disk electrode (RRDE) indicates an improved oxygen reduction activity in N-doped brownmillerite, with a 10 mV positive shift in the onset potential. RRDE measurements show that the compound exhibits 4-electron reduction pathways with lower H2O2 production in the N-doped system; also, the N-doped sample exhibited better stability. The observations will enable better design of ORR catalysts that are stable and cost-effective.

  16. A perovskite oxide optimized for oxygen evolution catalysis from molecular orbital principles.

    PubMed

    Suntivich, Jin; May, Kevin J; Gasteiger, Hubert A; Goodenough, John B; Shao-Horn, Yang

    2011-12-09

    The efficiency of many energy storage technologies, such as rechargeable metal-air batteries and hydrogen production from water splitting, is limited by the slow kinetics of the oxygen evolution reaction (OER). We found that Ba(0.5)Sr(0.5)Co(0.8)Fe(0.2)O(3-δ) (BSCF) catalyzes the OER with intrinsic activity that is at least an order of magnitude higher than that of the state-of-the-art iridium oxide catalyst in alkaline media. The high activity of BSCF was predicted from a design principle established by systematic examination of more than 10 transition metal oxides, which showed that the intrinsic OER activity exhibits a volcano-shaped dependence on the occupancy of the 3d electron with an e(g) symmetry of surface transition metal cations in an oxide. The peak OER activity was predicted to be at an e(g) occupancy close to unity, with high covalency of transition metal-oxygen bonds.

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

    SciTech Connect

    Malkhandi, S; Trinh, P; Manohar, AK; Manivannan, A; Balasubramanian, M; Prakash, GKS; Narayanan, SR

    2015-04-16

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

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

    SciTech Connect

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

    2015-04-16

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

  19. Accumulation of Fe oxyhydroxides in the Peruvian oxygen deficient zone implies non-oxygen dependent Fe oxidation

    NASA Astrophysics Data System (ADS)

    Heller, Maija I.; Lam, Phoebe J.; Moffett, James W.; Till, Claire P.; Lee, Jong-Mi; Toner, Brandy M.; Marcus, Matthew A.

    2017-08-01

    Oxygen minimum zones (OMZs) have been proposed to be an important source of dissolved iron (Fe) into the interior ocean. However, previous studies in OMZs have shown a sharp decrease in total dissolved Fe (dFe) and/or dissolved Fe(II) (dFe(II)) concentrations at the shelf-break, despite constant temperature, salinity and continued lack of oxygen across the shelf-break. The loss of both total dFe and dFe(II) suggests a conversion of the dFe to particulate form, but studies that have coupled the reduction-oxidation (redox) speciation of both dissolved and particulate phases have not previously been done. Here we have measured the redox speciation and concentrations of both dissolved and particulate forms of Fe in samples collected during the U.S. GEOTRACES Eastern tropical Pacific Zonal Transect (EPZT) cruise in 2013 (GP16). This complete data set allows us to assess possible mechanisms for loss of dFe. We observed an offshore loss of dFe(II) within the oxygen deficient zone (ODZ), where dissolved oxygen is undetectable, accompanied by an increase in total particulate Fe (pFe). Total pFe concentrations were highest in the upper ODZ. X-ray absorption spectroscopy revealed that the pFe maximum was primarily in the Fe(III) form as Fe(III) oxyhydroxides. The remarkable similarity in the distributions of total particulate iron and nitrite suggests a role for nitrite in the oxidation of dFe(II) to pFe(III). We present a conceptual model for the rapid redox cycling of Fe that occurs in ODZs, despite the absence of oxygen.

  20. Magnetism and metal-insulator transition in oxygen deficient SrTiO3

    NASA Astrophysics Data System (ADS)

    Lopez-Bezanilla, Alejandro; Ganesh, P.; Littlewood, Peter

    2015-03-01

    We report new findings in the electronic structure and magnetism of oxygen vacancies in SrTiO3. By means of first-principles calculations we show that the appearance of magnetism in oxygen-deficient SrTiO3 is not determined solely by the presence of a single oxygen vacancy but by the density of free carriers and the relative proximity of the vacant sites. While an isolated vacancy behaves as a non-magnetic double donor, manipulation of the doping conditions allows the stability of a single donor state with emergent local moments. Strong local lattice distortions enhance the binding of this state. Consequently we find that the free-carrier density and strain are fundamental components to obtaining trapped spin-polarized electrons in oxygen-deficient SrTiO3, which may have important implications in the design of switchable magneto-optic devices. AL-B and PBL were supported by DOE-BES under Contract No. DE-AC02-06CH11357. PG was sponsored by the Laboratory Directed Research and Development Program of Oak Ridge National Laboratory, managed by UT- Battelle, LLC, for the US Department of Energy.

  1. Undocumented water column sink for cadmium in open ocean oxygen-deficient zones

    PubMed Central

    Janssen, David J.; Conway, Tim M.; John, Seth G.; Christian, James R.; Kramer, Dennis I.; Pedersen, Tom F.; Cullen, Jay T.

    2014-01-01

    Cadmium (Cd) is a micronutrient and a tracer of biological productivity and circulation in the ocean. The correlation between dissolved Cd and the major algal nutrients in seawater has led to the use of Cd preserved in microfossils to constrain past ocean nutrient distributions. However, linking Cd to marine biological processes requires constraints on marine sources and sinks of Cd. Here, we show a decoupling between Cd and major nutrients within oxygen-deficient zones (ODZs) in both the Northeast Pacific and North Atlantic Oceans, which we attribute to Cd sulfide (CdS) precipitation in euxinic microenvironments around sinking biological particles. We find that dissolved Cd correlates well with dissolved phosphate in oxygenated waters, but is depleted compared with phosphate in ODZs. Additionally, suspended particles from the North Atlantic show high Cd content and light Cd stable isotope ratios within the ODZ, indicative of CdS precipitation. Globally, we calculate that CdS precipitation in ODZs is an important, and to our knowledge a previously undocumented marine sink of Cd. Our results suggest that water column oxygen depletion has a substantial impact on Cd biogeochemical cycling, impacting the global relationship between Cd and major nutrients and suggesting that Cd may be a previously unidentified tracer for water column oxygen deficiency on geological timescales. Similar depletions of copper and zinc in the Northeast Pacific indicate that sulfide precipitation in ODZs may also have an influence on the global distribution of other trace metals. PMID:24778239

  2. Undocumented water column sink for cadmium in open ocean oxygen-deficient zones.

    PubMed

    Janssen, David J; Conway, Tim M; John, Seth G; Christian, James R; Kramer, Dennis I; Pedersen, Tom F; Cullen, Jay T

    2014-05-13

    Cadmium (Cd) is a micronutrient and a tracer of biological productivity and circulation in the ocean. The correlation between dissolved Cd and the major algal nutrients in seawater has led to the use of Cd preserved in microfossils to constrain past ocean nutrient distributions. However, linking Cd to marine biological processes requires constraints on marine sources and sinks of Cd. Here, we show a decoupling between Cd and major nutrients within oxygen-deficient zones (ODZs) in both the Northeast Pacific and North Atlantic Oceans, which we attribute to Cd sulfide (CdS) precipitation in euxinic microenvironments around sinking biological particles. We find that dissolved Cd correlates well with dissolved phosphate in oxygenated waters, but is depleted compared with phosphate in ODZs. Additionally, suspended particles from the North Atlantic show high Cd content and light Cd stable isotope ratios within the ODZ, indicative of CdS precipitation. Globally, we calculate that CdS precipitation in ODZs is an important, and to our knowledge a previously undocumented marine sink of Cd. Our results suggest that water column oxygen depletion has a substantial impact on Cd biogeochemical cycling, impacting the global relationship between Cd and major nutrients and suggesting that Cd may be a previously unidentified tracer for water column oxygen deficiency on geological timescales. Similar depletions of copper and zinc in the Northeast Pacific indicate that sulfide precipitation in ODZs may also have an influence on the global distribution of other trace metals.

  3. Hydrogenated Oxygen-Deficient Blue Anatase as Anode for High-Performance Lithium Batteries.

    PubMed

    Zheng, Jing; Liu, Yousong; Ji, Guangbin; Zhang, Peng; Cao, Xingzhong; Wang, Baoyi; Zhang, Chuhong; Zhou, Xuguang; Zhu, Yan; Shi, Daning

    2015-10-28

    Blue oxygen-deficient nanoparticles of anatase TiO2 (H-TiO2) are synthesized using a modified hydrogenation process. Scanning electron microscope and transmission electron microscope images clearly demonstrate the evident change of the TiO2 morphology, from 60 nm rectangular nanosheets to much smaller round or oval nanoparticles of ∼17 nm, after this hydrogenation treatment. Importantly, electron paramagnetic resonance and positronium annihilation lifetime spectroscopy confirm that plentiful oxygen vacancies accompanied by Ti(3+) are created in the hydrogenated samples with a controllable concentration by altering hydrogenation temperature. Experiments and theory calculations demonstrate that the well-balanced Li(+)/e(-) transportation from a synergetic effect between Ti(3+)/oxygen vacancy and reduced size promises the optimal H-TiO2 sample a high specific capacity, as well as greatly enhanced cycling stability and rate performance in comparison with the other TiO2.

  4. The oxygen deficiency effect of VO{sub 2} thin films prepared by laser ablation

    SciTech Connect

    Nagashima, M.; Wada, H.

    1997-02-01

    Vanadium dioxide thin films (VO{sub 2}) have been deposited by laser ablation. The temperature dependence of resistivity and temperature coefficient of resistance (TCR) for each deposition condition were investigated. It was clarified that the TCR at room temperature (RT) can be optimized by controlling the oxygen pressure introduced during deposition as the deposition parameter. In the result, larger TCR{close_quote}s at RT were observed for the oxygen deficient condition of VO{sub 2} than for oxygen-richer samples. Obtained TCR values were 0.072/K and 0.045/K at 25{degree}C for VO{sub 2} thin films deposited onto R-cut sapphire and SiO{sub 2}/Si, respectively. {copyright} {ital 1997 Materials Research Society.}

  5. The lanthanum gallate-based mixed conducting perovskite ceramics

    NASA Astrophysics Data System (ADS)

    Politova, E. D.; Stefanovich, S. Yu.; Aleksandrovskii, V. V.; Kaleva, G. M.; Mosunov, A. V.; Avetisov, A. K.; Sung, J. S.; Choo, K. Y.; Kim, T. H.

    2005-01-01

    The structure, microstructure, dielectric, and transport properties of the anion deficient perovskite solid solutions (La,Sr)(Ga,Mg,M)O3- with M=Fe, Ni have been studied. Substitution of iron and nickel for gallium up to about 20 and 40 at.% respectively, leads to the perovskite lattice contraction due to the cation substitutions by the transition elements. The transition from pure ionic to mixed ionic-electronic conductivity was observed for both the systems studied. Both the enhancement of total conductivity and increasing in the thermal expansion coefficient values has been proved to correlate with the increasing amount of weakly bounded oxygen species in the Fe or Ni-doped ceramics. The oxygen ionic conductivity has been estimated from the kinetic experiments using the dc-conductivity and dilatometry methods under the condition of the stepwise change of the atmosphere from nitrogen to oxygen.

  6. Neurohistological Investigations on General Oxygen Deficiency of the Brain. 2. The Behavior of Astocytes After Acute and Subacute Death

    DTIC Science & Technology

    1951-03-01

    the cell bodies.the brain were examined histologically and stain’ At first sight this picture was suggestive of the formationed by methods common in...INVESTIGATIONS ON GENERAL OXYGEN DEFICIENCY OF THE BRAIN at 11 I. The Behavior of Astrocytes After Acute and Subacute Death A PROJECT NUMBER 21-23-004...c3, REPORT NUMBER 2 PROJECT IREPORT NEUROHISTOLOGICAL INVESTIGATIONS ON GENERAL OXYGEN DEFICIENCY OF THE BRAIN II. The Behavior of Astrocytes After

  7. Effect of manganese and calcium deficiency on the growth and oxygen exchange of Scenedesmus intermedius cultured for successive generations.

    PubMed

    Adam, M S; Issa, A A

    2000-01-01

    The green alga Scenedesmus intermedius was grown in synchronous culture under manganese or calcium deficiency for six successive generations. The growth rate, pigment and protein contents gradually decreased in comparison with the control. In Mn-deficient cells, the rate of oxygen evolution was sharply decreased. This inhibition was restored to normal in less than 1 h (40-60 min) by adding Mn salt to the suspension medium. In Ca-deficient cells, the inhibition of photosynthesis appears to be irreversible.

  8. Looking beyond stratification: a model-based analysis of the biological drivers of oxygen deficiency in the North Sea

    NASA Astrophysics Data System (ADS)

    Große, Fabian; Greenwood, Naomi; Kreus, Markus; Lenhart, Hermann-Josef; Machoczek, Detlev; Pätsch, Johannes; Salt, Lesley; Thomas, Helmuth

    2016-04-01

    Low oxygen conditions, often referred to as oxygen deficiency, occur regularly in the North Sea, a temperate European shelf sea. Stratification represents a major process regulating the seasonal dynamics of bottom oxygen, yet, lowest oxygen conditions in the North Sea do not occur in the regions of strongest stratification. This suggests that stratification is an important prerequisite for oxygen deficiency, but that the complex interaction between hydrodynamics and the biological processes drives its evolution. In this study we use the ecosystem model HAMSOM-ECOHAM to provide a general characterisation of the different zones of the North Sea with respect to oxygen, and to quantify the impact of the different physical and biological factors driving the oxygen dynamics inside the entire sub-thermocline volume and directly above the bottom. With respect to oxygen dynamics, the North Sea can be subdivided into three different zones: (1) a highly productive, non-stratified coastal zone, (2) a productive, seasonally stratified zone with a small sub-thermocline volume, and (3) a productive, seasonally stratified zone with a large sub-thermocline volume. Type 2 reveals the highest susceptibility to oxygen deficiency due to sufficiently long stratification periods (> 60 days) accompanied by high surface productivity resulting in high biological consumption, and a small sub-thermocline volume implying both a small initial oxygen inventory and a strong influence of the biological consumption on the oxygen concentration. Year-to-year variations in the oxygen conditions are caused by variations in primary production, while spatial differences can be attributed to differences in stratification and water depth. The large sub-thermocline volume dominates the oxygen dynamics in the northern central and northern North Sea and makes this region insusceptible to oxygen deficiency. In the southern North Sea the strong tidal mixing inhibits the development of seasonal stratification

  9. Ultrafast Atomic Layer-by-Layer Oxygen Vacancy-Exchange Diffusion in Double-Perovskite LnBaCo2O5.5+δ Thin Films

    PubMed Central

    Bao, Shanyong; Ma, Chunrui; Chen, Garry; Xu, Xing; Enriquez, Erik; Chen, Chonglin; Zhang, Yamei; Bettis, Jerry L.; Whangbo, Myung-Hwan; Dong, Chuang; Zhang, Qingyu

    2014-01-01

    Surface exchange and oxygen vacancy diffusion dynamics were studied in double-perovskites LnBaCo2O5.5+δ (LnBCO) single-crystalline thin films (Ln = Er, Pr; −0.5 < δ < 0.5) by carefully monitoring the resistance changes under a switching flow of oxidizing gas (O2) and reducing gas (H2) in the temperature range of 250 ~ 800°C. A giant resistance change ΔR by three to four orders of magnitude in less than 0.1 s was found with a fast oscillation behavior in the resistance change rates in the ΔR vs. t plots, suggesting that the oxygen vacancy exchange diffusion with oxygen/hydrogen atoms in the LnBCO thin films is taking the layer by layer oxygen-vacancy-exchange mechanism. The first principles density functional theory calculations indicate that hydrogen atoms are present in LnBCO as bound to oxygen forming O-H bonds. This unprecedented oscillation phenomenon provides the first direct experimental evidence of the layer by layer oxygen vacancy exchange diffusion mechanism. PMID:24751601

  10. Underestimation of oxygen deficiency hazard through use of linearized temperature profiles

    SciTech Connect

    Kerby, J.

    1989-06-15

    The failure mode analysis for any cryogenic system includes the effects of a large liquid spill due to vessel rupture or overfilling. The Oxygen Deficiency Hazard (ODH) analysis for this event is a strong function of the estimated heat flux entering the spilled liquid. A common method for estimating the heat flux is to treat the surface on which the liquid spills as a semi-infinite solid. This note addresses the effect of linearizing the temperature profile in this form of analysis, and shows it to cause the calculated flux to be underestimated by more than a factor of two. 3 refs., 2 figs.

  11. Polyketide Quinones Are Alternate Intermediate Electron Carriers during Mycobacterial Respiration in Oxygen-Deficient Niches.

    PubMed

    Anand, Amitesh; Verma, Priyanka; Singh, Anil Kumar; Kaushik, Sandeep; Pandey, Rajesh; Shi, Ce; Kaur, Harneet; Chawla, Manbeena; Elechalawar, Chandra Kumar; Kumar, Dhirendra; Yang, Yong; Bhavesh, Neel S; Banerjee, Rajkumar; Dash, Debasis; Singh, Amit; Natarajan, Vivek T; Ojha, Anil K; Aldrich, Courtney C; Gokhale, Rajesh S

    2015-11-19

    Mycobacterium tuberculosis (Mtb) adaptation to hypoxia is considered crucial to its prolonged latent persistence in humans. Mtb lesions are known to contain physiologically heterogeneous microenvironments that bring about differential responses from bacteria. Here we exploit metabolic variability within biofilm cells to identify alternate respiratory polyketide quinones (PkQs) from both Mycobacterium smegmatis (Msmeg) and Mtb. PkQs are specifically expressed in biofilms and other oxygen-deficient niches to maintain cellular bioenergetics. Under such conditions, these metabolites function as mobile electron carriers in the respiratory electron transport chain. In the absence of PkQs, mycobacteria escape from the hypoxic core of biofilms and prefer oxygen-rich conditions. Unlike the ubiquitous isoprenoid pathway for the biosynthesis of respiratory quinones, PkQs are produced by type III polyketide synthases using fatty acyl-CoA precursors. The biosynthetic pathway is conserved in several other bacterial genomes, and our study reveals a redox-balancing chemicocellular process in microbial physiology.

  12. Molecular tools for investigating microbial community structure and function in oxygen-deficient marine waters.

    PubMed

    Hawley, Alyse K; Kheirandish, Sam; Mueller, Andreas; Leung, Hilary T C; Norbeck, Angela D; Brewer, Heather M; Pasa-Tolic, Ljiljana; Hallam, Steven J

    2013-01-01

    Water column oxygen (O2)-deficiency shapes food-web structure by progressively directing nutrients and energy away from higher trophic levels into microbial community metabolism resulting in fixed nitrogen loss and greenhouse gas production. Although respiratory O2 consumption during organic matter degradation is a natural outcome of a productive surface ocean, global-warming-induced stratification intensifies this process leading to oxygen minimum zone (OMZ) expansion. Here, we describe useful tools for detection and quantification of potential key microbial players and processes in OMZ community metabolism including quantitative polymerase chain reaction primers targeting Marine Group I Thaumarchaeota, SUP05, Arctic96BD-19, and SAR324 small-subunit ribosomal RNA genes and protein extraction methods from OMZ waters compatible with high-resolution mass spectrometry for profiling microbial community structure and functional dynamics.

  13. Distribution change of oxygen vacancies in layered perovskite type(Sr, La){sub n+1}Fe{sub n}O{sub 3n+1} (n=3)

    SciTech Connect

    Kagomiya, Isao Jimbo, Keigo; Kakimoto, Ken-ichi

    2013-11-15

    To elucidate characteristic oxygen vacancy formation in layered perovskite (Sr, La){sub n+1}Fe{sub n}O{sub 3n+1} with the perovskite layer number: n=3, oxygen vacancy content δ of the (Sr{sub 0.775}La{sub 0.225}){sub 4}Fe{sub 3}O{sub 10−δ} (SLF4310) was investigated using a titration technique and a thermogravimetric analysis. The equilibrium constant K for the reduction reaction: Oo{sup ×}+2Fe{sub Fe}{sup ∙} (Fe{sup 4+})=1/2O{sub 2}+Vo{sup ∙∙}+2Fe{sub Fe}{sup ×}(Fe{sup 3+}) was estimated using the vacancy content δ. The Arrhenius plot of the K reveals slope change at approximately 775 °C. From the Rietveld analysis, the oxygen vacancies are the most remarkable at the O2 (O4) sites at lower (higher) temperatures than about 800 °C, which temperature is approximately comparable with that of slope change in the K. These facts mean that distribution of vacancy sites in the SLF4310 changes at approximately 775 °C, accompanying no structural phase transition. The vacancy distribution change affects to the ion conductivity of the SLF4310. - Graphical abstract: Crystal structure of (Sr{sub 0.775}La{sub 0.225}){sub 4}Fe{sub 3}O{sub 10−δ} (SLF4310) at 1000 °C. Display Omitted - Highlights: • Distribution change of oxygen vacancies is appeared at approximately 775 °C. • The distribution change with no structure phase transition is the first observation. • The vacancy distribution change affects the ion conductivity of the SLF4310.

  14. A persistent metal-insulator transition at the surface of an oxygen-deficient, epitaxial manganite film.

    PubMed

    Snijders, Paul C; Gao, Min; Guo, Hangwen; Cao, Guixin; Siemons, Wolter; Gao, Hongjun; Ward, Thomas Z; Shen, Jian; Gai, Zheng

    2013-10-21

    The oxygen stoichiometry has a large influence on the physical and chemical properties of complex oxides. Most of the functionality in e.g. catalysis and electrochemistry depends in particular on control of the oxygen stoichiometry. In order to understand the fundamental properties of intrinsic surfaces of oxygen-deficient complex oxides, we report on in situ temperature dependent scanning tunnelling spectroscopy experiments on pristine oxygen deficient, epitaxial manganite films. Although these films are insulating in subsequent ex situ in-plane electronic transport experiments at all temperatures, in situ scanning tunnelling spectroscopic data reveal that the surface of these films exhibits a metal-insulator transition (MIT) at 120 K, coincident with the onset of ferromagnetic ordering of small clusters in the bulk of the oxygen-deficient film. The surprising proximity of the surface MIT transition temperature of nonstoichiometric films with that of the fully oxygenated bulk suggests that the electronic properties in the surface region are not significantly affected by oxygen deficiency in the bulk. This carries important implications for the understanding and functional design of complex oxides and their interfaces with specific electronic properties in catalysis, oxide electronics and electrochemistry.

  15. Crystal Structure and Magnetic Properties of an oxygen deficient n = 2 Ruddlesden-Popper phase Sr3Co2O5.67

    NASA Astrophysics Data System (ADS)

    Hill, Julienne M.; Mitchell, John F.; Dabrowski, Bogdan

    2006-03-01

    Interest in charge, orbital, and spin state phenomena in perovskite and related cobalt oxides is a growing area of transition metal oxide physics. Recently, J. Matsuno et al. have found that epitaxial films of the n = 1 Ruddlesden-Popper (R-P) phase Sr2CoO4 are metallic ferromagnets with relatively high TC ˜ 250 K. This is particularly interesting in light of the formal oxidation state of Co, Co^4+, offering no clear source of carriers. To extend the materials chemistry and physics of the R-P series of cobaltites, we have synthesized the n = 2 R-P phase Sr3Co2O7-δ in bulk form. The crystal structure [from neutron powder diffraction (NPD) data] of our most oxygen-deficient sample, Sr3Co2O5.67 is orthorhombic Immm with a = 3.94025(9) å, b = 3.67479(9) å and c = 20.6642(5) å. The magnetization versus temperature data show two antiferromagnetic transitions at approximately 170 K and 220 K. To further elucidate the magnetic properties of this material, we have conducted a temperature-dependent NPD study. The low temperature magnetic structure is surprisingly complex and suggestive of an incommensurate ordering wave vector. Full details and results of the NPD study will be given. J. Matsuno et al., PRL 93, 167202 (2004).

  16. Calculation of arrangement of oxygen ions and vacancies in double perovskite GdBaCo2O(5+δ) by first-principles DFT with Monte Carlo simulations.

    PubMed

    Shiiba, Hiromasa; Nakayama, Masanobu; Kasuga, Toshihiro; Grimes, Robin W; Kilner, John A

    2013-07-07

    The configurations of oxygen ions and vacancies at various oxygen stoichiometries and temperatures in double perovskite oxides (GdBaCo2O(5+δ), 0 ≤ δ ≤ 1) have been determined by density functional theory (DFT) combined with Monte Carlo (MC) simulations. The MC simulations confirmed the existence of a superstructure at δ = 0.5, showing alternating linear ordering of oxygen ions and vacancies along the b-axis in the GdO layer. This structure is identical to that reported experimentally. Increasing the temperature up to 1200 K induces a phase transition manifested in the breaking of the oxygen/vacancy arrangement at around δ = 0.5. In the high-temperature phase, vacancies are distributed in the GdO and CoO2 layers, whereas there are no vacancies in the BaO layer. In addition, the characteristic linear arrangement is partly preserved even in the disordered high-temperature phase. Consequently, oxygen ions can migrate between the GdO and CoO2 layers, as reported in previous classical molecular dynamics simulation studies.

  17. Nitrogen metabolism and translocation in soybean plants subjected to root oxygen deficiency.

    PubMed

    Oliveira, Halley C; Freschi, Luciano; Sodek, Ladaslav

    2013-05-01

    Although nitrate (NO3(-)) but not ammonium (NH4(+)) improves plant tolerance to oxygen deficiency, the mechanisms involved in this phenomenon are just beginning to be understood. By using gas chromatography-mass spectrometry, we investigated the metabolic fate of (15)NO3(-) and (15)NH4(+) in soybean plants (Glycine max L. Merril cv. IAC-23) subjected to root hypoxia. This stress reduced the uptake of (15)NO3(-) and (15)NH4(+) from the medium and decreased the overall assimilation of these nitrogen sources into amino acids in roots and leaves. Root (15)NO3(-) assimilation was more affected by hypoxia than that of (15)NH4(+), resulting in enhanced nitrite and nitric oxide release in the solution. However, (15)NO3(-) was translocated in substantial amounts by xylem sap and considerable (15)NO3(-) assimilation into amino acids also occurred in the leaves, both under hypoxia and normoxia. By contrast, (15)NH4(+) assimilation occurred predominantly in roots, resulting in accumulation of mainly (15)N-alanine in this tissue during hypoxia. Analysis of lactate levels suggested higher fermentation in roots from NH4(+)-treated plants compared to the NO3(-) treatment. Thus, foliar NO3(-) assimilation may be relevant to plant tolerance to oxygen deficiency, since it would economize energy expenditure by hypoxic roots. Additionally, the involvement of nitric oxide synthesis from nitrite in the beneficial effect of NO3(-) is discussed. Copyright © 2013 Elsevier Masson SAS. All rights reserved.

  18. Responses of Soybean to Oxygen Deficiency and Elevated Root‐zone Carbon Dioxide Concentration

    PubMed Central

    BORU, G.; VANTOAI, T.; ALVES, J.; HUA, D.; KNEE, M.

    2003-01-01

    Root flooding is damaging to the growth of crop plants such as soybean (Glycine max L.). Field flooding for 3 d often results in leaf chlorosis, defoliation, cessation of growth and plant death. These effects have been widely attributed solely to a lack of oxygen in the root‐zone. However, an additional damaging factor may be CO2, which attains levels of 30 % (v/v) of total dissolved gases. Accordingly, the effects of root‐zone CO2 on oxygen‐deficient soybean plants were investigated in hydroponic culture. Soybean plants are shown to be very tolerant of excess water and anaerobiosis. No oxygen (100 % N2 gas) and low oxygen (non‐aerated) treatments for 14 d had no effect on soybean survival or leaf greenness, but plants became severely chlorotic and stunted when the roots were exposed to no oxygen together with CO2 concentrations similar to those in flooded fields (equilibrium concentrations of 30 %). When root‐zone CO2 was increased to 50 %, a quarter of soybean plants died. Those plants that survived showed severe symptoms of chlorosis, necrosis and root death. In contrast, rice (Oryza sativa L.) plants were not affected by the combination of no oxygen and elevated root‐zone CO2. A concentration of 50 % CO2 did not affect rice plant survival or leaf colour. These results suggest that the high susceptibility of soybean to soil flooding, compared with that of rice, is an outcome of its greater sensitivity to CO2. PMID:12588724

  19. Double perovskite oxides Sr{sub 2}MMoO{sub 6} (M = Fe and Co) as cathode materials for oxygen reduction in alkaline medium

    SciTech Connect

    Cheriti, Mabrouk; Kahoul, Abdelkrim

    2012-01-15

    Graphical abstract: The oxygen reduction over the surface of the electrocatalysts exhibiting high currents shows that SCMO/C electrocatalyst is slightly more active than the SFMO/C one. The relatively high electrochemical activity of the first may be ascribed to its high specific surface area providing a higher electrode current. Highlights: Black-Right-Pointing-Pointer SCMO/C and SFMO/C as catalysts for oxygen reduction were studied. Black-Right-Pointing-Pointer SCMO/C catalyst showed a relatively high activity. Black-Right-Pointing-Pointer A change in the reaction mechanism from a direct 'four-electron pathway' to a 'peroxide pathway' was observed. -- Abstract: The oxygen reduction reaction (ORR) was studied on Sr{sub 2}MMoO{sub 6} (M = Fe and Co) double perovskites, prepared by a solid-state reaction, in 0.5 M NaOH at 25 Degree-Sign C with a rotating disk electrode (RDE). The two oxide powders were characterized by X-ray diffraction, scanning electron microscopy and BET analysis. The electrochemical techniques considered are linear voltammetry, steady state polarization and ac impedance spectroscopy. The electrocatalysts (SFMO/C, SCMO/C) consisting of the double perovskite oxides and carbon (Vulcan XC-72) were mixed and spread out into a thin layer on a glassy carbon substrate. At room temperature, a significantly electrocatalytic activity is observed for both electrocatalysts. Compared to SFMO/C, the SCMO/C electrocatalyst was found to show a relatively high electrocatalytic activity for O{sub 2} reduction, which agrees well with the results obtained using the ac impedance spectroscopy.

  20. Research Update: Plentiful magnetic moments in oxygen deficient SrTiO{sub 3}

    SciTech Connect

    Lopez-Bezanilla, Alejandro; Ganesh, P.; Littlewood, Peter B.

    2015-10-01

    Correlated band theory is employed to investigate the magnetic and electronic properties of different arrangements of oxygen di- and tri-vacancy clusters in SrTiO{sub 3}. Hole and electron doping of oxygen deficient SrTiO{sub 3} yields various degrees of magnetization as a result of the interaction between localized magnetic moments at the defect sites. Different kinds of Ti atomic orbital hybridization are described as a function of the doping level and defect geometry. We find that magnetism in SrTiO{sub 3−δ} is sensitive to the arrangement of neighbouring vacancy sites, charge carrier density, and vacancy-vacancy interaction. Permanent magnetic moments in the absence of vacancy doping electrons are observed. Our description of the charged clusters of oxygen vacancies widens the previous descriptions of mono- and multi-vacancies and points out the importance of the controlled formation at the atomic level of defects for the realization of transition metal oxide based devices with a desirable magnetic performance.

  1. Plentiful magnetic moments in oxygen deficient SrTiO3

    DOE PAGES

    Ganesh, Panchapakesan; Lopez-Bezanilla, Alejandro; Littlewood, Peter B.

    2015-10-06

    In this research, correlated band theory is employed to investigate the magnetic and electronic properties of different arrangements of oxygen di- and tri-vacancy clusters in SrTiO3. Hole and electron doping of oxygen deficient SrTiO3 yields various degrees of magnetization as a result of the interaction between localized magnetic moments at the defect sites. Different kinds of Ti atomic orbital hybridization are described as a function of the doping level and defect geometry. We find that magnetism in SrTiO3–δ is sensitive to the arrangement of neighbouring vacancy sites, charge carrier density, and vacancy-vacancy interaction. Permanent magnetic moments in the absence ofmore » vacancy doping electrons are observed. Our description of the charged clusters of oxygen vacancies widens the previous descriptions of mono- and multi-vacancies and points out the importance of the controlled formation at the atomic level of defects for the realization of transition metal oxide based devices with a desirable magnetic performance.« less

  2. Plentiful magnetic moments in oxygen deficient SrTiO3.

    SciTech Connect

    Lopez Bezanilla, Alejandro; Ganesh, P.; Littlewood, Peter B.

    2015-10-01

    Correlated band theory is employed to investigate the magnetic and electronic properties of different arrangements of oxygen di- and tri-vacancy clusters in SrTiO3. Hole and electron doping of oxygen deficient SrTiO3 yields various degrees of magnetization as a result of the interaction between localized magnetic moments at the defected sites. Different kinds of Ti atomic orbital hybridization are described as a function of the doping level and defect geometry. We find that magnetism in SrTiO3-d is sensitive to the arrangement of neighbouring vacancy sites, charge carrier density, and vacancy-vacancy interaction. Permanent magnetic moments in the absence of vacancy doping electrons are observed. Our description of the charged clusters of oxygen vacancies widens the previous descriptions of mono and multi-vacancies and points out the importance of the controlled formation at the atomic level of defects for the realization of transition metal oxide based devices with a desirable magnetic performance.

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

    SciTech Connect

    Heinemann, M. D.; Unold, T.; Berry, J.; Teeter, G.; Ginley, D.

    2016-01-11

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

  4. Influence of phase stabilization and perovskite vanadate oxygen vacancies of the BINIVOX catalyst on photocatalytic degradation of azo dye under visible light irradiation

    NASA Astrophysics Data System (ADS)

    Al-Areqi, Niyazi A. S.; Al-Kamali, Ahmed S. N.; Ghaleb, Kh. A. S.; Al-Alas, Ahlam; Al-Mureish, Khalid

    2014-02-01

    A layered Aurivillius-perovskite-type BINIVOX system with the general formula ? was developed as a novel photocatalyst for degradation of organic dyes. A series of the BINIVOX.x catalysts in the compositional range 0≤x≤0.20 were successfully synthesized by the standard solid-state reaction and characterized using X-ray powder diffraction, differential thermal analysis, UV-vis diffuse reflectance spectroscopy and Brunauer-Emmett-Teller BET surface area. Then, the photocatalytic activities of prepared catalysts were investigated for the first time through the degradation of a new azo dye named sodium 4-[(E)-(4,5-dimethyl-1H-pyrazolo [3,4-c] pyridazin-3-yl) diazenyl] naphthalen-1-olate and denoted as 4-SPPN in aqueous solution under visible light irradiation. Adsorption efficiency and photocatalytic activity of BINIVOX.x catalysts were correlated well with the variation in phase crystal structures stabilized at room temperature as a function of composition. The stabilized γ‧-BINIVOX phases in the tetragonal crystal system with space group I4/m mm exhibited the best photocatalytic performance which can be attributed to their higher specific surface area, narrower band-gap energy and higher oxygen-vacancy concentration in the perovskite vanadate layers. In addition, the possible photocatalytic degradation mechanism of aqueous 4-SPPN dye was proposed under visible light irradiation.

  5. Effect of Oxygen-deficiencies on Resistance Switching in Amorphous YFe0.5Cr0.5O3−d films

    PubMed Central

    Wang, Xianjie; Hu, Chang; Song, Yongli; Zhao, Xiaofeng; Zhang, Lingli; Lv, Zhe; Wang, Yang; Liu, Zhiguo; Wang, Yi; Zhang, Yu; Sui, Yu; Song, Bo

    2016-01-01

    Herein, we demonstrate the contribution of the oxygen-deficiencies on the bipolar resistance switching (RS) properties of amorphous-YFe0.5Cr0.5O3−d (a-YFCO) films. The a-YFCO films were prepared under various oxygen pressures to tune the concentration of oxygen-deficiencies in the films. The XPS data verify that the oxygen-deficiencies increase with decreasing oxygen pressure. The RS property becomes more pronounced with more oxygen-deficiencies in a-YFCO films. Based on the Ohmic conduction measurements in the low resistance state, we confirm that the RS mechanism is related to the migration of oxygen-deficiencies. The enhanced RS and long retention in a-YFCO suggest a great potential for applications in nonvolatile memory devices. PMID:27452114

  6. Nb K-edge x-ray absorption investigation of the pressure induced amorphization in A-site deficient double perovskite La1/3NbO3.

    PubMed

    Marini, C; Noked, O; Kantor, I; Joseph, B; Mathon, O; Shuker, R; Kennedy, B J; Pascarelli, S; Sterer, E

    2016-02-03

    Nb K-edge x-ray absorption spectroscopy is utilized to investigate the changes in the local structure of the A-site deficient double perovskite La1/3NbO3 which undergoes a pressure induced irreversible amorphization. EXAFS results show that with increasing pressure up to 7.5 GPa, the average Nb-O bond distance decreases in agreement with the expected compression and tilting of the NbO6 octahedra. On the contrary, above 7.5 GPa, the average Nb-O bond distance show a tendency to increase. Significant changes in the Nb K-edge XANES spectrum with evident low energy shift of the pre-peak and the absorption edge is found to happen in La1/3NbO3 above 6.3 GPa. These changes evidence a gradual reduction of the Nb cations from Nb(5+) towards Nb(4+) above 6.3 GPa. Such a valence change accompanied by the elongation of the average Nb-O bond distances in the octahedra, introduces repulsion forces between non-bonding adjacent oxygen anions in the unoccupied A-sites. Above a critical pressure, the Nb reduction mechanism can no longer be sustained by the changing local structure and amorphization occurs, apparently due to the build-up of local strain. EXAFS and XANES results indicate two distinct pressure regimes having different local and electronic response in the La1/3NbO3 system before the occurence of the pressure induced amorphization at  ∼14.5 GPa.

  7. Nb K-edge x-ray absorption investigation of the pressure induced amorphization in A-site deficient double perovskite La1/3NbO3

    NASA Astrophysics Data System (ADS)

    Marini, C.; Noked, O.; Kantor, I.; Joseph, B.; Mathon, O.; Shuker, R.; Kennedy, B. J.; Pascarelli, S.; Sterer, E.

    2016-02-01

    Nb K-edge x-ray absorption spectroscopy is utilized to investigate the changes in the local structure of the A-site deficient double perovskite La1/3NbO3 which undergoes a pressure induced irreversible amorphization. EXAFS results show that with increasing pressure up to 7.5 GPa, the average Nb-O bond distance decreases in agreement with the expected compression and tilting of the NbO6 octahedra. On the contrary, above 7.5 GPa, the average Nb-O bond distance show a tendency to increase. Significant changes in the Nb K-edge XANES spectrum with evident low energy shift of the pre-peak and the absorption edge is found to happen in La1/3NbO3 above 6.3 GPa. These changes evidence a gradual reduction of the Nb cations from Nb5+ towards Nb4+ above 6.3 GPa. Such a valence change accompanied by the elongation of the average Nb-O bond distances in the octahedra, introduces repulsion forces between non-bonding adjacent oxygen anions in the unoccupied A-sites. Above a critical pressure, the Nb reduction mechanism can no longer be sustained by the changing local structure and amorphization occurs, apparently due to the build-up of local strain. EXAFS and XANES results indicate two distinct pressure regimes having different local and electronic response in the La1/3NbO3 system before the occurence of the pressure induced amorphization at  ˜14.5 GPa.

  8. Cantilever stress measurements for pulsed laser deposition of perovskite oxides at 1000 K in an oxygen partial pressure of 10{sup −4} millibars

    SciTech Connect

    Premper, J.; Sander, D.; Kirschner, J.

    2015-03-15

    An in situ stress measurement setup using an optical 2-beam curvature technique is described which is compatible with the stringent growth conditions of pulsed laser deposition (PLD) of perovskite oxides, which involves high substrate temperatures of 1000 K and oxygen partial pressures of up to 1 × 10{sup −4} millibars. The stress measurements are complemented by medium energy electron diffraction (MEED), Auger electron spectroscopy, and additional growth rate monitoring by a quartz microbalance. A shielded filament is used to allow for simultaneous stress and MEED measurements at high substrate temperatures. A computer-controlled mirror scans an excimer laser beam over a stationary PLD target. This avoids mechanical noise originating from rotating PLD targets, and the setup does not suffer from limited lifetime issues of ultra high vacuum (UHV) rotary feedthroughs.

  9. Preparation of perovskite-type oxides of cobalt by the malic acid aided process and their electrocatalytic surface properties in relation to oxygen evolution

    SciTech Connect

    Tiwari, S.K.; Chartier, P.; Singh, R.N. . Electrochemical Lab.)

    1995-01-01

    The electrocatalytic properties of perovskite-type cobalt oxides (La[sub 1[minus]x]Sr[sub x]CoO[sub 3], where x = 0, 0.2, 0.4), in the form of thin films on conductive supports, were studied by cyclic voltammetry and Tafel polarization techniques. The films had conductive and satisfactory adherent properties. The oxides were synthesized by a low temperature malic acid aided method. The cyclic voltammetry showed a pair of redox peaks prior to the onset of oxygen evolution on the oxide film with nickel support, while similar peaks were absent in the same oxide film on Pt and Ti. The anodic polarization studies indicated two Tafel slopes: 57 to 64 mV/decade at low and 100 to 130 mV/decade at high overpotentials, and first-order kinetics with respect to OH[sup [minus

  10. Cantilever stress measurements for pulsed laser deposition of perovskite oxides at 1000 K in an oxygen partial pressure of 10-4 millibars

    NASA Astrophysics Data System (ADS)

    Premper, J.; Sander, D.; Kirschner, J.

    2015-03-01

    An in situ stress measurement setup using an optical 2-beam curvature technique is described which is compatible with the stringent growth conditions of pulsed laser deposition (PLD) of perovskite oxides, which involves high substrate temperatures of 1000 K and oxygen partial pressures of up to 1 × 10-4 millibars. The stress measurements are complemented by medium energy electron diffraction (MEED), Auger electron spectroscopy, and additional growth rate monitoring by a quartz microbalance. A shielded filament is used to allow for simultaneous stress and MEED measurements at high substrate temperatures. A computer-controlled mirror scans an excimer laser beam over a stationary PLD target. This avoids mechanical noise originating from rotating PLD targets, and the setup does not suffer from limited lifetime issues of ultra high vacuum (UHV) rotary feedthroughs.

  11. Hollow spherical La0.8Sr0.2MnO3 perovskite oxide with enhanced catalytic activities for the oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Lu, Fanliang; Sui, Jing; Su, Jianmin; Jin, Chao; Shen, Ming; Yang, Ruizhi

    2014-12-01

    A hollow spherical La0.8Sr0.2MnO3 (HS-LSM) perovskite oxide has been prepared using a new carbonate-template route, and characterized by XRD, SEM and TEM. SEM and TEM results show that the pre-prepared oxides consist of porous microspheres composed of submicrometer-sized subunits with a secondary particle diameter of ∼20-50 nm. The catalytic activity of the oxide for the oxygen reduction reaction (ORR) in 0.1 M KOH solution has been studied using a rotating ring-disk electrode (RRDE). In the ORR tests, a maximum cathodic current density of 6.4 mA cm-2 at -0.9 V (vs. Ag/AgCl) with 2500 rpm has been obtained, and the ORR mainly favors a direct four-electron pathway. The chronoamperometric test shows that the HS-LSM exhibits excellent stability for the ORR.

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

    PubMed Central

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

    2016-01-01

    Defects in semiconductors can exhibit multiple charge states, which can be used for charge storage applications. Here we consider such charge storage in a series of oxygen deficient phases of TiO2, known as Magnéli phases. These Magnéli phases (TinO2n−1) present well-defined crystalline structures, i.e., their deviation from stoichiometry is accommodated by changes in space group as opposed to point defects. We show that these phases exhibit intermediate bands with an electronic quadruple donor transitions akin to interstitial Ti defect levels in rutile TiO2. Thus, the Magnéli phases behave as if they contained a very large pseudo-defect density: ½ per formula unit TinO2n−1. Depending on the Fermi Energy the whole material will become charged. These crystals are natural charge storage materials with a storage capacity that rivals the best known supercapacitors. PMID:27364139

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

    PubMed

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

    2016-07-01

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

  14. Microbial functional diversity alters the structure and sensitivity of oxygen deficient zones

    NASA Astrophysics Data System (ADS)

    Penn, Justin; Weber, Thomas; Deutsch, Curtis

    2016-09-01

    Oxygen deficient zones (ODZs) below the ocean surface regulate marine productivity by removing bioavailable nitrogen (N). A complex microbial community mediates N loss, but the interplay of its diverse metabolisms is poorly understood. We present an ecosystem model of the North Pacific ODZ that reproduces observed chemical distributions yet predicts different ODZ structure, rates, and climatic sensitivity compared to traditional geochemical models. An emergent lower O2 limit for aerobic nitrification lies below the upper O2 threshold for anaerobic denitrification, creating a zone of microbial coexistence that causes a larger ODZ but slower total rates of N loss. The O2-dependent competition for the intermediate nitrite produces gradients in its oxidation versus reduction, anammox versus heterotrophic denitrification, and the net ecological stoichiometry of N loss. The latter effect implies that an externally driven ODZ expansion should favor communities that more efficiently remove N, increasing the sensitivity of the N cycle to climate change.

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

    NASA Astrophysics Data System (ADS)

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

    2016-07-01

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

  16. Case Report of Severe Antithrombin Deficiency During Extracorporeal Membrane Oxygenation and Therapeutic Plasma Exchange for Double Lung Transplantation.

    PubMed

    Williams, Brittney; Mazzeffi, Michael A; Sanchez, Pablo G; Pham, Si M; Kon, Zachary; Tanaka, Kenichi A

    2017-01-01

    Acquired antithrombin (AT) deficiency is not uncommon in cardiothoracic surgery because of heparin exposure and dilutional or consumptive losses. We report a case of acquired AT deficiency and resultant multiple deep vein thrombosis in a patient with pulmonary fibrosis on veno-venous extracorporeal membrane oxygenation who underwent double lung transplantation with intraoperative therapeutic plasma exchange (TPE) as a part of an immunomodulation regimen for allosensitization. Preoperative heparin anticoagulation resulted in AT deficiency, which was further exacerbated by TPE using albumin. The recovery of AT activity after TPE with plasma was incomplete, and postoperative deficiencies of AT and other anticoagulants might have contributed to deep vein thromboses. The limitation of thromboelastometry in detecting AT deficiency was evident.

  17. Reactive Oxygen Species Function to Mediate the Fe Deficiency Response in an Fe-Efficient Apple Genotype: An Early Response Mechanism for Enhancing Reactive Oxygen Production

    PubMed Central

    Sun, Chaohua; Wu, Ting; Zhai, Longmei; Li, Duyue; Zhang, Xinzhong; Xu, Xuefeng; Ma, Huiqin; Wang, Yi; Han, Zhenhai

    2016-01-01

    Reactive oxygen species (ROS) are important signaling molecules in plants that contribute to stress acclimation. This study demonstrated that ROS play a critical role in Fe deficiency-induced signaling at an early stage in Malus xiaojinensis. Once ROS production has been initiated, prolonged Fe starvation leads to activation of ROS scavenging mechanisms. Further, we demonstrated that ROS scavengers are involved in maintaining the cellular redox homeostasis during prolonged Fe deficiency treatment. Taken together, our results describe a feedback repression loop for ROS to preserve redox homeostasis and maintain a continuous Fe deficiency response in the Fe-efficient woody plant M. xiaojinensis. More broadly, this study reveals a new mechanism in which ROS mediate both positive and negative regulation of plant responses to Fe deficiency stress. PMID:27899933

  18. Reactive Oxygen Species Function to Mediate the Fe Deficiency Response in an Fe-Efficient Apple Genotype: An Early Response Mechanism for Enhancing Reactive Oxygen Production.

    PubMed

    Sun, Chaohua; Wu, Ting; Zhai, Longmei; Li, Duyue; Zhang, Xinzhong; Xu, Xuefeng; Ma, Huiqin; Wang, Yi; Han, Zhenhai

    2016-01-01

    Reactive oxygen species (ROS) are important signaling molecules in plants that contribute to stress acclimation. This study demonstrated that ROS play a critical role in Fe deficiency-induced signaling at an early stage in Malus xiaojinensis. Once ROS production has been initiated, prolonged Fe starvation leads to activation of ROS scavenging mechanisms. Further, we demonstrated that ROS scavengers are involved in maintaining the cellular redox homeostasis during prolonged Fe deficiency treatment. Taken together, our results describe a feedback repression loop for ROS to preserve redox homeostasis and maintain a continuous Fe deficiency response in the Fe-efficient woody plant M. xiaojinensis. More broadly, this study reveals a new mechanism in which ROS mediate both positive and negative regulation of plant responses to Fe deficiency stress.

  19. Iron-based perovskite cathodes for solid oxide fuel cells

    DOEpatents

    Ralph, James M.; Rossignol, Cecile C.R.; Vaughey, John T.

    2007-01-02

    An A and/or A' site deficient perovskite of general formula of (A.sub.1-xA'.sub.x).sub.1-yFeO.sub.3-.delta. or of general formula A.sub.1-x-yA'.sub.xFeO.sub.3-67, wherein A is La alone or with one or more of the rare earth metals or a rare earth metal other than Ce alone or a combination of rare earth metals and X is in the range of from 0 to about 1; A' is Sr or Ca or mixtures thereof and Y is in the range of from about 0.01 to about 0.3; .delta. represents the amount of compensating oxygen loss. If either A or A' is zero the remaining A or A' is deficient. A fuel cell incorporating the inventive perovskite as a cathode is disclosed as well as an oxygen separation membrane. The inventive perovskite is preferably single phase.

  20. Enhancing the photoelectrochemical properties of titanium dioxide by thermal treatment in oxygen deficient environment

    NASA Astrophysics Data System (ADS)

    Singh, Aadesh P.; Kodan, Nisha; Mehta, Bodh R.

    2016-05-01

    The effect of thermal treatment on TiO2 thin films under oxygen deficient environment (5% H2 in Ar) at partial pressure of 2 × 10-2 Torr have been studied for photoelectrochemical (PEC) water splitting application. Thermal treatment in anatase TiO2 thin films exhibits a shift in optical absorption from UV to visible region and activates TiO2 for water splitting application under visible light. X-ray photoelectron spectroscopy results showed that the thermal treated thin films contain oxygen vacancies, which suggests improved charge transport. Optical absorption, X-ray spectroscopy (XPS) and Kelvin probe force microscope (KPFM) studies show reduction in band gap by 0.36 eV, shift in valence band maximum by 0.49 eV towards the Fermi level and work function values by 0.3 eV towards the vacuum level. The pristine TiO2 thin films exhibit very less photoactivity in terms of photocurrent density, whereas thermally treated thin films displayed a markedly enhanced photocurrent density of ∼2.41 mA/cm2 at 0.23 V vs. Ag/AgCl. Higher values of photocurrent density in thermal treated TiO2 films have been explained in terms of change in the optical and electrical properties along with energy band diagram.

  1. [Oxygen deficiency increases invasive activity and resistance of Yersinia pseudotuberculosis to heat stress].

    PubMed

    Bakholdina, S I; Shubin, F N; Solov'eva, T F

    2009-01-01

    To study effects of oxygen availability and presence of glucose in growth medium on adhesive and invasive properties of Yersinia pseudotuberculosis as well as its resistance to heat stress during sharp rise of temperature from 8 degrees C to 37 degrees C. Yersinia pseudotuberculosis was grown on nutrient broth with or without glucose at 8 degrees C and two regimen of aeration--during intensive stirring (180 rpm) and without it. Adhesive and invasive activities were studied on the model of HeLa human cell line. Effects of temperature stress on the bacterial growth were assessed from growth curves plotted on the basis of quantity of colony-forming cells. Morphology of bacterial cells was studied by electron microscopy. It was shown that cultivation of Y. pseudotuberculosis at 8 degrees C and low aeration increases its adhesive and invasive activity as well resistance to heat stress. Adding of glucose to growth medium decreases invasiveness of Y. pseudotuberculosis irrespective to aeration regimen. Oxygen deficiency during low temperature of growth promotes increasing of pathogenic potential of Y. pseudotuberculosis. Obtained data are useful for solving practical problems associated with development of prevention measures for pseudotuberculosis as well with food processing and storage.

  2. Characterization of the Phosphofructokinase Gene Family in Rice and Its Expression Under Oxygen Deficiency Stress

    PubMed Central

    Mustroph, Angelika; Stock, Johanna; Hess, Natalia; Aldous, Sophia; Dreilich, Anika; Grimm, Bernhard

    2013-01-01

    Plants possess two types of phosphofructokinase proteins for phosphorylation of fructose-6-phosphate, the ATP-dependent phosphofructokinase (PFK) and the pyrophosphate-(PPi) dependent pyrophosphate-fructose-6-phosphate-phosphotransferase (PFP). During oxygen deficiency ATP levels in rice seedlings are severely reduced, and it is hypothesized that PPi is used as an alternative energy source for the phosphorylation of fructose-6-phosphate during glycolysis. In this study, we analyzed the expression of 15 phosphofructokinase-encoding genes in roots and aerial tissues of anoxia-tolerant rice seedlings in response to anoxic stress and compared our data with transcript profiles obtained from microarray analyses. Furthermore, the intracellular localization of rice PFK proteins was determined, and the PFK and PFP isoforms were grouped in a phylogenetic tree. Two PFK and two PFP transcripts accumulated during anoxic stress, whereas mRNA levels of four PFK and three PFP genes were decreased. The total specific activity of both PFK and PFP changed only slightly during a 24-h anoxia treatment. It is assumed that expression of different isoforms and their catalytic properties differ during normoxic and anoxic conditions and contribute to balanced glycolytic activity during the low-oxygen stress. These characterizations of phosphofructokinase genes and the comparison to other plant species allowed us to suggest candidate rice genes for adaptation to anoxic stress. PMID:23717315

  3. Electronic structure and excitations in oxygen deficient CeO2-δ from DFT calculations

    NASA Astrophysics Data System (ADS)

    Jarlborg, T.; Barbiellini, B.; Lane, C.; Wang, Yung Jui; Markiewicz, R. S.; Liu, Zhi; Hussain, Zahid; Bansil, A.

    2014-04-01

    The electronic structures of supercells of CeO2-δ have been calculated within the density functional theory (DFT). The equilibrium properties such as lattice constants, bulk moduli, and magnetic moments are well reproduced by the generalized gradient approximation (GGA). Electronic excitations are simulated by robust total-energy calculations for constrained states with atomic core holes or valence holes. Pristine ceria CeO2 is found to be a nonmagnetic insulator with magnetism setting in as soon as oxygens are removed from the structure. In the ground state of defective ceria, the Ce-f majority band resides near the Fermi level but appears at about 2 eV below the Fermi level in photoemission spectroscopy experiments due to final-state effects. We also tested our computational method by calculating threshold energies in Ce-M5 and O-K x-ray absorption spectroscopy and comparing theoretical predictions with the corresponding measurements. Our result that f electrons reside near the Fermi level in the ground state of oxygen-deficient ceria is crucial for understanding the catalytic properties of CeO2 and related materials.

  4. Distribution and Magnitude of Dinitrogen Fixation in the Eastern Tropical North Pacific Oxygen Deficient Zone.

    NASA Astrophysics Data System (ADS)

    Selden, C.; Mulholland, M. R.; Widner, B.; Bernhardt, P. W.; Macías Tapia, A.; Jayakumar, A.

    2016-12-01

    The Eastern Tropical North Pacific Ocean (ETNP) hosts one of the world's three major open ocean oxygen deficient zones (ODZs). Hotspots for fixed nitrogen (N) loss processes, ODZs have classically been discounted as areas of significant dinitrogen (N2) fixation, the microbe-mediated reduction of N2 to ammonium (NH4+), which has historically been ascribed primarily to euphotic, nutrient-deplete tropical waters. Challenging this paradigm, active expression of nifH (the dinitrogen reductase structural gene) has recently been documented in the ETNP, Eastern Tropical South Pacific, and Arabian Sea ODZs, implying a closer coupling of fixed nitrogen input and loss processes than previously thought. Here, we report rates of N­2 fixation measured in the ETNP ODZ along vertical gradients of oxygen, light, and dissolved N concentrations. Detailed vertical profiles of N2 fixation rates and dissolved N concentrations made within the ODZ were compared with similar profiles from oxic waters outside the ODZ. In addition, different organic carbon sources were investigated as potential rate-limiting factors for N2 fixation in sub-euphotic waters. By establishing the magnitude and distribution of N­2 fixation in the ETNP ODZ, this study contributes to current understanding of N cycling in anoxic and aphotic waters, and serves to elucidate nuances in the global N budget, enabling more accurate biogeochemical modeling. Understanding these processes in present day ODZs is crucial for predicting how ongoing anthropogenic intensification of coastal ODZs will alter biogeochemical cycles in the future.

  5. Oxygen vacancy formation characteristics in the bulk and across different surface terminations of La(1₋x)SrxFe(1₋y)CoyO(3₋δ) perovskite oxides for CO2 conversion

    DOE PAGES

    Maiti, Debtanu; Daza, Yolanda A.; Yung, Matthew M.; ...

    2016-03-07

    Density functional theory (DFT) based investigation of two parameters of prime interest -- oxygen vacancy and surface terminations along (100) and (110) planes -- has been conducted for La(1-x)SrxFe(1-y)CoyO(3-more » $$\\delta$$) perovskite oxides in view of their application towards thermochemical carbon dioxide conversion reactions. The bulk oxygen vacancy formation energies for these mixed perovskite oxides are found to increase with increasing lanthanum and iron contents in the 'A' site and 'B' site, respectively. Surface terminations along (100) and (110) crystal planes are studied to probe their stability and their capabilities to accommodate surface oxygen vacancies. Amongst the various terminations, the oxygen-rich (110) surface and strontium-rich (100) surface are the most stable, while transition metal-rich terminations along (100) revealed preference towards the production of oxygen vacancies. The carbon dioxide adsorption strength, a key descriptor for CO2 conversion reactions, is found to increase on oxygen vacant surfaces thus establishing the importance of oxygen vacancies in CO2 conversion reactions. Amongst all the surface terminations, the lanthanum-oxygen terminated surface exhibited the strongest CO2 adsorption strength. Finally, the theoretical prediction of the oxygen vacancy trends and the stability of the samples were corroborated by the temperature-programmed reduction and oxidation reactions and in situ XRD crystallography.« less

  6. Ethylene and reactive oxygen species are involved in root aerenchyma formation and adaptation of wheat seedlings to oxygen-deficient conditions

    PubMed Central

    Yamauchi, Takaki

    2014-01-01

    Exposing plants to hypoxic conditions greatly improves their anoxic stress tolerance by enhancing the activities of glycolysis and fermentation in roots. Ethylene may also be involved in these adaptive responses because its synthesis is increased in roots under hypoxic conditions. Here it is reported that pre-treatment of wheat seedlings with an ethylene precursor, 1-aminocyclopropanecarboxylic acid (ACC), enhanced accumulation of ethylene in the roots of wheat seedlings, and enhanced their tolerance of oxygen-deficient conditions through increasing the expression of genes encoding ethanol fermentation enzymes, alcohol dehydrogenase and pyruvate decarboxylase, in the roots. Lysigenous aerenchyma formation in root was induced by ACC pre-treatment and was further induced by growth under oxygen-deficient conditions. ACC pre-treatment increased the expression of three genes encoding respiratory burst oxidase homologue (a plant homologue of gp91phox in NADPH oxidase), which has a role in the generation of reactive oxygen species (ROS), in roots of seedlings. Co-treatment with ACC and an NADPH oxidase inhibitor, diphenyleneiodonium, partly suppressed the ACC-induced responses. These results suggest that ethylene and ROS are involved in adaptation of wheat seedlings to oxygen-deficient conditions through controlling lysigenous aerenchyma formation and the expression of genes encoding ethanol fermentation enzymes. PMID:24253196

  7. Pulsed laser-induced oxygen deficiency at TiO{sub 2} surface: Anomalous structure and electrical transport properties

    SciTech Connect

    Nakajima, Tomohiko; Tsuchiya, Tetsuo; Kumagai, Toshiya

    2009-09-15

    We have studied pulsed laser-induced oxygen deficiencies at rutile TiO{sub 2} surfaces. The crystal surface was successfully reduced by excimer laser irradiation, and an oxygen-deficient TiO{sub 2-{delta}} layer with 160 nm thickness was formed by means of ArF laser irradiation at 140 mJ/cm{sup 2} for 2000 pulses. The TiO{sub 2-{delta}} layer fundamentally maintained a rutile structure, though this structure was distorted by many stacking faults caused by the large oxygen deficiency. The electrical resistivity of the obtained TiO{sub 2-{delta}} layer exhibited unconventional metallic behavior with hysteresis. A metal-insulator transition occurred at 42 K, and the electrical resistivity exceeded 10{sup 4} OMEGA cm below 42 K. This metal-insulator transition could be caused by bipolaronic ordering derived from Ti-Ti pairings that formed along the stacking faults. The constant magnetization behavior observed below 42 K is consistent with the bipolaronic scenario that has been observed previously for Ti{sub 4}O{sub 7}. These peculiar electrical properties are strongly linked to the oxygen-deficient crystal structure, which contains many stacking faults formed by instantaneous heating during excimer laser irradiation. - Graphical abstract: A pulsed laser-irradiated TiO{sub 2-{delta}} substrate showed an unconventional metallic phase, with hysteresis over a wide range of temperatures and a metal-insulator transition at 42 K.

  8. Facile Aluminum Reduction Synthesis of Blue TiO2 with Oxygen Deficiency for Lithium-Ion Batteries.

    PubMed

    Zheng, Jing; Ji, Guangbin; Zhang, Peng; Cao, Xingzhong; Wang, Baoyi; Yu, Linhui; Xu, Zhichuan

    2015-12-07

    An ultrafacile aluminum reduction method is reported herein for the preparation of blue TiO2 nanoparticles (donated as Al-TiO2 , anatase phase) with abundant oxygen deficiency for lithium-ion batteries. Under aluminum reduction, the morphology of the TiO2 nanosheets changes from well-defined rectangular into uniform round or oval nanoparticles and the particle size also decreases from 60 to 31 nm, which can aggressively accelerate the lithium-ion diffusion. Electron paramagnetic resonance (EPR) and positron annihilation lifetime spectroscopy (PALS) results reveal that plentiful oxygen deficiencies relative to the Ti(3+) species were generated in blue Al-TiO2 ; this effectively enhances the electron conductivity of the TiO2 . X-ray photoelectron spectrometry (XPS) analysis indicates that a small peak is observed for the Al-O bond, which probably plays a very important role in the stabilization of the oxygen deficiencies/Ti(3+) species. As a result, the blue Al-TiO2 possesses significantly higher capacity, better rate performance, and a longer cycle life than the white pure TiO2 . Such improvements can be attributed to the decreased particle size, as well as the existence of the oxygen deficiencies/Ti(3+) species.

  9. Fluctuation-induced anisotropic magnetoconductivity in oxygen-deficient YBa 2Cu 3O 7-δthin films

    NASA Astrophysics Data System (ADS)

    Göb, W.; Lang, W.; Kula, W.; Sobolewski, Roman

    1997-04-01

    We report on measurements of both the longitudinal and transverse magnetoresistivity (MR) of oxygen-reduced YBa2Cu3O7-δ(YBCO) thin films with critical temperatures betweenTc = 55 K andTc = 89 . We find the MR solely caused by the suppression of superconducting fluctuations by a magnetic field. In fully oxygenated samples both the Aslamazov-Larkin process (AL) and another, presumably the Maki-Thompson process (MT), contribute to the MR. In oxygen-deficient samples the MT process unambiguously is absent, thus indicating an unconventional (non-s-wave) pairing symmetry in YBCO.

  10. Achieving High Efficiency and Eliminating Degradation in Solid Oxide Electrochemical Cells Using High Oxygen-Capacity Perovskite.

    PubMed

    Jun, Areum; Kim, Junyoung; Shin, Jeeyoung; Kim, Guntae

    2016-09-26

    Recently, there have been efforts to use clean and renewable energy because of finite fossil fuels and environmental problems. Owing to the site-specific and weather-dependent characteristics of the renewable energy supply, solid oxide electrolysis cells (SOECs) have received considerable attention to store energy as hydrogen. Conventional SOECs use Ni-YSZ (yttria-stabilized zirconia) and LSM (strontium-doped lanthanum manganites)-YSZ as electrodes. These electrodes, however, suffer from redox-instability and coarsening of the Ni electrode along with delamination of the LSM electrode during steam electrolysis. In this study, we successfully design and fabricate highly efficient SOECs using layered perovskites, PrBaMn2 O5+δ (PBM) and PrBa0.5 Sr0.5 Co1.5 Fe0.5 O5+δ (PBSCF50), as both electrodes for the first time. The SOEC with layered perovskites as both-side electrodes shows outstanding performance, reversible cycling, and remarkable stability over 600 hours. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. Hierarchical Mesoporous/Macroporous Perovskite La0.5Sr0.5CoO3-x Nanotubes: A Bifunctional Catalyst with Enhanced Activity and Cycle Stability for Rechargeable Lithium Oxygen Batteries.

    PubMed

    Liu, Guoxue; Chen, Hongbin; Xia, Lu; Wang, Suqing; Ding, Liang-Xin; Li, Dongdong; Xiao, Kang; Dai, Sheng; Wang, Haihui

    2015-10-14

    Perovskites show excellent specific catalytic activity toward both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) in alkaline solutions; however, small surface areas of the perovskites synthesized by traditional sol-gel methods lead to low utilization of catalytic sites, which gives rise to poor Li-O2 batteries performance and restricts their application. Herein, a hierarchical mesporous/macroporous perovskite La0.5Sr0.5CoO3-x (HPN-LSC) nanotube is developed to promote its application in Li-O2 batteries. The HPN-LSC nanotubes were synthesized via electrospinning technique followed by postannealing. The as-prepared HPN-LSC catalyst exhibits outstanding intrinsic ORR and OER catalytic activity. The HPN-LSC/KB electrode displays excellent performance toward both discharge and charge processes for Li-O2 batteries, which enhances the reversibility, the round-trip efficiency, and the capacity of resultant batteries. The synergy of high catalytic activity and hierarchical mesoporous/macroporous nanotubular structure results in the Li-O2 batteries with good rate capability and excellent cycle stability of sustaining 50 cycles at a current density of 0.1 mA cm(-2) with an upper-limit capacity of 500 mAh g(-1). The results will benefit for the future development of high-performance Li-O2 batteries using hierarchical mesoporous/macroporous nanostructured perovskite-type catalysts.

  12. Hydrogen production from a combination of the water-gas shift and redox cycle process of methane partial oxidation via lattice oxygen over LaFeO3 perovskite catalyst.

    PubMed

    Dai, Xiao Ping; Wu, Qiong; Li, Ran Jia; Yu, Chang Chun; Hao, Zheng Ping

    2006-12-28

    A redox cycle process, in which CH4 and air are periodically brought into contact with a solid oxide packed in a fixed-bed reactor, combined with the water-gas shift (WGS) reaction, is proposed for hydrogen production. The sole oxidant for partial oxidation of methane (POM) is found to be lattice oxygen instead of gaseous oxygen. A perovskite-type LaFeO3 oxide was prepared by a sol-gel method and employed as an oxygen storage material in this process. The results indicate that, under appropriate reaction conditions, methane can be oxidized to CO and H2 by the lattice oxygen of LaFeO3 perovskite oxide with a selectivity higher than 95% and the consumed lattice oxygen can be replenished in a reoxidation procedure by a redox operation. It is suggested that the POM to H2/CO by using the lattice oxygen of the oxygen storage materials instead of gaseous oxygen should be possibly applicable. The LaFeO3 perovskite oxide maintained relatively high catalytic activity and structural stability, while the carbonaceous deposits, which come from the dissociation of CH4 in the pulse reaction, occurred due to the low migration rate of lattice oxygen from the bulk toward the surface. A new dissociation-oxidation mechanism for this POM without gaseous oxygen is proposed based on the transient responses of the products checked at different surface states via both pulse reaction and switch reaction over the LaFeO3 catalyst. In the absence of gaseous-phase oxygen, the rate-determining step of methane conversion is the migration rate of lattice oxygen, but the process can be carried out in optimized cycles. The product distribution for POM over LaFeO3 catalyst in the absence of gaseous oxygen was determined by the concentration of surface oxygen, which is relevant with the migration rate of lattice oxygen from the bulk toward the surface. This process of hydrogen production via selective oxidation of methane by lattice oxygen is better in avoiding the deep oxidation (to CO2) and

  13. Oxygen-Deficient Titanium Dioxide Nanosheets as More Effective Polysulfide Reservoirs for Lithium-Sulfur Batteries.

    PubMed

    Wang, Han-Chi; Fan, Chao-Ying; Zheng, Yan-Ping; Zhang, Xiao-Hua; Li, Wen-Hao; Liu, Si-Yu; Sun, Hai-Zhu; Zhang, Jing-Ping; Sun, Ling-Na; Wu, Xing-Long

    2017-07-18

    In this work, oxygen-deficient anatase TiO2 nanosheets (A-TiO2-x NSs) are proposed as a substrate to improve the electrochemical properties of sulfur electrodes for lithium-sulfur (Li-S) batteries. The A-TiO2-x NSs are prepared by partly reducing pristine TiO2 nanosheets (A-TiO2 NSs) in NaBH4 solution. With some oxygen vacancies on the surface of the TiO2 nanosheets, A-TiO2-x NSs not only promote electronic transfer, but also act as more effective polysulfide reservoirs to minimize the dissolution of lithium polysulfides (LiPSs) than the A-TiO2 NSs control. Hence, upon utilization as modifiers for cathodes of Li-S batteries, the A-TiO2-x NSs-modified sulfur (A-TiO2-x NSs-S) cathode exhibits a higher reversible specific capacity and greater cycling performance and rate capability than the A-TiO2 NSs-modified one (A-TiO2 NSs-S). For example, A-TiO2-x NSs-S delivers an initial specific capacity of 1277.1 mAh g(-1) at 0.1 C and maintains a stable Coulombic efficiency of approximately 99.2 % after the first five cycles; these values are higher than those of 997.3 mAh g(-1) and around 96.7 %, respectively, for A-TiO2 NSs-S. The enhanced electrochemical properties of the A-TiO2-x NSs-S cathode can be ascribed mainly to the more effective adsorption of dissolvable and diffused LiPSs by the oxygen vacancies. Therefore, utilization of the structure of oxygen vacancies in Li-S batteries demonstrates great prospects for practical application. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  14. Effects of Oxygen Deficiency and Dopping of pr in Gd1-x Prx Ba2Cu3O7-y

    NASA Astrophysics Data System (ADS)

    Zolfagharkhani, G.; Daadmehr, V.; Farzaneh, M.; Sedighiani, A.; Akhavan, M.

    2000-09-01

    Single phase crystalline samples of Gd1-x Prx Ba2Cu3O7-y with 0.0 ≤ x ≤ 0.2 have been prepared by standard solid state reaction technique and characterized by SEM and XRD. The electrical measurements show two plateaus in Tc versus y curve for GdBa2Cu3O7-y (0oxygen deficiency. In deoxygenation process of Pr dopant samples, the plateaus come down to lower temperatures and the first plateau becomes smaller than undoped samples. Simultaneous doping of Pr and oxygen deficiency are superimposed on increasing of ρ before transition and suppression of Tc by decreasing of hole concentration in CuO2 planes. The experiments indicate that in GdPr-123 samples, presence of Pr causes the oxygen bond to become stronger than in undoped samples.

  15. Acetylene hydrogenation on anatase TiO2(101) supported Pd4 cluster: oxygen deficiency effect.

    PubMed

    Yang, Jie; Cao, Li-Xin; Wang, Gui-Chang

    2012-07-01

    Acetylene hydrogenation on both the perfect and oxygen defective anatase TiO(2)(101) surfaces supported Pd(4) cluster has been studied using density functional theory calculations with a Hubbard U correction (DFT + U). The adsorbed Pd(4) cluster on the perfect surface prefers to form a tetrahedral structure, while it likely moves to the oxygen defective site to form a distorted tetrahedral structure by removing a bridging oxygen atom. For the defective surface, it exhibits a stronger ability to capture Pd(4) cluster as charge transfer is significantly performed due to the oxygen deficiency. Moreover, it is found that the oxygen defective surface shows higher activity for acetylene hydrogenation, and the possible reason may lie in the weaker adsorption strength between the Pd cluster and the adsorbed molecules on the defective surface as compared to the case on the perfect surface.

  16. The role of reactive oxygen species in the hearts of dystrophin-deficient mdx mice.

    PubMed

    Williams, Iwan A; Allen, David G

    2007-09-01

    Duchenne muscular dystrophy (DMD) is caused by deficiency of the cytoskeletal protein dystrophin. Oxidative stress is thought to contribute to the skeletal muscle damage in DMD; however, little is known about the role of oxidative damage in the pathogenesis of the heart failure that occurs in DMD patients. The dystrophin-deficient (mdx) mouse is an animal model of DMD that also lacks dystrophin. The current study investigates the role of the antioxidant N-acetylcysteine (NAC) on mdx cardiomyocyte function, Ca(2+) handling, and the cardiac inflammatory response. Treated mice received 1% NAC in their drinking water for 6 wk. NAC had no effect on wild-type (WT) mice. Immunohistochemistry experiments revealed that mdx mice had increased dihydroethidine (DHE) staining, an indicator of superoxide production; NAC-treatment reduced DHE staining in mdx hearts. NAC treatment attenuated abnormalities in mdx cardiomyocyte Ca(2+) handling. Mdx cardiomyocytes had decreased fractional shortening and decreased Ca(2+) sensitivity; NAC treatment returned mdx fractional shortening to WT values but did not affect the Ca(2+) sensitivity. Immunohistochemistry experiments revealed that mdx hearts had increased levels of collagen type III and the macrophage-specific protein, CD68; NAC-treatment returned collagen type III and CD68 expression close to WT values. Finally, mdx hearts had increased NADPH oxidase activity, suggesting it could be a possible source of increased reactive oxygen species in mdx mice. This study is the first to demonstrate that oxidative damage may be involved in the pathogenesis of the heart failure that occurs in mdx mice. Therapies designed to reduce oxidative damage might be beneficial to DMD patients with heart failure.

  17. Chlorophyll Fluorescence and Photon Yield of Oxygen Evolution in Iron-Deficient Sugar Beet (Beta vulgaris L.) Leaves 12

    PubMed Central

    Morales, Fermín; Abadía, Anunciación; Abadía, Javier

    1991-01-01

    The response of sugar beet (Beta vulgaris L.) leaves to iron deficiency can be described as consisting of two phases. In the first phase, leaves may lose a large part of their chlorophyll while maintaining a roughly constant efficiency of photosystem II photochemistry; ratios of variable to maximum fluorescence decreased by only 6%, and photon yields of oxygen evolution decreased by 30% when chlorophyll decreased by 70%. In the second phase, when chlorophyll decreased below a threshold level, iron deficiency caused major decreases in the efficiency of photosystem II photochemistry and in the photon yield of oxygen evolution. These decreases in photosystem II photochemical efficiency were found both in plants dark-adapted for 30 minutes and in plants dark-adapted overnight, indicating that photochemical efficiency cannot be repaired in that time scale. Decreases in photosystem II photochemical efficiency and in the photon yield of oxygen evolution were similar when measurements were made (a) with light absorbed by carotenoids and chlorophylls and (b) with light absorbed only by chlorophylls. Leaves of iron-deficient plants exhibited a room temperature fluorescence induction curve with a characteristic intermediate peak I that increases with deficiency symptoms. PMID:16668527

  18. Oxygen deficiency and salinity affect cell-specific ion concentrations in adventitious roots of barley (Hordeum vulgare).

    PubMed

    Kotula, Lukasz; Clode, Peta L; Striker, Gustavo G; Pedersen, Ole; Läuchli, André; Shabala, Sergey; Colmer, Timothy D

    2015-12-01

    Oxygen deficiency associated with soil waterlogging adversely impacts root respiration and nutrient acquisition. We investigated the effects of O2 deficiency and salinity (100 mM NaCl) on radial O2 concentrations and cell-specific ion distributions in adventitious roots of barley (Hordeum vulgare). Microelectrode profiling measured O2 concentrations across roots in aerated, aerated saline, stagnant or stagnant saline media. X-ray microanalysis at two positions behind the apex determined the cell-specific elemental concentrations of potassium (K), sodium (Na) and chloride (Cl) across roots. Severe O2 deficiency occurred in the stele and apical regions of roots in stagnant solutions. O2 deficiency in the stele reduced the concentrations of K, Na and Cl in the pericycle and xylem parenchyma cells at the subapical region. Near the root apex, Na declined across the cortex in roots from the aerated saline solution but was relatively high in all cell types in roots from the stagnant saline solution. Oxygen deficiency has a substantial impact on cellular ion concentrations in roots. Both pericycle and xylem parenchyma cells are involved in energy-dependent K loading into the xylem and in controlling radial Na and Cl transport. At root tips, accumulation of Na in the outer cell layers likely contributed to reduction of Na in inner cells of the tips.

  19. Microbial competition for N intermediates drives oscillating N loss from marine oxygen deficient zones

    NASA Astrophysics Data System (ADS)

    Penn, J. L.; Weber, T. S.; Deutsch, C. A.

    2014-12-01

    Small oxygen deficient zones (ODZs) below the ocean surface play a major role in regulating marine biological productivity, through the removal of bioavailable nitrogen (N). Recent observations have shown diverse microbial communities affecting N metabolic pathways, but the large-scale consequences of this complexity are unknown. Here we investigate the key microbial interactions and their importance for N loss in a circulation and ecosystem model of the largest ODZ, in the North Pacific. The microbial model replicates observed chemical distributions, but exhibits fundamentally distinct behavior from traditional models based on chemistry alone. The ecosystem undergoes local oscillations that create large variability in the regional rate of N loss, even in a steady circulation. These N loss fluctuations occur at the boundary between oxic and anoxic waters, where miniscule fluctuations in scarce resources are driven by competitive dynamics and dramatically shift the balance between aerobic and anaerobic bacteria. The coexistence of these populations and their competing geochemical effects reduces overall rates of N loss while expanding the scale of anoxic waters. Intrinsic ecosystem oscillations also cause dramatic swings in the ratio of heterotrophic to autotrophic N loss pathways, possibly underlying the wide variations observed in nature.

  20. Dynamics of photodoping and photoconductivity relaxation in oxygen-deficient YBa 2Cu 3O x

    NASA Astrophysics Data System (ADS)

    Markowitsch, W.; Stockinger, C.; Göb, W.; Lang, W.; Kula, W.; Sobolewski, Roman

    1996-02-01

    Studies of the time evolution of the photodoping process and of the relaxation of persistent photoconductivity (PPC) in oxygen-deficient YBa 2Cu 3O x are presented. We show that the resistance decrease during white light illumination of the samples does not saturate up to photon doses of 10 23-10 24 cm -2. The efficiency of the photodoping process is weakly temperature dependent, decreasing at low temperatures for extended illumination. The relaxation of PPC follows a Kohlrausch law with the time constant of several hours near room temperature and more than 1200 h at 254 K. Similarly to semiconducting samples, the temperature dependence of the relaxation rate follows the thermal activation process across an energy barrier of ≈0.9 eV. However, the dispersion parameter exhibits in our case the opposite temperature dependence - it increases with the temperature decrease. There is no indication of a threshold temperature around 270 K. The observed behavior suggests that two different mechanisms contribute to the photodoping process.

  1. Metallic-like to nonmetallic transitions in a variety of heavily oxygen deficient ferroelectrics

    SciTech Connect

    Bock, Jonathan A.; Trolier-McKinstry, Susan; Randall, Clive A.; Lee, Soonil

    2015-08-31

    The coupling between ferroelectric distortions and electron transport is an important factor in understanding ferroelectric/noncentrosymmetric materials with metallic conductivities and ferroelectric-based thermoelectrics. Here, multiple d{sup 0} ferroelectrics with a variety of crystal structures are doped via oxygen deficiency, resulting in metallic-like conduction in the paraelectric state. It is found that most of the studied systems show a metallic-like to nonmetallic transition near the paraelectric-ferroelectric transition. The metallic-like to nonmetallic transition temperature can be shifted using mechanisms that shift the paraelectric-ferroelectric transition temperature. It was found that the metallic-like to nonmetallic transition temperature could be shifted from 373 K to 273 K by varying (Ba{sub 1−x}Sr{sub x})TiO{sub 3−δ} from x = 0 to x = 0.3 and x = 1. The most probable mechanism for ferroelectric-electron transport coupling was determined to be Anderson localization associated with polarization with short-range order.

  2. Oxygen-deficient defects and hydrogen in irradiated Si/SiO2 systems

    NASA Astrophysics Data System (ADS)

    van Ginhoven, Renee; Hjalmarson, Harold

    2006-03-01

    Performance of Si/SiO2 devices is degraded by ionizing radiation through the production of interface traps and buildup of trapped charge in the oxide. This process is connected to the presence of hydrogen in the oxide. Exposure to ionizing radiation stimulates release of mobile hydrogen, which can migrate through the oxide to the Si/SiO2 interface and depassivate H-terminated Si-dangling bonds. The resulting interface trap states act as charge recombination centers. Our calculations focus on the interaction of hydrogen with oxygen deficient centers in the oxide. In the bulk oxide, these defects can release hydrogen from Si-H groups, or crack H2 molecules. These active sites may also act as border trap recombination centers when near the interface. Our presentation will describe molecular scale mechanisms for radiation-induced generation of free hydrogen using density functional theory applied to fully periodic models. The oxide is represented by both crystalline and amorphous configurations. Sandia is a multiprogram laboratory operated by the Sandia Corporation, a Lockheed Martin Company, for the United States Department of Energy under contract DE-AC04-94AL85000.

  3. Spin texture induced by oxygen vacancies in strontium perovskite (001) surfaces: A theoretical comparison between SrTiO3 and SrHfO3

    NASA Astrophysics Data System (ADS)

    Garcia-Castro, A. C.; Vergniory, M. G.; Bousquet, E.; Romero, A. H.

    2016-01-01

    The electronic structure of SrTiO3 and SrHfO3 (001) surfaces with oxygen vacancies is studied by means of first-principles calculations. We reveal how oxygen vacancies within the first atomic layer of the SrTiO3 surface (i) induce a large antiferrodistortive motion of the oxygen octahedra at the surface, (ii) drive localized magnetic moments on the Ti 3 d orbitals close to the vacancies, and (iii) form a two-dimensional electron gas localized within the first layers. The analysis of the spin texture of this system exhibits a splitting of the energy bands according to the Zeeman interaction, lowering of the Ti 3 dx y level in comparison with dx z and dy z, and also an in-plane precession of the spins. No Rashba-like splitting for the ground state or for the ab initio molecular dynamics trajectory at 400 K is recognized as suggested recently by A. F. Santander-Syro et al. [Nat. Mater. 13, 1085 (2014), 10.1038/nmat4107]. Instead, a sizable Rashba-like splitting is observed when the Ti atom is replaced by a heavier Hf atom with a much larger spin-orbit interaction. However, we observe the disappearance of the magnetism and the surface two-dimensional electron gas when full structural optimization of the SrHfO3 surface is performed. Our results uncover the sensitive interplay of spin-orbit coupling, atomic relaxations, and magnetism when tuning these Sr-based perovskites.

  4. Adventitious roots of wheat seedlings that emerge in oxygen-deficient conditions have increased root diameters with highly developed lysigenous aerenchyma.

    PubMed

    Yamauchi, Takaki; Abe, Fumitaka; Kawaguchi, Kentaro; Oyanagi, Atsushi; Nakazono, Mikio

    2014-01-01

    Exposing roots of plants to hypoxic conditions is known to greatly improve their anoxic stress tolerance. We previously showed that pre-treatment of wheat seedlings with an ethylene precursor, 1-aminocyclopropanecarboxylic acid (ACC), enhanced their tolerance of oxygen-deficient conditions. Although ACC-pretreated seminal roots of wheat seedlings grown under oxygen-deficient conditions avoided root tip death, they elongated very little. In the present study, we assessed the effects of ethylene on the responses of adventitious roots of wheat seedlings to oxygen-deficient conditions. Lysigenous aerenchyma formation in the adventitious roots of wheat seedlings pretreated with ACC appeared to reduce tip death under oxygen-deficient conditions, but the adventitious roots, like the seminal roots, hardly elongated. We also found that adventitious roots that emerge in oxygen-deficient conditions continued to elongate even under such conditions. The adventitious roots emerged in oxygen-deficient conditions were found to have thicker root diameters than those emerged in aerated conditions. These results suggest that the adventitious roots with thicker root diameters can better cope with oxygen-deficient conditions. Measurements of the area of the lysigenous aerenchyma confirmed that the increased root diameters have a greater amount of air space generated by lysigenous aerenchyma formation.

  5. Adventitious roots of wheat seedlings that emerge in oxygen-deficient conditions have increased root diameters with highly developed lysigenous aerenchyma

    PubMed Central

    Yamauchi, Takaki; Abe, Fumitaka; Kawaguchi, Kentaro; Oyanagi, Atsushi; Nakazono, Mikio

    2014-01-01

    Exposing roots of plants to hypoxic conditions is known to greatly improve their anoxic stress tolerance. We previously showed that pre-treatment of wheat seedlings with an ethylene precursor, 1-aminocyclopropanecarboxylic acid (ACC), enhanced their tolerance of oxygen-deficient conditions. Although ACC-pretreated seminal roots of wheat seedlings grown under oxygen-deficient conditions avoided root tip death, they elongated very little. In the present study, we assessed the effects of ethylene on the responses of adventitious roots of wheat seedlings to oxygen-deficient conditions. Lysigenous aerenchyma formation in the adventitious roots of wheat seedlings pretreated with ACC appeared to reduce tip death under oxygen-deficient conditions, but the adventitious roots, like the seminal roots, hardly elongated. We also found that adventitious roots that emerge in oxygen-deficient conditions continued to elongate even under such conditions. The adventitious roots emerged in oxygen-deficient conditions were found to have thicker root diameters than those emerged in aerated conditions. These results suggest that the adventitious roots with thicker root diameters can better cope with oxygen-deficient conditions. Measurements of the area of the lysigenous aerenchyma confirmed that the increased root diameters have a greater amount of air space generated by lysigenous aerenchyma formation. PMID:24690588

  6. Diversity, distribution, and expression of diazotroph nifH genes in oxygen-deficient waters of the Arabian Sea.

    PubMed

    Jayakumar, Amal; Al-Rshaidat, Mamoon M D; Ward, Bess B; Mulholland, Margaret R

    2012-12-01

    The Arabian Sea oxygen minimum zone (OMZ), the largest suboxic region in the world's oceans, is responsible for up to half of the global mesopelagic fixed nitrogen (N) loss from the ocean via denitrification and anammox. Dinitrogen (N(2)) fixation is usually attributed to cyanobacteria in the surface ocean. Model prediction and physiological inhibition of N(2) fixation by oxygen, however, suggest that N(2) fixation should be enhanced near the oxygen-deficient zone (ODZ) of the Arabian Sea. N(2) fixation and cyanobacterial nifH genes (the gene encoding dinitrogenase reductase) have been reported in surface waters overlying the Arabian Sea ODZ. Here, water samples from depths above and within the Arabian Sea ODZ were examined to explore the distribution, diversity, and expression of nifH genes. In surface waters, nifH DNA and cDNA sequences related to Trichodesmium, a diazotroph known to occur and fix N(2) in the Arabian Sea, were detected. Proteobacterial nifH phylotypes (DNA but not cDNA) were also detected in surface waters. Proteobacterial nifH DNA and cDNA sequences, as well as nifH DNA and cDNA sequences related to strictly anaerobic N -fixers, were obtained from oxygen-deficient depths. This first report of nifH gene expression in subsurface low-oxygen waters suggests that there is potential for active N(2) fixation by several phylogenetically and potentially metabolically diverse microorganisms in pelagic OMZs.

  7. An oxygen deficient fluorite with a tunnel structure: Bi sub 8 La sub 10 O sub 27

    SciTech Connect

    Michel, C.; Caignaert, V.; Raveau, B. )

    1991-02-01

    A new lanthanum bismuth oxide, Bi{sub 8}La{sub 10}O{sub 27}, has been synthesized. It crystallizes in the Immm space group with the following parameters: a = 12.079 (2) {angstrom}, b = 16.348 (4) {angstrom}, c = 4.0988 (5) {angstrom}. Its structure was determined from powder X-ray and neutron diffraction data. It can be described as an oxygen deficient fluorite superstructure (a {approx} 3a{sub F}/{radical}2, b {approx} 3a{sub F}, c {approx} a{sub F}/{radical}2) in which bismuth and lanthanum, as well as oxygen vacancies, are ordered. The structure consists of fully occupied (110) or ({bar 1}10) lanthanum planes (La) which alternate with mixed {l brace}{sub La}{sup Ba}{r brace} planes and fully occupied oxygen planes (A) which alternate with two sorts of oxygen deficient (110) or ({bar 1}10) planes (B and C) according to the sequence -{l brace} La A B {l brace}{sub La}{sup Bi}{r brace} C C {l brace}{sub La}{sup Bi}{r brace} B A {l brace}-. The anionic distribution determines tunnels where the bismuth ions are located, forming diamond-shaped based tunnels. The coordination of bismuth and lanthanum is discussed. The high thermal factor of some oxygen atoms suggests that this oxide exhibits ionic conductivity.

  8. Oxygen-vacancy concentration in A{sub 2}MgMoO{sub 6-{delta}} double-perovskite oxides

    SciTech Connect

    Matsuda, Y.; Karppinen, M.; Yamazaki, Y.; Yamauchi, H.

    2009-07-15

    Accurate oxygen-content analysis by means of a coulometric redox titration method specially devised for the purpose shows that as-synthesized (in 5% H{sub 2}/Ar) samples of the recently reported novel solid oxide fuel cells anode material Sr{sub 2}MgMoO{sub 6-{delta}} contain oxygen vacancies with a concentration of {delta}{approx}0.05. Oxygen contents and the resultant Mo-valence values are also analyzed for various A{sub 2}MgMoO{sub 6-{delta}} samples in order to reveal both the isovalent and aliovalent A-site cation substitution effects. - Graphical Abstract: A highly reproducible coulometric redox titration method has been developed to accurately analyze the mixed V/VI valence state of molybdenum and thereby the oxygen content in the recently reported SOFC-anode materials of A{sub 2}MgMoO{sub 6-{delta}}.

  9. Catalytic Activity Enhancement for Oxygen Reduction on Epitaxial Perovskite Thin Films for Solid-Oxide Fuel Cells

    SciTech Connect

    La O', Gerardo Jose; Ahn, Sung Jin; Crumlin, Ethan; Orikasa, Yuki; Biegalski, Michael D; Christen, Hans M; Shao-Horn, Yang

    2010-01-01

    The active ingredient: La{sub 0.8}Sr{sub 0.2}CoO{sub 3-{delta}} (LSC) epitaxial thin films are prepared on (001)-oriented yttria-stabilized zirconia (YSZ) single crystals with a gadolinium-doped ceria (GDC) buffer layer. The LSC epitaxial films exhibit better oxygen reduction kinetics than bulk LSC. The enhanced activity is attributed in part to higher oxygen nonstoichiometry.

  10. Numerical evaluation of the use of granulated coal ash to reduce an oxygen-deficient water mass.

    PubMed

    Yamamoto, Hironori; Yamamoto, Tamiji; Mito, Yugo; Asaoka, Satoshi

    2016-06-15

    Granulated coal ash (GCA), which is a by-product of coal thermal electric power stations, effectively decreases phosphate and hydrogen sulfide (H2S) concentrations in the pore water of coastal marine sediments. In this study, we developed a pelagic-benthic coupled ecosystem model to evaluate the effectiveness of GCA for diminishing the oxygen-deficient water mass formed in coastal bottom water of Hiroshima Bay in Japan. Numerical experiments revealed the application of GCA was effective for reducing the oxygen-deficient water masses, showing alleviation of the DO depletion in summer increased by 0.4-3mgl(-1). The effect of H2S adsorption onto the GCA lasted for 5.25years in the case in which GCA was mixed with the sediment in a volume ratio of 1:1. The application of this new GCA-based environmental restoration technique could also make a substantial contribution to form a recycling-oriented society.

  11. Thermal Assisted Oxygen Annealing for High Efficiency Planar CH3NH3PbI3 Perovskite Solar Cells

    PubMed Central

    Ren, Zhiwei; Ng, Annie; Shen, Qian; Gokkaya, Huseyin Cem; Wang, Jingchuan; Yang, Lijun; Yiu, Wai-Kin; Bai, Gongxun; Djurišić, Aleksandra B.; Leung, Wallace Woon-fong; Hao, Jianhua; Chan, Wai Kin; Surya, Charles

    2014-01-01

    We report investigations on the influences of post-deposition treatments on the performance of solution-processed methylammonium lead triiodide (CH3NH3PbI3)-based planar solar cells. The prepared films were stored in pure N2 at room temperature or annealed in pure O2 at room temperature, 45°C, 65°C and 85°C for 12 hours prior to the deposition of the metal electrodes. It is found that annealing in O2 leads to substantial increase in the power conversion efficiencies (PCEs) of the devices. Furthermore, strong dependence on the annealing temperature for the PCEs of the devices suggests that a thermally activated process may underlie the observed phenomenon. It is believed that the annealing process may facilitate the diffusion of O2 into the spiro-MeOTAD for inducing p-doping of the hole transport material. Furthermore, the process can result in lowering the localized state density at the grain boundaries as well as the bulk of perovskite. Utilizing thermal assisted O2 annealing, high efficiency devices with good reproducibility were attained. A PCE of 15.4% with an open circuit voltage (VOC) 1.04 V, short circuit current density (JSC) 23 mA/cm2, and fill factor 0.64 had been achieved for our champion device. PMID:25341527

  12. Nitrous oxide cycling in the Eastern Tropical South Pacific Oxygen Deficient Zone

    NASA Astrophysics Data System (ADS)

    Casciotti, K. L.; Forbes, M. S.; Vedamati, J.; Peters, B. D.

    2016-12-01

    Marine sources of nitrous oxide (N2O), a potent greenhouse gas that also contributes to stratospheric ozone depletion, account for up to 25% of global emissions. Much of this N2O is produced in upwelling regions near the ocean's oxygen deficient zones (ODZs), areas known for intense N2O cycling. The Eastern Tropical South Pacific (ETSP) ODZ is one such area, and the balance of the processes regulating the production and emission of N2O in the ETSP is uncertain. Here we examined the concentration, isotopic and isotopomeric measurements of dissolved N2O, in concert with nitrate (NO3-) and nitrite (NO2-) isotopic ratios from seven stations on the NBP1305 cruise to the ETSP to understand the mechanisms that drive N2O production and consumption throughout the water column. Keeling plot analysis identified N2O produced with a low site preference (5-9‰) and moderate d15Nbulk (6-8‰) in the surface and oxycline layers. In the deep layer, N2O was produced with a higher site preference (18-20‰) but similar d15Nbulk (6-7‰). In the ODZ significant enrichment was apparent in δ15Nbulk (14-22‰), δ18O (68-100‰) and site preference (SP = 39-60‰), implying active N2O consumption in this layer. Further scrutiny of the ODZ N2O isotope data identifies a deviation from the relative increases in d18O and SP expected for bacterial denitrification. At high levels of N2O consumption, SP increases more than expected for the increase in d18O. Examination of these signals in conjunction with parallel analysis of nitrate and nitrite d15N and d18O measurements are used to evaluate potential N2O sources in this region.

  13. Generalizable, Electroless, Template-Assisted Synthesis and Electrocatalytic Mechanistic Understanding of Perovskite LaNiO3 Nanorods as Viable, Supportless Oxygen Evolution Reaction Catalysts in Alkaline Media

    DOE PAGES

    McBean, Coray L.; Liu, Haiqing; Scofield, Megan E.; ...

    2017-07-17

    We present that the oxygen evolution reaction (OER) is a key reaction for water electrolysis cells and air-powered battery applications. However, conventional metal oxide catalysts, used for high-performing OER, tend to incorporate comparatively expensive and less abundant precious metals such as Ru and Ir, and, moreover, suffer from poor stability. To attempt to mitigate for all of these issues, we have prepared one-dimensional (1D) OER-active perovskite nanorods using a unique, simple, generalizable, and robust method. Significantly, our work demonstrates the feasibility of a novel electroless, seedless, surfactant-free, wet solution-based protocol for fabricating “high aspect ratio” LaNiO3 and LaMnO3 nanostructures. Asmore » the main focus of our demonstration of principle, we prepared as-synthesized LaNiO3 rods and correlated the various temperatures at which these materials were annealed with their resulting OER performance. In addition, we observed generally better OER performance for samples prepared with lower annealing temperatures. Specifically, when annealed at 600 °C, in the absence of a conventional conductive carbon support, our as-synthesized LaNiO3 rods not only evinced (i) a reasonable level of activity toward OER but also displayed (ii) an improved stability, as demonstrated by chronoamperometric measurements, especially when compared with a control sample of commercially available (and more expensive) RuO2.« less

  14. TrxR2 deficiencies promote chondrogenic differentiation and induce apoptosis of chondrocytes through mitochondrial reactive oxygen species.

    PubMed

    Yan, Jidong; Xu, Jing; Fei, Yao; Jiang, Congshan; Zhu, Wenhua; Han, Yan; Lu, Shemin

    2016-05-15

    Thioredoxin reductase 2 (TrxR2) is a selenium (Se) containing protein. Se deficiency is associated with an endemic osteoarthropathy characterized by impaired cartilage formation. It is unclear whether TrxR2 have roles in cartilage function. We examined the effects of TrxR2 on chondrogenic ATDC5 cells through shRNA-mediated gene silencing of TrxR2. We demonstrated TrxR2 deficiencies could enhance chondrogenic differentiation and apoptosis of ATDC5 cells. TrxR2 deficiencies increased accumulation of cartilage glycosaminoglycans (GAGs) and mineralization. TrxR2 deficiencies also stimulated expression of extracellular (ECM) gene including Collagen II and Aggrecan. The enhanced chondrogenic properties were further confirmed by activation of Akt signaling which are required for chondrogenesis. In addition, TrxR2 deficiencies promoted chondrocyte proliferation through acceleration of cell cycle progression by increase in both S and G2/M phase cell distribution accompanied with induction of parathyroid hormone-related protein (PTHrP). Moreover, TrxR2 deficiencies induced chondrocyte death via apoptosis and increased cell sensitivity to exogenous oxidative stress. Furthermore, TrxR2 deficiencies induced emission of mitochondrial reactive oxygen species (ROS) without alteration of mitochondrial membrane potential and intracellular ATP content. Finally, treatment of TrxR2 deficiency cells with N-acetylcysteine (NAC) inhibited mitochondrial ROS production and chondrocyte apoptosis. NAC also prevented chondrogenic differentiation of TrxR2 deficiency cells by suppression of ECM gene expression, GAGs accumulation and mineralization, as well as attenuation of Akt signaling. Thus, TrxR2-mediated mitochondrial integrity is indispensable for chondrogenic differentiation of ATDC5 cells. TrxR2 deficiency-induced impaired proliferation and death of chondrocytes may be the pathological mechanism of the osteoarthropathy due to Se deficiency. Notably, this study also uncover the roles of

  15. Design principles for oxygen-reduction activity on perovskite oxide catalysts for fuel cells and metal-air batteries

    NASA Astrophysics Data System (ADS)

    Suntivich, Jin; Gasteiger, Hubert A.; Yabuuchi, Naoaki; Nakanishi, Haruyuki; Goodenough, John B.; Shao-Horn, Yang

    2011-07-01

    The prohibitive cost and scarcity of the noble-metal catalysts needed for catalysing the oxygen reduction reaction (ORR) in fuel cells and metal-air batteries limit the commercialization of these clean-energy technologies. Identifying a catalyst design principle that links material properties to the catalytic activity can accelerate the search for highly active and abundant transition-metal-oxide catalysts to replace platinum. Here, we demonstrate that the ORR activity for oxide catalysts primarily correlates to σ*-orbital (eg) occupation and the extent of B-site transition-metal-oxygen covalency, which serves as a secondary activity descriptor. Our findings reflect the critical influences of the σ* orbital and metal-oxygen covalency on the competition between O22-/OH- displacement and OH- regeneration on surface transition-metal ions as the rate-limiting steps of the ORR, and thus highlight the importance of electronic structure in controlling oxide catalytic activity.

  16. Design principles for oxygen-reduction activity on perovskite oxide catalysts for fuel cells and metal-air batteries.

    PubMed

    Suntivich, Jin; Gasteiger, Hubert A; Yabuuchi, Naoaki; Nakanishi, Haruyuki; Goodenough, John B; Shao-Horn, Yang

    2011-06-12

    The prohibitive cost and scarcity of the noble-metal catalysts needed for catalysing the oxygen reduction reaction (ORR) in fuel cells and metal-air batteries limit the commercialization of these clean-energy technologies. Identifying a catalyst design principle that links material properties to the catalytic activity can accelerate the search for highly active and abundant transition-metal-oxide catalysts to replace platinum. Here, we demonstrate that the ORR activity for oxide catalysts primarily correlates to σ-orbital (e(g)) occupation and the extent of B-site transition-metal-oxygen covalency, which serves as a secondary activity descriptor. Our findings reflect the critical influences of the σ orbital and metal-oxygen covalency on the competition between O(2)(2-)/OH(-) displacement and OH(-) regeneration on surface transition-metal ions as the rate-limiting steps of the ORR, and thus highlight the importance of electronic structure in controlling oxide catalytic activity.

  17. An insight into the effects of B-site transition metals on the activity, activation effect and stability of perovskite oxygen electrodes for solid oxide electrolysis cells

    NASA Astrophysics Data System (ADS)

    Bi, Jiaxin; Yang, Shengbing; Zhong, Shaohua; Wang, Jian-Qiang; Fan, Chou; Chen, Xinbing; Liu, Yihui

    2017-09-01

    Here, effects of B-site transition metals (TMs) in the (La0.6Sr0.4)XO3-δ (X = Mn, Fe, Co) perovskite structure on the activity and stability of the oxygen electrodes during high temperature electrolysis are discussed to provide a deep understanding of the phenomena observed for different oxygen electrodes under anodic polarizations. Performance and stability of the electrodes vary significantly at 800 °C as the TMs changed from Mn to Fe and Co, which is attributed to the different ionic conductivities and surface chemistry of the materials that have a strong dependence on the valence state and electronic structure of TMs. Under an anodic current passage of 200 mA cm-2 at 800 °C, electrode polarization resistance (RE) and overpotential (η) of the (La0.6Sr0.4)MnO3-δ (LSM) electrode decrease significantly by 1.75 Ω cm2 and 101 mV during the 1200 min test, compared with the constant values of RE and η for the (La0.6Sr0.4)FeO3-δ (LSF) and (La0.6Sr0.4)CoO3-δ (LSC) electrodes, an indication of the influence of B-site TMs on the electrode performance and stability. Most serious degradation is observed at the (La0.6Sr0.4)MnO3-δ electrode due to the electrode detachment arising from the accelerated SrO surface segregation and related disintegration of LSM particles near the electrode/electrolyte interface.

  18. Accumulation of organic matter in Cretaceous oxygen-deficient depositional environments in the central Pacific Ocean

    USGS Publications Warehouse

    Dean, W.E.; Claypool, G.E.; Thide, J.

    1984-01-01

    and intercepts of C-S regression lines however, are different for each site and all are different from regression lines for samples from modern anoxic marine sediments and from Black Sea cores. The organic-carbon-rich limestones on Hess Rise, the Mid-Pacific Mountains, and other plateaus and seamounts in the Pacific Ocean are not synchronous but do occur within the same general middle Cretaceous time period as organic-carbon-rich lithofacies elsewhere in the world ocean, particularly in the Atlantic Ocean. Strata of equivalent age in the deep basins of the Pacific Ocean are not rich in organic carbon, and were deposited in oxygenated environments. This observation, together with the evidence that the plateau sites were considerably shallower and closse to the equator during the middle Creataceous suggests that local tectonic and hydrographic conditions may have resulted in high surface-water productivity and the preservation of organic matter in an oxygen-deficient environment where an expanded mid-water oxygen minimum developed and impinged on elevated platforms and seamounts. ?? 1984.

  19. Do dislocations act as atomic autobahns for oxygen in the perovskite oxide SrTiO3?

    PubMed

    Metlenko, Veronika; Ramadan, Amr H H; Gunkel, Felix; Du, Hongchu; Schraknepper, Henning; Hoffmann-Eifert, Susanne; Dittmann, Regina; Waser, Rainer; De Souza, Roger A

    2014-11-07

    The transport properties of edge dislocations comprising a symmetrical 6° [001] tilt grain boundary in weakly acceptor-doped SrTiO3 were investigated by means of various experimental and computational techniques. Oxygen transport along the dislocation array was probed by means of (18)O/(16)O exchange experiments under (standard) oxidising conditions (pO2 = 5 × 10(-1) bar) and also under reducing conditions (pO2 = 7 × 10(-22) bar) at T = 973 K. In both cases, isotope profiles obtained by Secondary Ion Mass Spectrometry (SIMS) indicated no evidence of fast diffusion along the dislocation array. Charge transport across the dislocation array was probed in equilibrium electrical conductivity measurements as a function of oxygen partial pressure, 10(-23) ≤ pO2/bar ≤ 1 at temperatures of T/K = 950, 1050, 1100. A significant decrease in the conductivity of the bicrystal (relative to that of a single crystal) was observed under oxidising conditions, but not under reducing conditions. These studies were complemented by static lattice simulations employing empirical pair-potentials. The simulations predict, that the tilt boundary comprises two types of dislocation cores, that the formation of oxygen vacancies is energetically preferred at both cores relative to the bulk, and that the migration of oxygen ions along both cores is hindered relative to the bulk. Combining all results and literature reports, we present a comprehensive and consistent picture of the transport properties of dislocations in SrTiO3.

  20. Cerebral perfusion and oxygenation are impaired by folate deficiency in rat: absolute measurements with noninvasive near-infrared spectroscopy

    PubMed Central

    Hallacoglu, Bertan; Sassaroli, Angelo; Fantini, Sergio; Troen, Aron M

    2011-01-01

    Brain microvascular pathology is a common finding in Alzheimer's disease and other dementias. However, the extent to which microvascular abnormalities cause or contribute to cognitive impairment is unclear. Noninvasive near-infrared spectroscopy (NIRS) can address this question, but its use for clarifying the role of microvascular dysfunction in dementia has been limited due to theoretical and practical considerations. We developed a new noninvasive NIRS method to obtain quantitative, dynamic measurements of absolute brain hemoglobin concentration and oxygen saturation and used it to show significant cerebrovascular impairments in a rat model of diet-induced vascular cognitive impairment. We fed young rats folate-deficient (FD) and control diets and measured absolute brain hemoglobin and hemodynamic parameters at rest and during transient mild hypoxia and hypercapnia. With respect to control animals, FD rats featured significantly lower brain hemoglobin concentration (72±4 μmol/L versus 95±6 μmol/L) and oxygen saturation (54%±3% versus 65%±2%). By contrast, resting arterial oxygen saturation was the same for both groups (96%±4%), indicating that decrements in brain hemoglobin oxygenation were independent of blood oxygen carrying capacity. Vasomotor reactivity in response to hypercapnia was also impaired in FD rats. Our results implicate microvascular abnormality and diminished oxygen delivery as a mechanism of cognitive impairment. PMID:21386853

  1. Investigation of trimethylacetic acid adsorption on stoichiometric and oxygen-deficient CeO2 (111) surfaces

    SciTech Connect

    Sanghavi, Shail; Wang, Weina; Nandasiri, Manjula I.; Karakoti, Ajay S.; Wang, Wenliang; Yang, Ping; Thevuthasan, S.

    2016-05-12

    We studied the interactions between the carboxylate anchoring group from trimethylacetic acid (TMAA) and CeO2(111) surfaces as a function of oxygen stoichiometry using in situ X-ray photoelectron spectroscopy (XPS). The stoichiometric CeO2(111) surface was obtained by annealing the thin film under 2.0 × 10–5 Torr of oxygen at ~550 °C for 30 min. In order to reduce the CeO2(111) surface, the thin film was annealed under ~5.0 × 10–10 Torr vacuum conditions at 550 °C, 650 °C, 750 °C and 850 °C for 30 min to progressively increase the oxygen defect concentration on the surface. The saturated TMAA coverage on the CeO2(111) surface determined from XPS elemental composition is found to increase with increasing oxygen defect concentration. This is attributed to the increase of under-coordinated cerium sites on the surface with the increase in the oxygen defect concentrations. Furthermore, XPS results were in agreement with periodic density functional theory (DFT) calculations and indicate a stronger binding between the carboxylate group from TMAA and the oxygen deficient CeO2–δ(111) surface through dissociative adsorption.

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

    SciTech Connect

    Sanghavi, Shail; Wang, Weina; Nandasiri, Manjula I.; Karakoti, Ajay S.; Wang, Wenliang; Yang, Ping; Thevuthasan, S.

    2016-01-01

    We studied the interactions between the carboxylate anchoring group from trimethylacetic acid (TMAA) and CeO2(111) surfaces as a function of oxygen stoichiometry using in-situ x-ray photoelectron spectroscopy (XPS). Stoichiometric CeO2(111) surface was obtained by annealing the thin film under 2.0x10-5 Torr of oxygen at ~550°C for 30 min. In order to reduce the CeO2(111) surface, the thin film was annealed in ~5.0x10-10 Torr vacuum at 550°C, 650°C, 750°C and 850°C for 30 min to progressively increase the oxygen defect concentration on the surface. The saturated TMAA coverage on CeO2(111) surface determined from XPS elemental composition is found to increase with increasing oxygen defect concentration. This is attributed to the increase of under-coordinated cerium sites on the surface with increase in the oxygen defect concentrations. Periodic density functional theory (DFT) calculations are in agreement with XPS results and indicate a stronger binding between carboxylate group from TMAA with oxygen deficient CeO2-δ(111) surface. In addition DFT calculations reveal that dissociative mode of carboxylate adsorption is more favored than the molecular state and that carboxylate moiety bind to CeO2(111) surface in a bidentate configuration.

  3. Investigation of trimethylacetic acid adsorption on stoichiometric and oxygen-deficient CeO2 (111) surfaces

    SciTech Connect

    Sanghavi, Shail; Wang, Weina; Nandasiri, Manjula I.; Karakoti, Ajay S.; Wang, Wenliang; Yang, Ping; Thevuthasan, S.

    2016-05-12

    We studied the interactions between the carboxylate anchoring group from trimethylacetic acid (TMAA) and CeO2(111) surfaces as a function of oxygen stoichiometry using in situ X-ray photoelectron spectroscopy (XPS). The stoichiometric CeO2(111) surface was obtained by annealing the thin film under 2.0 × 10–5 Torr of oxygen at ~550 °C for 30 min. In order to reduce the CeO2(111) surface, the thin film was annealed under ~5.0 × 10–10 Torr vacuum conditions at 550 °C, 650 °C, 750 °C and 850 °C for 30 min to progressively increase the oxygen defect concentration on the surface. The saturated TMAA coverage on the CeO2(111) surface determined from XPS elemental composition is found to increase with increasing oxygen defect concentration. This is attributed to the increase of under-coordinated cerium sites on the surface with the increase in the oxygen defect concentrations. Furthermore, XPS results were in agreement with periodic density functional theory (DFT) calculations and indicate a stronger binding between the carboxylate group from TMAA and the oxygen deficient CeO2–δ(111) surface through dissociative adsorption.

  4. Investigation of trimethylacetic acid adsorption on stoichiometric and oxygen-deficient CeO2 (111) surfaces

    DOE PAGES

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

    2016-05-12

    We studied the interactions between the carboxylate anchoring group from trimethylacetic acid (TMAA) and CeO2(111) surfaces as a function of oxygen stoichiometry using in situ X-ray photoelectron spectroscopy (XPS). The stoichiometric CeO2(111) surface was obtained by annealing the thin film under 2.0 × 10–5 Torr of oxygen at ~550 °C for 30 min. In order to reduce the CeO2(111) surface, the thin film was annealed under ~5.0 × 10–10 Torr vacuum conditions at 550 °C, 650 °C, 750 °C and 850 °C for 30 min to progressively increase the oxygen defect concentration on the surface. The saturated TMAA coverage onmore » the CeO2(111) surface determined from XPS elemental composition is found to increase with increasing oxygen defect concentration. This is attributed to the increase of under-coordinated cerium sites on the surface with the increase in the oxygen defect concentrations. Furthermore, XPS results were in agreement with periodic density functional theory (DFT) calculations and indicate a stronger binding between the carboxylate group from TMAA and the oxygen deficient CeO2–δ(111) surface through dissociative adsorption.« less

  5. Structural Properties of MgSiO3 Perovskite, Twin Walls and Their Binding to Oxygen Vacancies at High Pressures from Force Field Simulations

    NASA Astrophysics Data System (ADS)

    Goncalves-Ferreira, L.; Redfern, S. A.; Artacho, E.

    2007-12-01

    Aiming to understand possible origins of seismic wave attenuation and variations in the quality factor (Q) of minerals at the Earth's interior, it has been accepted that the friction in the motion of twin domain walls under applied stress leads to a reduction in Q [1]. To interpret this behaviour one must first appreciate the influence of pressure on wall motion and dynamics. Experimental observations of twin wall motion at high pressure are difficult at present. For this reason, we have undertaken a computational study of wall structure and dynamics in MgSiO3 perovskite, in the absence or presence of defects, as a function of pressure between 0 and 140 GPa. This work is based on previous studies on CaTiO3 perovskite [2,3] (symmetry Pbnm) with 7800 atoms and orthorhombic periodic boundary conditions. It has been geometrically adapted to lower mantle's MgSiO3 perovskite. The system comprises two (100) ferroelastic twin walls separated by 34.2 Å, relaxed within a variable supercell of 26x10x6 unit cells, with the rigid ion set of interatomic potentials with partial ionic charges employed by Alfredsson et al., 2005 [4]. The degree of distortion in the system is manifest in the octahedral tilting angles along each of the crystallographic directions. The octahedral tilting orientations close to the walls are well described by the behaviour of two order parameters: the main one, defining the wall, goes as α tanh(2(x - x')/w) , where α = 11.14° is the bulk value for the tilt, and w = 11.11 Å is the wall width. The secondary order parameters describe a slight breather at the wall. As wall dynamics are influenced by the presence of oxygen vacancies, we have calculated their binding energies to the described twin walls as a function of pressure. We find that this binding strongly depends on the vacancy disposition. For a vacancy between Si atoms in an axis perpendicular to the wall the binding energy is 1.09 eV at zero pressure. For vacancies along Si-Si axes parallel

  6. Kinetics of oxygen reduction in perovskite cathodes for solid oxide fuel cells: A combined modeling and experimental approach

    NASA Astrophysics Data System (ADS)

    Miara, Lincoln James

    Solid oxide fuel cells (SOFCs) have the potential to replace conventional stationary power generation technologies; however, there are major obstacles to commercialization, the most problematic of which is poor cathode performance. Commercialization of SOFCs will follow when the mechanisms occurring at the cathode are more thoroughly understood and adapted for market use. The catalytic reduction of oxygen occurring in SOFC cathodes consists of many elementary steps such as gas phase diffusion, chemical and/or electrochemical reactions which lead to the adsorption and dissociation of molecular oxygen onto the cathode surface, mass transport of oxygen species along the surface and/or through the bulk of the cathode, and full reduction and incorporation of the oxygen at the cathode/electrolyte two or three phase boundary. Electrochemical impedance spectroscopy (EIS) is the main technique used to identify the occurrence of these different processes, but when this technique is used without an explicit model describing the kinetics it is difficult to unravel the interdependence of each of these processes. The purpose of this dissertation is to identify the heterogeneous reactions occurring at the cathode of an SOFC by combining experimental EIS results with mathematical models describing the time dependent behavior of the system. This analysis is performed on two different systems. In the first case, experimental EIS results from patterned half cells composed of Ca-doped lanthanum manganite (LCM)| yttria-doped ZrO2 (YSZ) are modeled to investigate the temperature and partial pressure of oxygen, pO2, dependence of oxygen adsorption/dissociation onto the LCM surface, surface diffusion of atomic oxygen, and electrochemical reduction and incorporation of the oxygen into the electrolyte in the vicinity of the triple phase boundary (TPB). This model determines the time-independent state-space equations from which the Faradaic admittance transfer function is obtained. The

  7. Perovskite fever

    NASA Astrophysics Data System (ADS)

    2014-09-01

    Staggering increases in the performance of organic-inorganic perovskite solar cells have renewed the interest in these materials. However, further developments and the support from academic and industrial partners will hinge on the reporting of accurate efficiency values.

  8. The characteristic of strontium-site deficient perovskites SrxFe1.5Mo0.5O6-δ (x = 1.9-2.0) as intermediate-temperature solid oxide fuel cell cathodes

    NASA Astrophysics Data System (ADS)

    Yang, Guoquan; Feng, Jie; Sun, Wang; Dai, Ningning; Hou, Mingyue; Hao, Xiaoming; Qiao, Jinshuo; Sun, Kening

    2014-12-01

    As the cathodes for intermediate-temperature solid oxide fuel cells (IT-SOFCs), A-site deficient SrxFe1.5Mo0.5O6-δ (x = 1.9-2.0) (SxFM) materials have been successfully synthesized using the sol-gel combustion method. In the perovskite structure of these oxides, the unit cell varies from pseudocubic to cubic with increasing deficiency. Thermal expansion coefficient of SxFM has also been measured and compared with that of Scandium-stabilized zirconium (ScSZ) electrolyte. X-ray photoelectron spectroscopy (XPS) results indicate that the Sr-deficiency has changed the proportion of Fe2+/Fe3+ and Mo6+/Mo5+ ratios, which directly influences the conductivity of SxFM materials. S1.950FM possesses the largest electrical conductivity and the lowest polarization resistance (Rp) among all the samples. The maximum power densities of a single cell with the S1.950FM cathode reaches 1083 mW cm-2, and the area specific resistance value is 0.17 Ω cm2 at 800 °C. These results indicate that the A-site deficiency could promote the electrochemical performance of SFM materials as cathodes for IT-SOFCs.

  9. Magnetization Studies of the Effects of Oxygen Deficiency Delta on the Superconductive Properties of Aligned Yttrium BARIUM(2) COPPER(3) OXYGEN(7-DELTA) Materials

    NASA Astrophysics Data System (ADS)

    Ossandon, Jorge G.

    Magnetically aligned samples of sintered YBa _2Cu_3O_ {7-delta} were used to test the effects of oxygen-deficiency delta (with 0<=qdelta<=q 0.2) on the superconductive magnetization M, critical current density J_{c}, irreversibility field B_{irr }, upper critical field H_{ rm c2}, coherence length xi , condensation energy F_{c}, London penetration depth lambda and related properties as functions of temperature T and applied magnetic field H | c. In selected cases, studies were also made with H | ab. The open porosity and granularity of the material allowed rapid and homogeneous oxygenation. The oxygen content was monitored in situ by Thermo-Gravimetric Analysis. We found no significant enhancement of intragrain J_{c} with chain -site O-defects. With few exceptions, maximum J _{c} occurred at full oxygenation. This implies that chain-site O-defects are not strong or effective pinning centers over most of the field-temperature regime investigated. Except for T _{c}, which was practically independent of delta within the interval 0<=qdelta<=q 0.11 (so called "T_{c} -plateau"), most properties such as J_{ c}, F_{c}, H_{c2} , B_{irr}(T), lambda and xi were strongly and continuously influenced by the oxygen deficiency. The observed abnormal magnetization ("fishtail" or "bowtie" effect) with H | c was weak at low T but became more pronounced as T and delta increased. No abnormal magnetization was detected with H | ab. As oxygen was removed, B_{irr }(T) and H_{c2}(T) separated and both lines shifted to lower T and lower H. Moreover, B_{irr} was strongly correlated with J _{c} at low temperature. Determination of the thermodynamic critical field H_{ c} yielded condensation energies F _{c}(delta) that suffered a strong reduction with increasing delta. As predicted by a simple, single-site pinning model, a good correlation was found between J _{c}(delta) and the product F_{c}xi _{ab} (where xi_{ab} is the coherence length in the a-b plane). This correlation was corroborated by

  10. Oxygen-Deficient TiO2 - x/Methylene Blue Colloids: Highly Efficient Photoreversible Intelligent Ink.

    PubMed

    Imran, M; Yousaf, Ammar B; Zhou, Xiao; Liang, Kuang; Jiang, Yi-Fan; Xu, An-Wu

    2016-09-06

    Oxygen-sensitive photoreversible intelligent ink capable of assessment with the human eye is an ongoing demand in the modern era. In the food industry, redox-dye-based oxygen indicator films have been proposed, but the leaching of dyes from the film that contaminates the food is one unsolved issue. On the other hand, it is also highly desirable to develop rewritable paper that significantly reduces the pressure on modern society for the production and consumption of paper. Herein, we have developed an oxygen-deficient TiO2 - x/methylene blue (MB) sol without relying on external sacrificial electron donors (SEDs) for photoreversible color switching. Oxygen vacancies in TiO2 - x can work as electron donor to favor the adsorption of the substrate and improve the charge separation that is required for the redox-based color-switching system. The problems of rewriteable paper and food packaging are addressed as two sides of a single coin in this article. We have used hydroxyethyl cellulose (HEC) for rewritable paper that can significantly delay the oxidation of leuco-MB (LMB) through hydrogen bonding and retain the printed information for a long time. The dye leaching from oxygen indicator films is also significantly reduced (only 1.54%) by using furcelleran as the coating polymer that is extracted from edible red seaweed.

  11. Erasable photoinduced change of carrier density and coherence lengths in oxygen-deficient YBa 2Cu 3O x

    NASA Astrophysics Data System (ADS)

    Göb, W.; Lang, W.; Markowitsch, W.; Schlosser, V.; Kula, W.; Soblewski, Roman

    1995-11-01

    We report on the persistent and erasable photoinduced change of normal-state transport and superconducting properties of oxygen-deficient YBa 2Cu 3O 6.6 thin films. After illumination with white light for several hours at 150K, a decrease of the electrical resistivity, an increase of the number of mobile holes, and a change of the magnetoresistance caused by superconducting order-parameter fluctuations, were observed. From the latter measurement, we find a photoinduced enhancement of the superconducting coherence lengths in both in-plane and out-of-plane directions.

  12. Interrelation of epitaxial strain and oxygen deficiency in La0.7Ca0.3MnO3-δ thin films

    NASA Astrophysics Data System (ADS)

    Kawashima, K.; Logvenov, G.; Christiani, G.; Habermeier, H.-U.

    2015-03-01

    The interrelation between the epitaxial strain and oxygen deficiency in La0.7Ca0.3MnO3-δ thin films was studied in terms of structural and functional properties. The films with a thickness of 1000 Å were prepared using a PLD system equipped with a RHEED facility and a pyrometric film temperature control. The epitaxial strain and the oxygen deficiency in the samples were systematically modified using three different substrates: SrTiO3, (LaAlO3)0.3-(Sr2AlTaO6)0.7 and LaSrAlO4, and four different oxygen pressures during film growth ranging from 0.27 mbar to 0.1 mbar. It could be demonstrated that the oxygen incorporation depends on the epitaxial strain: oxygen vacancies were induced to accommodate tensile strain whereas the compressive strain suppressed the generation of oxygen vacancies.

  13. Atomic structure and oxygen deficiency of the ultrathin aluminium oxide barrier in Al/AlOx/Al Josephson junctions

    NASA Astrophysics Data System (ADS)

    Zeng, Lunjie; Tran, Dung Trung; Tai, Cheuk-Wai; Svensson, Gunnar; Olsson, Eva

    2016-07-01

    Al/AlOx/Al Josephson junctions are the building blocks of a wide range of superconducting quantum devices that are key elements for quantum computers, extremely sensitive magnetometers and radiation detectors. The properties of the junctions and the superconducting quantum devices are determined by the atomic structure of the tunnel barrier. The nanoscale dimension and disordered nature of the barrier oxide have been challenges for the direct experimental investigation of the atomic structure of the tunnel barrier. Here we show that the miniaturized dimension of the barrier and the interfacial interaction between crystalline Al and amorphous AlOx give rise to oxygen deficiency at the metal/oxide interfaces. In the interior of the barrier, the oxide resembles the atomic structure of bulk aluminium oxide. Atomic defects such as oxygen vacancies at the interfaces can be the origin of the two-level systems and contribute to decoherence and noise in superconducting quantum circuits.

  14. Atomic structure and oxygen deficiency of the ultrathin aluminium oxide barrier in Al/AlOx/Al Josephson junctions.

    PubMed

    Zeng, Lunjie; Tran, Dung Trung; Tai, Cheuk-Wai; Svensson, Gunnar; Olsson, Eva

    2016-07-12

    Al/AlOx/Al Josephson junctions are the building blocks of a wide range of superconducting quantum devices that are key elements for quantum computers, extremely sensitive magnetometers and radiation detectors. The properties of the junctions and the superconducting quantum devices are determined by the atomic structure of the tunnel barrier. The nanoscale dimension and disordered nature of the barrier oxide have been challenges for the direct experimental investigation of the atomic structure of the tunnel barrier. Here we show that the miniaturized dimension of the barrier and the interfacial interaction between crystalline Al and amorphous AlOx give rise to oxygen deficiency at the metal/oxide interfaces. In the interior of the barrier, the oxide resembles the atomic structure of bulk aluminium oxide. Atomic defects such as oxygen vacancies at the interfaces can be the origin of the two-level systems and contribute to decoherence and noise in superconducting quantum circuits.

  15. Atomic structure and oxygen deficiency of the ultrathin aluminium oxide barrier in Al/AlOx/Al Josephson junctions

    PubMed Central

    Zeng, Lunjie; Tran, Dung Trung; Tai, Cheuk-Wai; Svensson, Gunnar; Olsson, Eva

    2016-01-01

    Al/AlOx/Al Josephson junctions are the building blocks of a wide range of superconducting quantum devices that are key elements for quantum computers, extremely sensitive magnetometers and radiation detectors. The properties of the junctions and the superconducting quantum devices are determined by the atomic structure of the tunnel barrier. The nanoscale dimension and disordered nature of the barrier oxide have been challenges for the direct experimental investigation of the atomic structure of the tunnel barrier. Here we show that the miniaturized dimension of the barrier and the interfacial interaction between crystalline Al and amorphous AlOx give rise to oxygen deficiency at the metal/oxide interfaces. In the interior of the barrier, the oxide resembles the atomic structure of bulk aluminium oxide. Atomic defects such as oxygen vacancies at the interfaces can be the origin of the two-level systems and contribute to decoherence and noise in superconducting quantum circuits. PMID:27403611

  16. Influence of oxygen deficiency on the superconductive properties of grain-aligned YBa2Cu3O7-δ

    NASA Astrophysics Data System (ADS)

    Ossandon, J. G.; Thompson, J. R.; Christen, D. K.; Sales, B. C.; Kerchner, H. R.; Thomson, J. O.; Sun, Y. R.; Lay, K. W.; Tkaczyk, J. E.

    1992-06-01

    Magnetically aligned samples of sintered YBa2Cu3O7-δ were used to test the effects of oxygen-deficiency δ (with δ<=0.2) on the superconductive magnetization M, critical current density Jc, irreversibility field Birr, upper critical field Hc2, coherence length ξ, condensation energy Fc, penetration depth λ, and related properties as a function of temperature T and applied field H∥c. In selected cases, studies were also made with H∥ab. The O content was monitored in situ by thermogravimetric analysis. The open porosity and granularity of the material allowed rapid and homogeneous oxygenation. We found no significant enhancement of intragrain Jc with chain-site O defects. With few exceptions, maximum Jc occurred at full oxygenation. This implies that chain-site O defects are not strong or effective pinning centers over most of the field-temperature regime investigated. Except for Tc, which was practically independent of δ within the interval 0<=δ<=0.11 (so called ``90-K Tc plateau''), most properties such as Jc, Fc, Hc2, Birr(T), λ, and ξ were strongly and continuously influenced by the O deficiency. The observed abnormal magnetization with Hc was weak at low T but became more pronounced as T and δ increased. No abnormal magnetization was detected with Hab. As oxygen was removed, Birr(T) and Hc2(T) separated, and both lines shifted to lower T and lower B. Moreover, Birr was strongly correlated with Jc at low temperature. Determination of the thermodynamic critical field Hc yielded condensation energies Fc(δ) that were well correlated with Jc(δ). The results indicate that O defects weaken the energy barrier of the existing pinning sites and have a negative overall effect on the capacity of YBa2Cu3O7-δ to carry loss-free currents.

  17. The Origin of Elastic Anomalies in Thin Films of Oxygen Deficient Ceria CeO(2-x)

    SciTech Connect

    A Kossoy; A Frenkel; Y Feldman; E Wachtel; A Milner; I Lubomirsky

    2011-12-31

    Self-supported films of CeO{sub 1.95} display time-scale dependent elastic moduli, a phenomenon which has been termed the chemical strain effect. In order to probe the possible structural origins of this behavior, extended X-ray absorption fine structure spectroscopy and X-ray diffraction were used. Evidence was found that, although this oxygen deficient ceria appears to maintain the fluorite structure on average, the mean Ce-O bond length is shorter than the mean Ce-oxygen vacancy distance. This finding is consistent with crystallographic data from more strongly reduced ceria in which the oxygen vacancies are ordered. By studying strain induced structural changes, we show that it is possible to relate this lattice distortion to the chemical strain effect. Similar conclusions were previously reached for films of Ce{sub 0.8}Gd{sub 0.2}O{sub 1.9}. Since the ionic radii of both Gd{sup 3+} and Ce{sup 3+} are larger than that of Ce{sup 4+}, we suggest that when cation dopants are larger than the host, ceria compounds containing a high concentration of oxygen vacancies may exhibit elastic anomalies.

  18. Thermochemistry of perovskites in the lanthanum-strontium-manganese-iron oxide system

    NASA Astrophysics Data System (ADS)

    Marinescu, Cornelia; Vradman, Leonid; Tanasescu, Speranta; Navrotsky, Alexandra

    2015-10-01

    The enthalpies of formation from binary oxides of perovskites (ABO3) based on lanthanum strontium manganite La(Sr)MnO3 (LSM) and lanthanum strontium ferrite La(Sr)FeO3 (LSF) and mixed lanthanum strontium manganite ferrite La(Sr)Mn(Fe)O3 (LSMF) were measured by high temperature oxide melt solution calorimetry. Using iodometric titration, the oxygen content was derived. The perovskites with A-site cation deficiency have greater oxygen deficiency than the corresponding A-site stoichiometric series. Stability of LSMF decreases with increasing iron content. Increasing oxygen deficiency clearly destabilizes the perovskites. The results suggest an enthalpy of oxygen incorporation that is approximately independent of composition. 0.35La2O3 (xl, 25 °C)+Mn2O3 (xl, 25 °C)+0.3SrO (xl, 25 °C)+Fe2O3 (xl, 25 °C)+O2 (g, 25 °C)→La0.7Sr0.3Mn1-yFeyO3-δ (xl, 25 °C). (b) ∆ Hf,ox* (La0.7Sr0.3Mn1-yFeyO3-δ) .0.35 La2O3 (xl, 25 ººC) + (0.7-y+ 2δ)/2 Mn2O3 (xl, 25 ºC) + 0.3 SrO (xl, 25 ºC) + y/2Fe2O3 (xl, 25 ºC) + (0.3-2δ) MnO2 (xl, 25 ºC)→La0.7Sr0.3Mn1-yFeyO3-δ (xl, 25 ºC).

  19. Laser-induced photodissociation of oxyhemoglobin: Optical method of elimination of hypoxia (oxygen deficiency in biotissue)

    NASA Astrophysics Data System (ADS)

    Asimov, M. M.; Thanh, Nguyen Cong

    2011-08-01

    We consider the effect of laser-induced in vivo photodissociation of blood oxyhemoglobin on gas exchange in biological tissues. An optical method of laser-induced oxygenation of biotissues is developed and proposed. We show that, in the region of the action of the laser radiation, the degree of oxygenation of a tissue increases. We experimentally confirm that the phenomenon of laser-induced in vivo photodissociation of oxyhemoglobin opens up a new possibility of controlling the local concentration of free molecular oxygen in tissues, eliminating tissue hypoxia, and stimulating aerobic metabolism of cells. We show that the efficiency of the proposed method of laser-induced oxygenation of biotissues proves to be comparable with the efficiency of the hyperbaric oxygenation, but has the advantage of the locality of the action. The proposed optical method of local oxygenation of biotissues will make it possible to eliminate the problem of hypoxia in cancerous tumor tissue and to considerably increase the efficiency of photodynamic, radiation, and chemotherapy in modern oncology.

  20. Characterizing Redox Conditions in Oxygen-deficient Waters Off Peru During the 2013 US GEOTRACES Zonal Transect

    NASA Astrophysics Data System (ADS)

    Cutter, G. A.; Nielsdottir, M.

    2014-12-01

    The oxygen-deficient zone that extends from coastal Peru well into the tropical Pacific Ocean has been described as "suboxic," but recent measurements of sulfate reduction suggest it may have some anoxic characteristics (e.g., free sulfide). The redox poise of suboxia strongly affects the solubility/stability of a wide variety of trace elements and therefore their vertical and horizontal transport. The problem is that suboxic is not chemically well defined, but certainly represents a very wide range of redox conditions (pE of ca. 10 to -2). During the 2013 US GEOTRACES Pacific cruise (International GEOTRACES section GP16) we determined a suite of redox couples to help define the redox poise in the water column: oxygen(/water), iodate/iodide, nitrate/nitrite, selenate/elemental Se, arsenate/arsenite, and sulfate/hydrogen sulfide. Using the RV Thomas Thompson we occupied a total of 11 stations along 12° S from coastal Peru to 94° W to sample the oxygen deficient waters using a conventional CTD/rosette and the trace metal-clean US GEOTRACES CTD/carousel. Determinations of all the redox tracers were made on board ship except for selenium. On the Peru shelf, oxygen concentrations were less than 10 μM from 30m to the bottom, while farther offshore the depth of this oxygen minimum was 700 m thick starting at ca. 80 m depth; the layer thickness steadily decreased moving west. In spite of the low oxygen conditions, nitrate and iodate were still detectable, while their corresponding reduced species had maxima in the low O2 waters. Dissolved hydrogen sulfide was below the detection limit of 70 pM, and no evidence of As(V) reduction was found; selenium speciation has yet to be determined. The lack of detectable dissolved hydrogen sulfide shows the redox conditions are certainly not anoxic, and incomplete iodate and nitrate reduction suggest the redox environment is more oxidizing than previously reported. The apparent temporal and spatial variability of the redox poise will

  1. Effect of zinc deficiency on NADPH and cytochrome P-450 dependent active oxygen generation in rat lung and liver

    SciTech Connect

    Hammermueller, J.D.; Bray, T.M.; Bettger, W.J.

    1986-03-05

    The cyt. P-450 system and cyt. P-450 reductase are involved in the generation of active oxygen species such as H/sub 2/O/sub 2/. The objective of this study was to investigate the effect of short term, severe, dietary zinc deficiency in rats on the formation of active oxygen in vitro. Weanling male Wistar rats were fed egg white-based diets containing less than 1 ppm Zn (ZnD). Controls were fed ad libitum (ZnAl) or pair-fed (ZnPF) a diet containing 100 ppm Zn. After 3 weeks lung and liver microsomes were assayed for H/sub 2/O/sub 2/ production (pmol H/sub 2/O/sub 2//mg protein/min) and cyt. P-450 reductase activity (nmol cyt. C reduced/mg protein/min). For the measurement of H/sub 2/O/sub 2/ production exogenous substrate (aminopyrine) and NADPH (cofactor) were provided to drive the cyt. P-450 system and NaN/sub 3/ was used to inhibit catalase. The results showed a significant effect of dietary Zn on NADPH and cyt. P-450 dependent active oxygen generation and support the hypothesis that Zn has a role in the function of biomembranes.

  2. CD73 and AMPD3 deficiency enhance metabolic performance via erythrocyte ATP that decreases hemoglobin oxygen affinity

    PubMed Central

    O’Brien III, William G.; Berka, Vladimir; Tsai, Ah-Lim; Zhao, Zhaoyang; Lee, Cheng Chi

    2015-01-01

    Erythrocytes are the key target in 5′-AMP induced hypometabolism. To understand how regulation of endogenous erythrocyte AMP levels modulates systemic metabolism, we generated mice deficient in both CD73 and AMPD3, the key catabolic enzymes for extracellular and intra-erythrocyte AMP, respectively. Under physiological conditions, these mice displayed enhanced capacity for physical activity accompanied by significantly higher food and oxygen consumption, compared to wild type mice. Erythrocytes from Ampd3−/− mice exhibited higher half-saturation pressure of oxygen (p50) and about 3-fold higher levels of ATP and ADP, while they maintained normal 2,3-bisphosphoglycerate (2,3-BPG), methemoglobin levels and intracellular pH. The affinity of mammalian hemoglobin for oxygen is thought to be regulated primarily by 2,3-BPG levels and pH (the Bohr effect). However, our results show that increased endogenous levels of ATP and ADP, but not AMP, directly increase the p50 value of hemoglobin. Additionally, the rise in erythrocyte p50 directly correlates with an enhanced capability of systemic metabolism. PMID:26249166

  3. ETA receptor blockade attenuates hypertension and decreases reactive oxygen species in ETB receptor-deficient rats.

    PubMed

    Elmarakby, Ahmed A; Dabbs Loomis, E; Pollock, Jennifer S; Pollock, David M

    2004-11-01

    We hypothesize that endothelin-A receptor stimulation contributes to the elevated blood pressure and superoxide production in endothelin-B receptor-deficient rats on a high salt diet. Experiments were conducted on homozygous endothelin-B-deficient (sl/sl) and wild-type rats (wt) fed a high salt diet (8% NaCl) for 3 weeks. Separate groups were given normal drinking water or water containing the endothelin-A receptor antagonist, ABT-627 (5 mg/kg per day; n = 8-9 in all groups). On a normal salt diet, (sl/sl) rats had a significantly elevated systolic blood pressure compared with wt (138 +/- 3 vs 117 +/- 4 mmHg, respectively; P < 0.05). High salt diet caused a significant increase in systolic blood pressure in (sl/sl) rats compared with wt (158 +/- 2 vs 138 +/- 3 mmHg, respectively; P < 0.05). Endothelin-A receptor blockade decreased systolic blood pressure in (sl/sl) rats on high salt (125 +/- 5 mmHg; P < 0.05 vs without antagonist) without affecting the systolic blood pressure in wt (119 +/- 4 mmHg). Aortic superoxide production (lucigenin chemiluminescence) and plasma 8-isoprostane were elevated in sl/sl rats and were significantly reduced by endothelin-A receptor blockade in sl/sl, but not in wt rats. These findings suggest that endothelin-1, through the endothelin-A receptor, contributes to salt-induced hypertension and vascular superoxide production in endothelin-B-deficient rats.

  4. Optimal levels of oxygen deficiency in the visible light photocatalyst TiO2-x and long-term stability of catalytic performance

    NASA Astrophysics Data System (ADS)

    Nakano, Takuma; Ito, Ryosuke; Kogoshi, Sumio; Katayama, Noboru

    2016-11-01

    The dependence of the visible light-responsive photocatalytic activity of oxygen deficient TiO2 (TiO2-x) prepared by Ar/H2 plasma surface treatment on the degree of oxygen deficiency (x) was assessed to determine the deficiency region associated with highest performance. The highest activity was obtained at x=0.06 (TiO1.94). The maximum visible light activity for this material, estimated from the formaldehyde (HCHO) removal rate, was three times higher than that exhibited by nitrogen-doped TiO2 (TiO2-xNx). The catalytic ability was found to decrease over the first week after fabrication of the material, after which it became stable, and the performance of TiO2-x at this point was found to be nearly equal to that of TiO2-xNx. The results of ab initio calculations of density of states for TiO2-x suggest that new oxygen deficiency states emerge at almost the exact center between the valence and conduction bands when x>0.06, which increases the recombination rate between electrons and holes. Therefore the declining performance of TiO2-x at larger x values is attributed to the emergence of new oxygen deficient states.

  5. Paired N and O isotopic analysis of nitrate and nitrite in the Arabian Sea oxygen deficient zone

    NASA Astrophysics Data System (ADS)

    Martin, T. S.; Casciotti, K. L.

    2017-03-01

    The Arabian Sea is home to one of the three main oceanic oxygen deficient zones (ODZs). We present paired nitrogen (N) and oxygen (O) isotope measurements of nitrate (NO3-) and nitrite (NO2-) from the central Arabian Sea in order to understand the effects of N biogeochemistry on the distribution of these species in the low oxygen waters. Within the ODZ, NO2- accumulated in a secondary NO2- maximum (SNM), though the shape and magnitude of the SNM, along with the isotopic composition of NO3- and NO2-, were highly dependent on the location within the ODZ. We also explored water mass mixing within the Arabian Sea as an explanatory factor in the distribution of NO2- in the SNM. The intrusion of Persian Gulf Water at depth may influence the shape of the NO2- peak by introducing small amounts of dissolved oxygen (O2), favoring NO2- oxidation. There was also evidence that vertical mixing may play a role in shaping the top of the SNM peak. Finally, we present evidence for NO2- oxidation and NO2- reduction co-occurring within the ODZ, as has been previously suggested in the Arabian Sea, as well as in other ODZs. The decoupling of the N and O isotopes of NO3-, deviating from the expected 1:1 ratio for dissimilatory NO3- reduction, indicates that NO2- oxidation has a significant influence on the isotopic composition of NO3-. Additionally, the N isotopes of NO2- were generally fit well by Rayleigh curves for NO2- oxidation. However, the removal of dissolved inorganic nitrogen (DIN) within the domain reflects the importance of NO2- reduction to N2.

  6. Magnetic resonance imaging (MRI) investigation of the effect of dietary Zn or Cu deficiency and hyperoxia on the oxygen free radical defense system in rats

    SciTech Connect

    Taylor, C.G.; Towner, R.A.; Bray, T.M. )

    1990-02-26

    The role of Zn/Cu nutrition in oxygen free radical defense was investigate. Although endogenous free radical generation is increased in Zn and Cu deficiency, the free radical defense system in the lung and liver of Zn or Cu deficient rats was not compromised. The key oxygen radical defense enzyme, CuZn-superoxide dismutase (CuZnSOD) activity was directly related to tissue Cu and inversely related to tissue Zn concentrations. When oxidative stress (85% oxygen exposure for 7 days) was superimposed on Zn or Cu deficiency, Cu but not Zn deficient rats were able to increase lung CuZnSOD activity. The changes in lung CuZnSOD activity during oxidative stress were not correlated with lung Cu or Zn concentrations. In a pioneering application of proton MRI, lung damage was monitored in vivo and non-invasively to evaluate the overall capacity of the free radical defense system for protection against oxidative stress. Zn deficient rats displayed the most severe lung damage by MRI. Repletion of Zn in the diet prevented MRI-detectable hyperoxia-induced lung damage. Volume selective spectroscopy (VOSY) verified lung damage was due to an increased water content. Inability of Zn deficient rats to increase lung CuZnSOD activity appears to contribute to the severe free radical-induced lung damage.

  7. “Ba{sub 6}Nb{sub 4}RuO{sub 18}” and “LaBa{sub 4}Nb{sub 3}RuO{sub 15}” – The structural consequences of substituting paramagnetic cations into A{sub n}B{sub n−1}O{sub 3n} cation-deficient perovskite oxides

    SciTech Connect

    Kamil, Elynor L.; Morgan, Harry W.T.; Hayward, Michael A.

    2016-06-15

    The B-cation deficient perovskite phases Ba{sub 6}Nb{sub 4}RuO{sub 18} and LaBa{sub 4}Nb{sub 3}RuO{sub 15} were prepared by ceramic synthesis. Neutron powder diffraction analysis indicates that rather than the 6-layer and 5-layer cation-deficient perovskite structures expected for these phases (by analogy to the known structures of Ba{sub 6}Nb{sub 4}TiO{sub 18} and LaBa{sub 4}Nb{sub 3}TiO{sub 15}) they adopt 5-layer and 4-layer B-cation deficient perovskite structures respectively, and are better described as Ba{sub 5}Nb{sub 3.33}Ru{sub 0.81}O{sub 15} and Ba{sub 3.16}La{sub 0.84}Nb{sub 2.36}Ru{sub 0.72}O{sub 12}. The factors that lead to the compositionally analogous Nb/Ru and Nb/Ti phases adopting different structures are discussed on the basis of the difference between d{sup 0} and non-d{sup 0} transition metal cations. - Graphical abstract: The ruthenium-containing B-cation deficient perovskite phases, Ba{sub 5}Nb{sub 3.33}Ru{sub 0.81}O{sub 15} and Ba{sub 3.16}La{sub 0.84}Nb{sub 2.36}Ru{sub 0.72}O{sub 12}, adopt 5-layer and 4-layer structures respectively, rather than the 6-layer and 5-layer cation-deficient structures adopted by the analogous titanium-containing phases Ba{sub 6}Nb{sub 4}TiO{sub 18} and LaBa{sub 4}Nb{sub 3}TiO{sub 15}. Display Omitted - Highlights: • B-cation deficient perovskite containing paramagnetic cations. • B-cation deficient structure determined by neutron powder diffraction. • Low ‘solubility’ of BaRuO{sub 3} in Ba{sub 5}Nb{sub 4}O{sub 15} leads to novel structure.

  8. Structural evolution across the insulator-metal transition in oxygen-deficient BaTiO3-δ studied using neutron total scattering and Rietveld analysis

    DOE PAGES

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

    2011-08-29

    Oxygen-deficient BaTiO3-δ exhibits an insulator-metal transition with increasing δ. We performed neutron total scattering measurements to study structural evolution across an insulator-metal transition in BaTiO3-δ. Despite its significant impact on resistivity, slight oxygen reduction (δ=0.09) caused only a small disturbance on the local doublet splitting of Ti-O bond. This finding implies that local polarization is well preserved under marginal electric conduction. In the highly oxygen-deficient metallic state (δ=0.25), however, doublet splitting of the Ti-O bond became smeared. The smearing of the local Ti-O doublet is complemented with long-range structural analysis and demonstrates that the metallic conduction in the highly oxygen-reducedmore » BaTiO3-δ is due to the appearance of nonferroelectric cubic lattice.« less

  9. Adrenal-derived 11-Oxygenated 19-Carbon Steroids are the Dominant Androgens in Classic 21-Hydroxylase Deficiency

    PubMed Central

    Turcu, Adina F.; Nanba, Aya T.; Chomic, Robert; Upadhyay, Sunil K.; Giordano, Thomas J.; Shields, James J.; Merke, Deborah P.; Rainey, William E.; Auchus, Richard J.

    2016-01-01

    Objective To comprehensively characterize androgens and androgen precursors in classic 21-hydroxylase deficiency (21OHD) and to gain insight to the mechanisms of their formation. Design Serum samples were obtained from 38 patients (19 men) with classic 21OHD, age 3-59, and 38 sex- and age-matched controls; 3 patients with 11β-hydroxylase deficiency; 4 patients with adrenal insufficiency; and 16 patients (8 men) undergoing adrenal vein sampling. Paraffin-embedded normal (n=5) and 21OHD adrenal tissue (n=3) was used for immunohistochemical studies. Methods We measured 11 steroids in all sera using liquid chromatography-tandem mass spectrometry. Immunofluroescence localized 3β-hydroxysteroid dehydrogenase type 2 (HSD3B2) and cytochrome b5 (CYB5A) within the normal and 21OHD adrenals. Results Four 11-oxygenated 19-carbon (11oxC19) steroids were significantly higher in male and female 21OHD patients than in controls: 11β-hydroxyandrostenedione, 11-ketoandrostenedione 11β-hydroxytestosterone, and 11-ketotestosterone (3-4-fold, p< 0.0001). For 21OHD patients, testosterone and 11-ketotestosterone were positively correlated in females, but inversely correlated in males. All 11oxC19 steroids were higher in adrenal vein than in inferior vena cava samples from men and women and rose with cosyntropin stimulation. Only trace amounts of 11oxC19 steroids were found in sera from patients with 11β-hydroxylase deficiency and adrenal insufficiency, confirming their adrenal origin. HSD3B2 and CYB5A immunoreactivities were sharply segregated in the normal adrenal glands, whereas areas of overlapping expression were identified in the 21OHD adrenals. Conclusions All four 11oxC19 steroids are elevated in both men and women with classic 21OHD. Our data suggest that 11oxC19 steroids are specific biomarkers of adrenal-derived androgen excess. PMID:26865584

  10. Magnetization and flux pinning in high-Tc cuprates: Irradiated and oxygen deficient materials

    NASA Astrophysics Data System (ADS)

    Thompson, J. R.; Sun, Yang Ren; Ossandon, J. G.; Christen, D. K.; Kerchner, H. R.; Sales, B. C.; Chakoumakos, B. C.; Civale, L.; Marwick, A. C.; Holtzberg, F.

    1992-11-01

    Recent studies of the intragrain current density J and vortex pinning in high Tc superconductors are surveyed. Materials include Y1Ba2Cu3O(7-delta) and Bi2Sr2Ca1Cu2O8 single crystals and aligned polycrystals. To probe the flux pinning, the strength, number, and morphology of defects were modified. Varying the oxygen content (7-delta) in YBa2Cu3O(7-delta) or irradiating the materials with ions, having either light or heavy masses, gives systematic changes in the character of the all-important defects.

  11. Oxygen-Deficient Zirconia (ZrO2−x): A New Material for Solar Light Absorption

    PubMed Central

    Sinhamahapatra, Apurba; Jeon, Jong-Pil; Kang, Joonhee; Han, Byungchan; Yu, Jong-Sung

    2016-01-01

    Here, we present oxygen-deficient black ZrO2−x as a new material for sunlight absorption with a low band gap around ~1.5 eV, via a controlled magnesiothermic reduction in 5% H2/Ar from white ZrO2, a wide bandgap(~5 eV) semiconductor, usually not considered for solar light absorption. It shows for the first time a dramatic increase in solar light absorbance and significant activity for solar light-induced H2 production from methanol-water with excellent stability up to 30 days while white ZrO2 fails. Generation of large amounts of oxygen vacancies or surface defects clearly visualized by the HR-TEM and HR-SEM images is the main reason for the drastic alteration of the optical properties through the formation of new energy states near valence band and conduction band towards Fermi level in black ZrO2−x as indicated by XPS and DFT calculations of black ZrO2−x. Current reduction method using Mg and H2 is mild, but highly efficient to produce solar light-assisted photocatalytically active black ZrO2−x. PMID:27264788

  12. Transport properties and metal-insulator transition in oxygen deficient LaNiO3: a density functional theory study

    NASA Astrophysics Data System (ADS)

    Misra, D.; Kundu, T. K.

    2016-09-01

    Density functional theory with appropriate functional has been employed to investigate the metal to insulator transition in oxygen deficient LaNiO3-x (x = 0.0, 0.25, 0.5, 1.0) compounds. While the metallic nature of LaNiO3 is characterized by the low temperature Fermi liquid behavior of resistivity and a finite density of states at the Fermi level, the density of states and the transport properties clearly identify LaNiO2.75 as a semiconductor, and LaNiO2.5 as an insulator, which is followed by another insulator to semiconductor transition with further increase of x to ‘1’ in LaNiO2. This oxygen vacancy controlled metal to insulator transition is explained on the basis of non-adiabatic polaronic transport. From the covalency metric calculation of the chemical bonding and the Bader charge transfer analysis, this metal to insulator transition is attributed to the enhanced covalent part in the chemical bonding and reduced charge transfer from Ni to O atoms in LaNiO3-x compounds.

  13. A Novel Anoxic Pathway for Urea and Cyanate in Marine Oxygen Deficient Zones Revealed by Combined Microbiological and Biogeochemical Tools

    NASA Astrophysics Data System (ADS)

    Widner, B.; Fuchsman, C. A.; Babbin, A. R.; Ji, Q.; Mulholland, M. R.

    2016-02-01

    Urea and cyanate are reduced nitrogen compounds that can serve as nitrogen and carbon sources for marine microbes, and cyanate forms from decomposition of urea. Some marine bacteria, including cyanobacteria, possess genes encoding an ABC-type cyanate transporter and an intracellular cyanate hydratase, and genes for urea uptake and assimilation are widespread. To investigate cyanate distribution and availability in the ocean, we recently developed a nanomolar cyanate assay specific to seawater. In an oxygenated water column, urea and cyanate concentrations are generally low in surface waters and exhibit a concentration maximum near the base of the euphotic zone likely due to production from organic matter degradation. Below the euphotic zone, urea and cyanate concentrations decrease, likely due to oxidation reactions. It has been suggested that simple organic nitrogen compounds may support anaerobic ammonium oxidation (anammox) in oxygen deficient zones (ODZs). We mapped urea and cyanate distributions and used stable isotope-labeled urea and cyanate to measure their potential support of anammox and their uptake within the Eastern Tropical North and South Pacific ODZs. We also employed metagenomic techniques to determine the abundance and distribution of genes for the uptake and assimilation of urea and cyanate. The combined data indicate that, in ODZs, urea is used primarily as a nitrogen source while cyanate is used as both a nitrogen source and to generate energy.

  14. Combined increases in mitochondrial cooperation and oxygen photoreduction compensate for deficiency in cyclic electron flow in Chlamydomonas reinhardtii.

    PubMed

    Dang, Kieu-Van; Plet, Julie; Tolleter, Dimitri; Jokel, Martina; Cuiné, Stéphan; Carrier, Patrick; Auroy, Pascaline; Richaud, Pierre; Johnson, Xenie; Alric, Jean; Allahverdiyeva, Yagut; Peltier, Gilles

    2014-07-01

    During oxygenic photosynthesis, metabolic reactions of CO2 fixation require more ATP than is supplied by the linear electron flow operating from photosystem II to photosystem I (PSI). Different mechanisms, such as cyclic electron flow (CEF) around PSI, have been proposed to participate in reequilibrating the ATP/NADPH balance. To determine the contribution of CEF to microalgal biomass productivity, here, we studied photosynthesis and growth performances of a knockout Chlamydomonas reinhardtii mutant (pgrl1) deficient in PROTON GRADIENT REGULATION LIKE1 (PGRL1)-mediated CEF. Steady state biomass productivity of the pgrl1 mutant, measured in photobioreactors operated as turbidostats, was similar to its wild-type progenitor under a wide range of illumination and CO2 concentrations. Several changes were observed in pgrl1, including higher sensitivity of photosynthesis to mitochondrial inhibitors, increased light-dependent O2 uptake, and increased amounts of flavodiiron (FLV) proteins. We conclude that a combination of mitochondrial cooperation and oxygen photoreduction downstream of PSI (Mehler reactions) supplies extra ATP for photosynthesis in the pgrl1 mutant, resulting in normal biomass productivity under steady state conditions. The lower biomass productivity observed in the pgrl1 mutant in fluctuating light is attributed to an inability of compensation mechanisms to respond to a rapid increase in ATP demand.

  15. Structural and magnetic phase transitions in the A(n)B(n)O(3n-2) anion-deficient perovskites Pb2Ba2BiFe5O13 and Pb(1.5)Ba(2.5)Bi2Fe6O16.

    PubMed

    Abakumov, A M; Batuk, M; Tsirlin, A A; Tyablikov, O A; Sheptyakov, D V; Filimonov, D S; Pokholok, K V; Zhidal, V S; Rozova, M G; Antipov, E V; Hadermann, J; Van Tendeloo, G

    2013-07-15

    Novel anion-deficient perovskite-based ferrites Pb2Ba2BiFe5O13 and Pb(1.5)Ba(2.5)Bi2Fe6O16 were synthesized by solid-state reaction in air. Pb2Ba2BiFe5O13 and Pb(1.5)Ba(2.5)Bi2Fe6O16 belong to the perovskite-based A(n)B(n)O(3n-2) homologous series with n = 5 and 6, respectively, with a unit cell related to the perovskite subcell a(p) as a(p)√2 × a(p) × na(p)√2. Their structures are derived from the perovskite one by slicing it with 1/2[110]p(101)p crystallographic shear (CS) planes. The CS operation results in (101)p-shaped perovskite blocks with a thickness of (n - 2) FeO6 octahedra connected to each other through double chains of edge-sharing FeO5 distorted tetragonal pyramids which can adopt two distinct mirror-related configurations. Ordering of chains with a different configuration provides an extra level of structure complexity. Above T ≈ 750 K for Pb2Ba2BiFe5O13 and T ≈ 400 K for Pb(1.5)Ba(2.5)Bi2Fe6O16 the chains have a disordered arrangement. On cooling, a second-order structural phase transition to the ordered state occurs in both compounds. Symmetry changes upon phase transition are analyzed using a combination of superspace crystallography and group theory approach. Correlations between the chain ordering pattern and octahedral tilting in the perovskite blocks are discussed. Pb2Ba2BiFe5O13 and Pb(1.5)Ba(2.5)Bi2Fe6O16 undergo a transition into an antiferromagnetically (AFM) ordered state, which is characterized by a G-type AFM ordering of the Fe magnetic moments within the perovskite blocks. The AFM perovskite blocks are stacked along the CS planes producing alternating FM and AFM-aligned Fe-Fe pairs. In spite of the apparent frustration of the magnetic coupling between the perovskite blocks, all n = 4, 5, 6 A(n)Fe(n)O(3n-2) (A = Pb, Bi, Ba) feature robust antiferromagnetism with similar Néel temperatures of 623-632 K.

  16. Low Levels of Pyrophosphate in Transgenic Potato Plants Expressing E. coli Pyrophosphatase Lead to Decreased Vitality Under Oxygen Deficiency

    PubMed Central

    MUSTROPH, ANGELIKA; ALBRECHT, GERD; HAJIREZAEI, MOHAMMAD; GRIMM, BERNHARD; BIEMELT, SOPHIA

    2005-01-01

    • Background and Aims The aim of this study was to investigate the importance of pyrophosphate (PPi) for plant metabolism and survival under low oxygen stress. Responses of roots of wild-type potato plants were compared with roots of transgenic plants containing decreased amounts of PPi as a result of the constitutive expression of Escherichia coli pyrophosphatase in the cytosol. • Methods For the experiments, roots of young wild-type and transgenic potato plants growing in nutrient solution were flushed for 4 d with nitrogen, and subsequently metabolite contents as well as enzyme activities of the glycolytic pathway were determined. • Key Results and Conclusions In roots of transgenic plants containing 40 % less PPi, UDPglucose accumulated while the concentrations of hexose-6-phosphate, other glycolytic intermediates and ATP were decreased, leading to a growth retardation in aerated conditions. Apart from metabolic alterations, the activity of sucrose synthase was increased to a lower extent in the transgenic line than in wild type during hypoxia. These data suggest that sucrose cleavage was inhibited due to PPi deficiency already under aerated conditions, which has severe consequences for plant vitality under low oxygen. This is indicated by a reduction in the glycolytic activity, lower ATP levels and an impaired ability to resume growth after 4 d of hypoxia. Interestingly, the phosphorylation of fructose-6-phosphate via PPi-dependent phosphofructokinase was not altered in roots of transgenic plants. Nevertheless, our data provide some evidence for the importance of PPi to maintain plant growth and metabolism under oxygen deprivation. PMID:16027130

  17. Oxygen-deficient GdK2Nb5O15 ferroelectric epitaxial thin film

    NASA Astrophysics Data System (ADS)

    Allouche, B.; Gagou, Y.; Le Marrec, F.; Fremy, M.-A.; El Marssi, M.

    2016-12-01

    The ferroelectric compound GdK2Nb5O15 (GKN) thin film with tetragonal-tungsten-bronze–type structure was grown by pulsed-laser deposition on (001)SrRuO3/La0.5Sr0.5CoO3/MgO substrate. Using X-ray diffraction analysis we demonstrate that the phase transition temperature in the GKN thin film was shifted to high temperatures due to substrate-induced stress. Impedance spectroscopy investigations show Maxwell-Wagner–type conduction at low frequencies, which leads to resistive switching. Oxygen vacancies and temperature effects were studied to highlight the stability of the resistive switching behavior in the GKN thin film.

  18. Growth of praseodymium oxide on Si(111) under oxygen-deficient conditions

    SciTech Connect

    Schaefer, A.; Zielasek, V.; Baeumer, M.; Schmidt, Th.; Schowalter, M.; Schulz, Ch.; Rosenauer, A.; Falta, J.; Sandell, A.; Seifarth, O.; Schroeder, T.; Wollschlaeger, J.

    2009-07-15

    Surface science studies of thin praseodymium oxide films grown on silicon substrates are of high interest in view of applications in such different fields as microelectronics and heterogeneous catalysis. In particular, a detailed characterization of the growth and the final structure of the films are mandatory to achieve a fundamental understanding of such topics as oxygen mobility and defect structure, and their role for the electronic and chemical properties. In this paper, the MBE growth of praseodymium oxide films on Si(111) substrates was investigated at low-deposition rates (0.06 nm/min) and low-oxygen partial pressures (p(O{sub 2})<1x10{sup -10} mbar). To obtain insight into the structure and chemical composition of the growing film, spot profile analyzing low-energy electron diffraction (SPA-LEED), transmission electron microscopy, and synchrotron radiation-based x-ray photoelectron spectroscopy (XPS) and x-ray absorption spectroscopy (XAS) were applied. SPA-LEED reveals the formation of an initial closed layer followed by continuous roughening and formation of ordered three-dimensional structures. This result is in contrast to observations at higher-deposition rates, were a layer-by-layer growth was reported. XAS and XPS provide evidence that a continuous reaction takes place in the growing Pr{sub 2}O{sub 3} film leading to the formation of silicate and silicide structures within the film. Combining all data, a consistent picture of the deposition of praseodymium oxide on Si(111) emerges which clearly shows that in contrast to higher-throughput molecular beam epitaxy conditions the reactivity of the growing film strongly influences the growth behavior at low-deposition rates and low pressures.

  19. Electrical conductivity in oxygen-deficient phases of transition metal oxides from first-principles calculations.

    SciTech Connect

    Bondi, Robert James; Desjarlais, Michael Paul; Thompson, Aidan Patrick; Brennecka, Geoffrey L.; Marinella, Matthew

    2013-09-01

    Density-functional theory calculations, ab-initio molecular dynamics, and the Kubo-Greenwood formula are applied to predict electrical conductivity in Ta2Ox (0 x 5) as a function of composition, phase, and temperature, where additional focus is given to various oxidation states of the O monovacancy (VOn; n=0,1+,2+). Our calculations of DC conductivity at 300K agree well with experimental measurements taken on Ta2Ox thin films and bulk Ta2O5 powder-sintered pellets, although simulation accuracy can be improved for the most insulating, stoichiometric compositions. Our conductivity calculations and further interrogation of the O-deficient Ta2O5 electronic structure provide further theoretical basis to substantiate VO0 as a donor dopant in Ta2O5 and other metal oxides. Furthermore, this dopant-like behavior appears specific to neutral VO cases in both Ta2O5 and TiO2 and was not observed in other oxidation states. This suggests that reduction and oxidation reactions may effectively act as donor activation and deactivation mechanisms, respectively, for VO0 in transition metal oxides.

  20. Preparation of La1-xCaxMnO3 perovskite-graphene composites as oxygen reduction reaction electrocatalyst in alkaline medium

    NASA Astrophysics Data System (ADS)

    Hu, Jie; Wang, Lina; Shi, Lina; Huang, Hao

    2014-12-01

    La1-xCaxMnO3 perovskite-graphene composites are synthesized as catalysts for Zn-air cell cathodes. The samples are characterized by thermogravimetry-differential thermal analysis, X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and X-ray photoelectron spectroscopy. Results show that perovskite particles are homogeneously dispersed on graphene nanosheets, and that doping Ca does not change the perovskite structure. Electrochemical properties are investigated by galvanostatic discharge, linear sweep voltammetry, and electrochemical impedance spectroscopy techniques. LaMnO3-graphene composites show superior performance than pure LaMnO3. Doping Ca into the composites can tune their catalytic activity and sample prepared with x = 0.4 possesses the highest electrocatalytic activity. The measurement of the rotating ring-disk electrode reveals that the electron transfer number of La0.6Ca0.4MnO3-graphene is 3.6. These results indicate that the La1-xCaxMnO3-graphene composites are potential air electrodes catalysts.

  1. New Opportunity for in Situ Exsolution of Metallic Nanoparticles on Perovskite Parent.

    PubMed

    Sun, Yi-Fei; Zhang, Ya-Qian; Chen, Jian; Li, Jian-Hui; Zhu, Ying-Tao; Zeng, Yi-Min; Amirkhiz, Babak Shalchi; Li, Jian; Hua, Bin; Luo, Jing-Li

    2016-08-10

    One of the main challenges for advanced metallic nanoparticles (NPs) supported functional perovskite catalysts is the simultaneous achievement of a high population of NPs with uniform distribution as well as long-lasting high performance. These are also the essential requirements for optimal electrode catalysts used in solid oxide fuel cells and electrolysis cells (SOFCs and SOECs). Herein, we report a facile operando manufacture way that the crystal reconstruction of double perovskite under reducing atmosphere can spontaneously lead to the formation of ordered layered oxygen deficiency and yield segregation of massively and finely dispersed NPs. The real-time observation of this emergent process was performed via an environmental transmission electron microscope. Density functional theory calculations prove that the crystal reconstruction induces the loss of coordinated oxygen surrounding B-site cations, serving as the driving force for steering fast NP growth. The prepared material shows promising capability as an active and stable electrode for SOFCs in various fuels and SOECs for CO2 reduction. The conception exemplified here could conceivably be extended to fabricate a series of supported NPs perovskite catalysts with diverse functionalities.

  2. Non-volatile memory based on transition metal perovskite oxide resistance switching

    NASA Astrophysics Data System (ADS)

    Nian, Yibo

    Driven by the non-volatile memory market looking for new advanced materials, this dissertation focuses on the study of non-volatile resistive random access memory (RRAM) based on transition metal perovskite oxides. Pr0.7Ca0.3MnO3 (PCMO), one of the representative materials in this family, has demonstrated a large range of resistance change when short electrical pulses with different polarity are applied. Such electrical-pulse-induced resistance (EPIR), with attractive features such as fast response, low power, high-density and non-volatility, makes PCMO and related materials promising candidates for non-volatile RRAM application. The objective of this work is to investigate, optimize and understand the properties of this universal EPIR behavior in transition metal perovskite oxide, represented by PCMO thin film devices. The research work includes fabrication of PCMO thin film devices, characterization of these EPIR devices as non-volatile memories, and investigation of their resistive switching mechanisms. The functionality of this perovskite oxide RRAM, including pulse magnitude/width dependence, power consumption, retention, endurance and radiation-hardness has been investigated. By studying the "shuttle tail" in hysteresis switching loops of oxygen deficient devices, a diffusion model with oxygen ions/vacancies as active agents at the metal/oxide interface is proposed for the non-volatile resistance switching effect in transition metal perovskite oxide thin films. The change of EPIR switching behavior after oxygen/argon ion implantation also shows experiment support for the proposed model. Furthermore, the universality, scalability and comparison with other non-volatile memories are discussed for future application.

  3. Functional Deficiency of Aryl Hydrocarbon Receptor Augments Oxygen Toxicity-Induced Alveolar Simplification in Newborn Mice

    PubMed Central

    Shivanna, Binoy; Zhang, Wenyan; Jiang, Weiwu; Welty, Stephen E.; Couroucli, Xanthi I.; Wang, Lihua; Moorthy, Bhagavatula

    2013-01-01

    Hyperoxia contributes to the development of bronchopulmonary dysplasia (BPD) in premature infants. New BPD is characterized as having alveolar simplification. We reported previously that aryl hydrocarbon receptor (AhR) deficiency increased susceptibility to hyperoxic lung injury in adult mice, and this was associated with decreased expression of cytochrome P450 1A enzymes and increased lung inflammation. Whether AhR protects newborn mice against hyperoxia-induced alveolar simplification is unknown. Thus, we tested the hypothesis that decreased activation of the pulmonary AhR augments hyperoxia-induced alveolar simplification and lung inflammation in newborn mice. Experimental groups included one-day old wild type (WT) and AhR dysfunctional (AhRd) mice exposed to 21% O2 (air) or 85% O2 (hyperoxia) for 14 d. Exposure of newborn WT mice to hyperoxia resulted in increased protein, enzyme and mRNA expression of the AhR-regulated lung cytochrome P450 1A1, NAD(P)H quinone oxidoreductase-1, and microsomal glutathione S-transferase 1 enzymes, suggesting that hyperoxia increases activation of the pulmonary AhR. On the other hand, in the AhRd mice, hyperoxia induced the AhR-regulated enzymes to a lesser extent probably due to the dysfunctional AhR in these mice. Alveolar simplification and lung inflammation was increased in mice exposed to hyperoxia compared to those exposed to air, and AhRd mice were more susceptible to hyperoxia-induced alveolar simplification and lung inflammation compared to WT mice. These findings suggest that decreased activation of the pulmonary AhR in newborn AhRd mice augments hyperoxia-induced alveolar simplification and lung inflammation in these mice. PMID:23337360

  4. Atomic layer deposition of amorphous oxygen-deficient TiO2-x on carbon nanotubes as cathode materials for lithium-air batteries

    NASA Astrophysics Data System (ADS)

    Yang, Jingbo; Ma, Dingtao; Li, Yongliang; Zhang, Peixin; Mi, Hongwei; Deng, Libo; Sun, Lingna; Ren, Xiangzhong

    2017-08-01

    The amorphous oxygen-deficient TiO2-x thin layer coated carbon nanotubes (CNTs) are synthesized by atomic layer deposition and employed as cathode materials for lithium-air battery. The cathode demonstrates high electrocatalytic activity toward electrode reactions, resulting from the introduction of oxygen-deficient TiO2-x into the nanocomposites. It is found that the intrinsically isotropic nature of amorphous TiO2 which a certain amount of Ti3.5+ and Ti3+ can improve the catalytic activity. Consequently, the battery with the corresponded CNT@TiO2-x cathode shows high discharge/charge capacities and good cycling performance, which the cyclic retention of more than 90 cycles are achieved, while with the pristine CNTs only 50 cycles are obtained. This study provides an approach to fabricate cathode materials for lithium-air battery and moreover clarifies the influence of oxygen vacancies of TiO2 on the electrochemical performance.

  5. Colossal positive magnetoresistance in surface-passivated oxygen-deficient strontium titanite

    PubMed Central

    David, Adrian; Tian, Yufeng; Yang, Ping; Gao, Xingyu; Lin, Weinan; Shah, Amish B.; Zuo, Jian-Min; Prellier, Wilfrid; Wu, Tom

    2015-01-01

    Modulation of resistance by an external magnetic field, i.e. magnetoresistance effect, has been a long-lived theme of research due to both fundamental science and device applications. Here we report colossal positive magnetoresistance (CPMR) (>30,000% at a temperature of 2 K and a magnetic field of 9 T) discovered in degenerate semiconducting strontium titanite (SrTiO3) single crystals capped with ultrathin SrTiO3/LaAlO3 bilayers. The low-pressure high-temperature homoepitaxial growth of several unit cells of SrTiO3 introduces oxygen vacancies and high-mobility carriers in the bulk SrTiO3, and the three-unit-cell LaAlO3 capping layer passivates the surface and improves carrier mobility by suppressing surface-defect-related scattering. The coexistence of multiple types of carriers and inhomogeneous transport lead to the emergence of CPMR. This unit-cell-level surface engineering approach is promising to be generalized to others oxides, and to realize devices with high-mobility carriers and interesting magnetoelectronic properties. PMID:25975606

  6. Nano Ce2O2S with Highly Enriched Oxygen-Deficient Ce(3+) Sites Supported by N and S Dual-Doped Carbon as an Active Oxygen-Supply Catalyst for the Oxygen Reduction Reaction.

    PubMed

    Yang, Liu; Cai, Zhuang; Hao, Liang; Xing, Zipeng; Dai, Ying; Xu, Xin; Pan, Siyu; Duan, Yaqiang; Zou, Jinlong

    2017-07-12

    The design of rare-earth-metal oxide/oxysulfide catalysts with high activity and durability for the oxygen reduction reaction (ORR) is still a grand challenge at present. In this study, Ce-species (Ce2O2S/CeO2)/N, S dual-doped carbon (Ce-species/NSC) catalysts with promising oxygen storage/release capacities are prepared at different temperatures (800-1000 °C) to enhance the ORR efficiency. Mechanisms for the effects of temperature on crystalline phase transition between CeO2 and Ce2O2S and structure evolution of Ce-species/NSCs are inferred to better understand their catalytic activity. Porous Ce2O2S/NSC (950 °C) catalyst as the air-breathing cathode exhibits a maximum power density of 1087.2 mW m(-2), which is higher than those of other Ce-species/NSCs and commercial Pt/C (989.13 mW m(-2)) in microbial fuel cells. The decline of the power density of Ce2O2S/NSC (950 °C) cathode is 8.7% after 80 days of operation, which is far lower than that of Pt/C (36.7%). Ce2O2S/NSC (950 °C) has a four-electron selectivity toward the ORR and a low charge-transfer resistance (5.49 Ω), contributing to high ORR activity and durability. The promising ORR catalytic activity of Ce2O2S/NSC (950 °C) is attributed to its high specific surface area (338.9 m(2) g(-1)), varied active sites, high electrical conductivity, and sufficient oxygen vacancies in the Ce2O2S skeleton. The high content of Ce(3+) in Ce2O2S/NSC (950 °C) facilitates the formation of more oxygen-deficient Ce(3+) sites that generate more oxygen vacancies to release/store more oxygen to stabilize the available oxygen for the ORR. Thus, this study provides a new perspective for preparation and application of this new type of the ORR catalyst.

  7. Pb{sub 2.85}Ba{sub 2.15}Fe{sub 4}SnO{sub 13}: A new member of the A{sub n}B{sub n}O{sub 3n-2} anion-deficient perovskite-based homologous series

    SciTech Connect

    Korneychik, Oleg E.; Batuk, Maria; Abakumov, Artem M.; Hadermann, Joke; Rozova, Marina G.; Sheptyakov, Denis V.; Pokholok, Konstantin V.; Filimonov, Dmitry S.; Antipov, Evgeny V.

    2011-12-15

    Pb{sub 2.85}Ba{sub 2.15}Fe{sub 4}SnO{sub 13}, a new n=5 member of the anion-deficient perovskite based A{sub n}B{sub n}O{sub 3n-2} (A=Pb, Ba, B=Fe, Sn) homologous series, was synthesized by the solid state method. The crystal structure of Pb{sub 2.85}Ba{sub 2.15}Fe{sub 4}SnO{sub 13} was investigated using a combination of neutron powder diffraction, electron diffraction, high angle annular dark field scanning transmission electron microscopy and Moessbauer spectroscopy. It crystallizes in the Ammm space group with unit cell parameters a=5.7990(1) A, b=4.04293(7) A and c=26.9561(5) A. The Pb{sub 2.85}Ba{sub 2.15}Fe{sub 4}SnO{sub 13} structure consists of quasi two-dimensional perovskite blocks separated by 1/2[110](1-bar 01){sub p} crystallographic shear (CS) planes. The corner-sharing FeO{sub 6} octahedra at the CS planes are transformed into edge-sharing FeO{sub 5} distorted tetragonal pyramids. The octahedral positions in the perovskite blocks between the CS planes are jointly taken up by Fe and Sn, with a preference of Sn towards the position at the center of the perovskite block. The chains of FeO{sub 5} pyramids and (Fe,Sn)O{sub 6} octahedra of the perovskite blocks delimit six-sided tunnels at the CS planes occupied by double chains of Pb atoms. The compound is antiferromagnetically ordered below T{sub N}=368{+-}15 K. Highlights: Black-Right-Pointing-Pointer Compound Pb{sub 2.85}Ba{sub 2.15}Fe{sub 4}SnO{sub 13} was synthesized and characterized for the first time. Black-Right-Pointing-Pointer It is a new member of the anion-deficient perovskite based homologous series A{sub n}B{sub n}O{sub 3n-2} with n=5. Black-Right-Pointing-Pointer Its structure consists of quasi two-dimensional perovskite blocks separated by interfaces. Black-Right-Pointing-Pointer Interfaces are made up of edge-sharing FeO{sub 5} distorted tetragonal pyramids. Black-Right-Pointing-Pointer Pb{sub 2.85}Ba{sub 2.15}Fe{sub 4}SnO{sub 13} is antiferromagnetically ordered below T{sub N}=368

  8. Oxygen vacancy formation characteristics in the bulk and across different surface terminations of La(1₋x)SrxFe(1₋y)CoyO(3₋δ) perovskite oxides for CO2 conversion

    SciTech Connect

    Maiti, Debtanu; Daza, Yolanda A.; Yung, Matthew M.; Kuhn, John N.; Bhethanabotla, Venkat R.

    2016-01-01

    Density functional theory (DFT) based investigation of two parameters of prime interest -- oxygen vacancy and surface terminations along (100) and (110) planes -- has been conducted for La(1-x)SrxFe(1-y)CoyO(3-..delta..) perovskite oxides in view of their application towards thermochemical carbon dioxide conversion reactions. The bulk oxygen vacancy formation energies for these mixed perovskite oxides are found to increase with increasing lanthanum and iron contents in the 'A' site and 'B' site, respectively. Surface terminations along (100) and (110) crystal planes are studied to probe their stability and their capabilities to accommodate surface oxygen vacancies. Amongst the various terminations, the oxygen-rich (110) surface and strontium-rich (100) surface are the most stable, while transition metal-rich terminations along (100) revealed preference towards the production of oxygen vacancies. The carbon dioxide adsorption strength, a key descriptor for CO2 conversion reactions, is found to increase on oxygen vacant surfaces thus establishing the importance of oxygen vacancies in CO2 conversion reactions. Amongst all the surface terminations, the lanthanum-oxygen terminated surface exhibited the strongest CO2 adsorption strength. The theoretical prediction of the oxygen vacancy trends and the stability of the samples were corroborated by the temperature-programmed reduction and oxidation reactions and in situ XRD crystallography.

  9. Oxygen vacancy formation characteristics in the bulk and across different surface terminations of La(1₋x)SrxFe(1₋y)CoyO(3₋δ) perovskite oxides for CO2 conversion

    SciTech Connect

    Maiti, Debtanu; Daza, Yolanda A.; Yung, Matthew M.; Kuhn, John N.; Bhethanabotla, Venkat R.

    2016-03-07

    Density functional theory (DFT) based investigation of two parameters of prime interest -- oxygen vacancy and surface terminations along (100) and (110) planes -- has been conducted for La(1-x)SrxFe(1-y)CoyO(3-$\\delta$) perovskite oxides in view of their application towards thermochemical carbon dioxide conversion reactions. The bulk oxygen vacancy formation energies for these mixed perovskite oxides are found to increase with increasing lanthanum and iron contents in the 'A' site and 'B' site, respectively. Surface terminations along (100) and (110) crystal planes are studied to probe their stability and their capabilities to accommodate surface oxygen vacancies. Amongst the various terminations, the oxygen-rich (110) surface and strontium-rich (100) surface are the most stable, while transition metal-rich terminations along (100) revealed preference towards the production of oxygen vacancies. The carbon dioxide adsorption strength, a key descriptor for CO2 conversion reactions, is found to increase on oxygen vacant surfaces thus establishing the importance of oxygen vacancies in CO2 conversion reactions. Amongst all the surface terminations, the lanthanum-oxygen terminated surface exhibited the strongest CO2 adsorption strength. Finally, the theoretical prediction of the oxygen vacancy trends and the stability of the samples were corroborated by the temperature-programmed reduction and oxidation reactions and in situ XRD crystallography.

  10. Magnetic, specific heat and electrical transport properties of oxygen-deficient nanosized rutile TiO2‑δ

    NASA Astrophysics Data System (ADS)

    Tran, Vinh Hung; Thi Quynh Hoa, Nguyen

    2017-03-01

    An oxygen-deficient nanosized {{TiO}}2-δ , δ ∼ 0.7 sample was synthesized by a solvothermal method, and was characterized to have both ∼3 nm amorphous solid and ∼36–46 nm diameter rutile nanowires. Physical properties of the sample were investigated by measuring magnetic, specific heat, electrical resistance and magnetoresitance properties. DC magnetization M(H) data confirm ferromagnetic behavior previously reported for undoped TiO2. Furthermore, M(T) dependence follows the power-law relation M{(T)\\propto (1-T/{T}C)}β in the near-critical regime, yielding Curie temperature {T}C ∼ 415 K and critical exponent β = 0.2. Moreover, our results of AC magnetic susceptibility measurements suggest an additional phase transition at {T}* ∼ 310 K, presumably due to spin orientation. The metallic-like electrical resistance exhibits a distinct drop below {T}* with a strong thermal hysteresis in the temperature range 225–275 K. Specific heat in the temperature range 20–300 K is well described by the sum of contributions from acoustic phonons with Debye temperature 605 K and optical phonons with Einstein temperature 113 K. Below 10 K the specific heat divulges a large excess, which can be interpreted as an additional contribution originating from soft potentials.

  11. Phosphorus and Iron Deficiencies Influences Rice Shoot Growth in an Oxygen Dependent Manner: Insight from Upland and Lowland Rice

    PubMed Central

    Mongon, Jenjira; Chaiwong, Nanthana; Bouain, Nadia; Prom-u-thai, Chanakan; Secco, David; Rouached, Hatem

    2017-01-01

    Rice is the main staple crop for one-third of the world population. To maximize yields, large quantities and constant input of fertilizers containing essential nutrients such as phosphorus (P) and iron (Fe) are added. Rice can germinate in both aerobic and anaerobic conditions, but the crosstalk between oxygen (O2) and nutrients such as P and Fe on plant growth remains obscure. The aim of this work was to test whether such interactions exist, and, if so, if they are conserved between up- and lowland rice varieties. To do so, we assessed shoot and root biomass as well as inorganic phosphate (Pi) accumulation in four rice varieties, including two lowland rice varieties Nipponbare and Suphanburi 1 (SPR1) (adapted to non-aerated condition) and two upland rice varieties CMU122 and Sew Mae Jun (SMJ) (adapted to aerated condition) under various conditions of Pi and/or Fe deficiencies, in aerated and non-areated solution. Under these different experimental conditions, our results revealed that the altered shoot biomass in Nipponbare and SPR1 was O2-dependent but to a lesser extent in CMU122 and SMJ cultivars. In this perspective, discovering the biological significance and molecular basis of these mineral elements and O2 signal interaction is needed to fully appreciate the performance of plants to multiple environmental changes. PMID:28287426

  12. Phosphorus and Iron Deficiencies Influences Rice Shoot Growth in an Oxygen Dependent Manner: Insight from Upland and Lowland Rice.

    PubMed

    Mongon, Jenjira; Chaiwong, Nanthana; Bouain, Nadia; Prom-U-Thai, Chanakan; Secco, David; Rouached, Hatem

    2017-03-10

    Rice is the main staple crop for one-third of the world population. To maximize yields, large quantities and constant input of fertilizers containing essential nutrients such as phosphorus (P) and iron (Fe) are added. Rice can germinate in both aerobic and anaerobic conditions, but the crosstalk between oxygen (O₂) and nutrients such as P and Fe on plant growth remains obscure. The aim of this work was to test whether such interactions exist, and, if so, if they are conserved between up- and lowland rice varieties. To do so, we assessed shoot and root biomass as well as inorganic phosphate (Pi) accumulation in four rice varieties, including two lowland rice varieties Nipponbare and Suphanburi 1 (SPR1) (adapted to non-aerated condition) and two upland rice varieties CMU122 and Sew Mae Jun (SMJ) (adapted to aerated condition) under various conditions of Pi and/or Fe deficiencies, in aerated and non-areated solution. Under these different experimental conditions, our results revealed that the altered shoot biomass in Nipponbare and SPR1 was O₂-dependent but to a lesser extent in CMU122 and SMJ cultivars. In this perspective, discovering the biological significance and molecular basis of these mineral elements and O₂ signal interaction is needed to fully appreciate the performance of plants to multiple environmental changes.

  13. AC Electrical Conduction of Cr-Doped SrTiO3 Thin Films with an Oxygen-Deficient Interface Layer

    NASA Astrophysics Data System (ADS)

    Phan, Bach Thang; Eom, Ki Tae; Lee, Jaichan

    2017-01-01

    The ac electrical conduction of Cr-doped SrTiO3 thin films with an oxygen-deficient interface layer was investigated as a function of temperature and frequency. The Cr-doped SrTiO3 (Cr-STO) thin films with an ultra-thin (˜2 nm) oxygen-deficient layer inserted between the top electrode and the Cr-STO layer exhibited two ac conduction mechanisms, i.e., variable-range hopping and small-polaron hopping conduction, accompanied by a relaxation process. Since high oxygen deficiency induces large lattice distortion in the depletion layer, the first relaxation process occurs at low frequencies in the thin oxygen depletion layer Cr-SrTiO3-δ , and the corresponding conduction behavior follows the small-polaron tunneling model. In the high frequency range, an additional relaxation process is involved and is associated with the variable-range hopping between the localized states in the band gap of the thick Cr-SrTiO3 layer.

  14. Electrochemical studies of perovskite mixed conductors

    SciTech Connect

    Brosha, E.L.; Chung, B.W.; Garzon, F.H.

    1994-12-01

    Research into the growth of high-quality single crystal thin films of high transition temperature {Tc} superconductors have stimulated interest in other perovskite metal oxides with a variety of physical properties. Thin films of perovskite materials are among the major focal research areas for optical, sensor, electronic, and superconducting applications. Two lanthanum-based oxygen/electronic conducting perovskite oxides of particular interest for high temperature fuel cell electrodes and interconnects and for other electrochemical applications such as oxygen separation devices are La{sub 1{minus}x}Sr{sub x}MnO{sub 3{minus}y} and La{sub 1{minus}x}Sr{sub x}CoO{sub 3{minus}y}. The La-based perovskites are valuable for these technologies because they reduce interfacial resistances by eliminating the need for a three phase contact area (gas, metal electrode, electrolyte). In addition, these oxides may also serve a valuable role as novel catalysts or catalytic supports; however, little is known about what catalytic properties they may possess. Fundamental study of the electrochemical, diffusional oxygen transport, and surface catalytic properties of these materials can be greatly simplified if the complications associated with the presence of grain boundaries and multiple crystallite orientations can be avoided. Therefore, single crystals of these La-based perovskites become highly desirable. In this work, the authors report the structural and electrical properties of highly oriented thin films of La{sub 0.84}Sr{sub 0.16}MnO{sub 3} and La{sub 0.8}Sr{sub 0.2}CoO{sub 3} grown on single crystal Y-ZrO{sub 2} substrates. An addition, the authors have demonstrated growing, in situ, epitaxial multilayer perovskite/fluorite/perovskite configurations for fundamental fuel cell modeling.

  15. Crystallographic and magnetic structure of the perovskite-type compound BaFeO2.5: unrivaled complexity in oxygen vacancy ordering.

    PubMed

    Clemens, Oliver; Gröting, Melanie; Witte, Ralf; Perez-Mato, J Manuel; Loho, Christoph; Berry, Frank J; Kruk, Robert; Knight, Kevin S; Wright, Adrian J; Hahn, Horst; Slater, Peter R

    2014-06-16

    We report here on the characterization of the vacancy-ordered perovskite-type structure of BaFeO2.5 by means of combined Rietveld analysis of powder X-ray and neutron diffraction data. The compound crystallizes in the monoclinic space group P2(1)/c [a = 6.9753(1) Å, b = 11.7281(2) Å, c = 23.4507(4) Å, β = 98.813(1)°, and Z = 28] containing seven crystallographically different iron atoms. The coordination scheme is determined to be Ba7(FeO4/2)1(FeO3/2O1/1)3(FeO5/2)2(FeO6/2)1 = Ba7Fe([6])1Fe([5])2Fe([4])4O17.5 and is in agreement with the (57)Fe Mössbauer spectra and density functional theory based calculations. To our knowledge, the structure of BaFeO2.5 is the most complicated perovskite-type superstructure reported so far (largest primitive cell, number of ABX2.5 units per unit cell, and number of different crystallographic sites). The magnetic structure was determined from the powder neutron diffraction data and can be understood in terms of "G-type" antiferromagnetic ordering between connected iron-containing polyhedra, in agreement with field-sweep and zero-field-cooled/field-cooled measurements.

  16. Efficient Suppression of Electron-Hole Recombination in Oxygen-Deficient Hydrogen-Treated TiO2 Nanowires for Photoelectrochemical Water Splitting.

    PubMed

    Pesci, Federico M; Wang, Gongming; Klug, David R; Li, Yat; Cowan, Alexander J

    2013-12-05

    There is an increasing level of interest in the use of black TiO2 prepared by thermal hydrogen treatments (H:TiO2) due to the potential to enhance both the photocatalytic and the light-harvesting properties of TiO2. Here, we examine oxygen-deficient H:TiO2 nanotube arrays that have previously achieved very high solar-to-hydrogen (STH) efficiencies due to incident photon-to-current efficiency (IPCE) values of >90% for photoelectrochemical water splitting at only 0.4 V vs RHE under UV illumination. Our transient absorption (TA) mechanistic study provides strong evidence that the improved electrical properties of oxygen-deficient TiO2 enables remarkably efficient spatial separation of electron-hole pairs on the submicrosecond time scale at moderate applied bias, and this coupled to effective suppression of microsecond to seconds charge carrier recombination is the primary factor behind the dramatically improved photoelectrochemical activity.

  17. Influence of oxygen deficiency and of neutron-induced defects on flux pinning in melt textured bulk YBa 2Cu 3O 7- x samples

    NASA Astrophysics Data System (ADS)

    Wisniewski, A.; Czurda, C.; Weber, H. W.; Baran, M.; Reissner, M.; Steiner, W.; Zhang, P. X.; Zhou, L.

    1996-02-01

    Critical current densities ( Jc), irreversibility lines (IL) and the time dependence of magnetic moments in melt-textured YBa 2Cu 3O 7- x with different oxygen contents (92.4 K < Tc < 27.4 K) were investigated. The samples show an increasing tendency towards two-dimensional pinning with decreasing oxygen content. The values of Jc and the effective activation energy decrease systematically and all the ILs shift to lower magnetic fields and temperatures with decreasing oxygen content. The ILs show a crossover from a power law dependence Hirr = β(1 - Tirr/ Tc) α with α ∼ {3}/{2} to a more rapid temperature dependence at higher fields. The field Hcr, at which the crossover occurs, is lower for samples with higher oxygen deficiency. After neutron irradiation Jc increases in all cases except for the material with Tc = 27.4 K, and the temperature dependence of Jc becomes flatter than in the unirradiated state. After irradiation the ILs change differently depending on oxygen content, i.e. they shift markedly to higher fields and temperature at intermediate oxygen content, change only slightly or shift to lower fields and temperatures at high and low oxygen contents. For all the samples the crossover field Hcr increases after irradiation.

  18. Marine Oxygen-Deficient Zones Harbor Depauperate Denitrifying Communities Compared to Novel Genetic Diversity in Coastal Sediments.

    PubMed

    Bowen, Jennifer L; Weisman, David; Yasuda, Michie; Jayakumar, Amal; Morrison, Hilary G; Ward, Bess B

    2015-08-01

    Denitrification is a critically important biogeochemical pathway that removes fixed nitrogen from ecosystems and thus ultimately controls the rate of primary production in nitrogen-limited systems. We examined the community structure of bacteria containing the nirS gene, a signature gene in the denitrification pathway, from estuarine and salt marsh sediments and from the water column of two of the world's largest marine oxygen-deficient zones (ODZs). We generated over 125,000 nirS gene sequences, revealing a large degree of genetic diversity including 1,815 unique taxa, the vast majority of which formed clades that contain no cultured representatives. These results underscore how little we know about the genetic diversity of metabolisms underlying this critical biogeochemical pathway. Marine sediments yielded 1,776 unique taxa when clustered at 95 % sequence identity, and there was no single nirS denitrifier that was a competitive dominant; different samples had different highly abundant taxa. By contrast, there were only 39 unique taxa identified in samples from the two ODZs, and 99 % of the sequences belonged to 5 or fewer taxa. The ODZ samples were often dominated by nirS sequences that shared a 92 % sequence identity to a nirS found in the anaerobic ammonium-oxidizing (anammox) genus Scalindua. This sequence was abundant in both ODZs, accounting for 38 and 59 % of all sequences, but it was virtually absent in marine sediments. Our data indicate that ODZs are remarkably depauperate in nirS genes compared to the remarkable genetic richness found in coastal sediments.

  19. Polarization twist in perovskite ferrielectrics

    PubMed Central

    Kitanaka, Yuuki; Hirano, Kiyotaka; Ogino, Motohiro; Noguchi, Yuji; Miyayama, Masaru; Moriyoshi, Chikako; Kuroiwa, Yoshihiro

    2016-01-01

    Because the functions of polar materials are governed primarily by their polarization response to external stimuli, the majority of studies have focused on controlling polar lattice distortions. In some perovskite oxides, polar distortions coexist with nonpolar tilts and rotations of oxygen octahedra. The interplay between nonpolar and polar instabilities appears to play a crucial role, raising the question of how to design materials by exploiting their coupling. Here, we introduce the concept of ‘polarization twist’, which offers enhanced control over piezoelectric responses in polar materials. Our experimental and theoretical studies provide direct evidence that a ferrielectric perovskite exhibits a large piezoelectric response because of extended polar distortion, accompanied by nonpolar octahedral rotations, as if twisted polarization relaxes under electric fields. The concept underlying the polarization twist opens new possibilities for developing alternative materials in bulk and thin-film forms. PMID:27586824

  20. Structure and electrical and transport properties of cation-deficient samples of perovskite ferrocuprates RBaCuFeO5 + δ ( R = Y, La)

    NASA Astrophysics Data System (ADS)

    Klyndyuk, A. I.; Chizhova, E. A.

    2008-04-01

    The structure, thermal expansion, and electrical properties of cation-deficient ferrocuprates RBaCuFeO5 + δ ( R = Y, La), which are p-type semiconductors, are investigated. The linear thermal expansion coefficient of the yttrium-barium ferrocuprate decreases upon formation of vacancies in the A sublattice (Y, Ba), while the unit cell parameters remain practically unchanged upon the formation of vacancies in different sublattices (Y, Ba, Cu/Fe) of the crystal structure. From analyzing the results of the thermopower measurements, it is assumed that the YBaCuFeO5 + δ ferrocuprate is actually a “nanocomposite” consisting of nanoregions of the Y2Cu2O5 and BaFeO3 - δ phases. The lanthanum deficiency brings about an increase in the LaBaCuFeO5 + δ unit cell while leaving very nearly unaffected its linear thermal expansion coefficient and electrical properties. The formation of cation vacancies in extended [Ba(Cu,Fe)2O5] blocks of the LaBaCuFeO5 + δ phase gives rise to tetragonal distortion of its cubic structure, a decrease in the linear thermal expansion coefficient, and an increase in the electrical resistivity of the samples, the latter resulting primarily from an increase in the carrier transport energy in (Cu,Fe)O2 layers of LaBaCuFeO5 + δ.

  1. Resonant halide perovskite nanoparticles

    NASA Astrophysics Data System (ADS)

    Tiguntseva, Ekaterina Y.; Ishteev, Arthur R.; Komissarenko, Filipp E.; Zuev, Dmitry A.; Ushakova, Elena V.; Milichko, Valentin A.; Nesterov-Mueller, Alexander; Makarov, Sergey V.; Zakhidov, Anvar A.

    2017-09-01

    The hybrid halide perovskites is a prospective material for fabrication of cost-effective optical devices. Unique perovskites properties are used for solar cells and different photonic applications. Recently, perovskite-based nanophotonics has emerged. Here, we consider perovskite like a high-refractive index dielectric material, which can be considered to be a basis for nanoparticles fabrication with Mie resonances. As a result, we fabricate and study resonant perovskite nanoparticles with different sizes. We reveal, that spherical nanoparticles show enhanced photoluminescence signal. The achieved results lay a cornerstone in the field of novel types of organic-inorganic nanophotonics devices with optical properties improved by Mie resonances.

  2. Influence of Ca-deficiency on the magneto-transport properties in La0.8Ca0.2MnO3 perovskite and estimation of magnetic entropy change

    NASA Astrophysics Data System (ADS)

    Khlifi, M.; Bejar, M.; Dhahri, E.; Lachkar, P.; Hlil, E. K.

    2012-05-01

    La0.8Ca0.2 - x□xMnO3 (x = 0.00, 0.10, and 0.20) perovskite was prepared by the conventional solid-state reaction and annealed at 1473 K. X-ray diffraction and scanning electron microscopy shown the existence of a secondary phase attributed to the unreacted Mn3O4 oxide. The magneto transport properties have been investigated based on the temperature dependence of the resistivity ρ(T) measurements under several applied magnetic fields. We note that the La0.8Ca0.2MnO3 (x = 0.00) sample has a classical metal-insulator transition at Tρ. But we have observed that the lacunars samples (x = 0.10 and 0.20) include a metallic and insulator behavior simultaneously below Tρ and the resistivity is dominated by tunneling through the barriers associated with the insulating phase. In other words, the calcium deficiency favors the enhancement of the insulator behavior. The electrical resistivity is fitted with the phenomenological percolation model, which is based on the phase segregation of ferromagnetic metallic clusters and paramagnetic insulating regions. Furthermore, we found that the estimated results are in good agreement with experimental data. Above all, the resistivity dependence on the temperature and magnetic field data is used to deduce the magnetic entropy change. We have found that these magnetic entropy change values are similar to those calculated in our previous work from the magnetic measurements. Finally, we have found an excellent estimation of the magnetic entropy change based on the Landau theory.

  3. Influence of Ca-deficiency on the magneto-transport properties in La(0.8)Ca(0.2)MnO(3) perovskite and estimation of magnetic entropy change.

    PubMed

    Khlifi, M; Bejar, M; Dhahri, E; Lachkar, P; Hlil, E K

    2012-05-15

    La(0.8)Ca(0.2 - x)□(x)MnO(3) (x = 0.00, 0.10, and 0.20) perovskite was prepared by the conventional solid-state reaction and annealed at 1473 K. X-ray diffraction and scanning electron microscopy shown the existence of a secondary phase attributed to the unreacted Mn(3)O(4) oxide. The magneto transport properties have been investigated based on the temperature dependence of the resistivity ρ(T) measurements under several applied magnetic fields. We note that the La(0.8)Ca(0.2)MnO(3) (x = 0.00) sample has a classical metal-insulator transition at T(ρ). But we have observed that the lacunars samples (x = 0.10 and 0.20) include a metallic and insulator behavior simultaneously below T(ρ) and the resistivity is dominated by tunneling through the barriers associated with the insulating phase. In other words, the calcium deficiency favors the enhancement of the insulator behavior. The electrical resistivity is fitted with the phenomenological percolation model, which is based on the phase segregation of ferromagnetic metallic clusters and paramagnetic insulating regions. Furthermore, we found that the estimated results are in good agreement with experimental data. Above all, the resistivity dependence on the temperature and magnetic field data is used to deduce the magnetic entropy change. We have found that these magnetic entropy change values are similar to those calculated in our previous work from the magnetic measurements. Finally, we have found an excellent estimation of the magnetic entropy change based on the Landau theory.

  4. Understanding chemical expansion in perovskite-structured oxides.

    PubMed

    Marrocchelli, Dario; Perry, Nicola H; Bishop, Sean R

    2015-04-21

    In this work, chemical expansion in perovskite oxides was characterized in detail, motivated, inter alia, by a desire to understand the lower chemical expansion coefficients observed for perovskites in comparison to fluorite-structured oxides. Changes in lattice parameter and in local atomic arrangements taking place during compositional changes of perovskites, i.e., stoichiometric expansion, were investigated by developing an empirical model and through molecular dynamics and density functional theory atomistic simulations. An accurate empirical expression for predicting lattice constants of perovskites was developed, using a similar approach to previous reports. From this equation, analytical expressions relating chemical expansion coefficients to separate contributions from the cation and anion sublattices, assuming Shannon ionic radii, were developed and used to isolate the effective radius of an oxygen vacancy, rV. Using both experimental and simulated chemical expansion coefficient data, rV for a variety of perovskite compositions was estimated, and trends in rV were studied. In most cases, rV was slightly smaller than or similar to the radius of an oxide ion, but larger than in the fluorite structured materials. This result was in good agreement with the atomistic simulations, showing contractive relaxations of the closest oxide ions towards the oxygen vacancy. The results indicate that the smaller chemical expansion coefficients of perovskites vs. fluorites are largely due to the smaller change in cation radii in perovskites, given that the contraction around the oxygen vacancy appears to be less in this structure. Limitations of applicability for the model are discussed.

  5. Hybrid Perovskite/Perovskite Heterojunction Solar Cells.

    PubMed

    Hu, Yinghong; Schlipf, Johannes; Wussler, Michael; Petrus, Michiel L; Jaegermann, Wolfram; Bein, Thomas; Müller-Buschbaum, Peter; Docampo, Pablo

    2016-06-28

    Recently developed organic-inorganic hybrid perovskite solar cells combine low-cost fabrication and high power conversion efficiency. Advances in perovskite film optimization have led to an outstanding power conversion efficiency of more than 20%. Looking forward, shifting the focus toward new device architectures holds great potential to induce the next leap in device performance. Here, we demonstrate a perovskite/perovskite heterojunction solar cell. We developed a facile solution-based cation infiltration process to deposit layered perovskite (LPK) structures onto methylammonium lead iodide (MAPI) films. Grazing-incidence wide-angle X-ray scattering experiments were performed to gain insights into the crystallite orientation and the formation process of the perovskite bilayer. Our results show that the self-assembly of the LPK layer on top of an intact MAPI layer is accompanied by a reorganization of the perovskite interface. This leads to an enhancement of the open-circuit voltage and power conversion efficiency due to reduced recombination losses, as well as improved moisture stability in the resulting photovoltaic devices.

  6. Ba{sub 3}Fe{sub 2}WO{sub 9-{delta}}: Effect of oxygen non-stoichiometry on structural and magnetic properties

    SciTech Connect

    Ivanov, S.A. . E-mail: ivan@cc.nifhi.ac.ru; Eriksson, S.-G. . E-mail: stene@chalmers.se; Tellgren, R. . E-mail: rte@mkem.uu.se; Rundlof, H.; Nordblad, P.; Eriksen, J.

    2006-08-15

    The magnetic and structural properties of oxygen-deficient perovskites with composition Ba{sub 3}Fe{sub 2}WO{sub 9-{delta}} (BFWO) have been systematically studied for two different oxygen contents corresponding to {delta}=0.00 and 0.55 in the chemical formula in order to determine and correlate their chemical composition, structural and magnetic properties. The evolution of nuclear and magnetic structures with temperature has been investigated by neutron powder diffraction. It was shown that at room temperature the stoichiometric compound ({delta}=0.00) adopts a hexagonal 6H-perovskite structure (space group P6{sub 3}/mmc). This phase, when heated at high temperature under a stream of Ar gas, transforms to an oxygen-deficient phase {delta}=0.55), which is an ordered cubic perovskite structure (space group Fm-3m). The crystallographic and magnetic properties of the obtained phases are compared, and it is clear that the magnetic properties are significantly affected by oxygen non-stoichiometry. These changes of magnetic properties for such a slight decrease in oxygen content are interpreted as a result of structural transformations. Together with the experimental results based on neutron powder diffraction data a discussion of some aspects of the structural transformation (P6{sub 3}/mmc->Fm-3m) is presented.

  7. Unraveling the effect of La A-site substitution on oxygen ion diffusion and oxygen catalysis in perovskite BaFeO3 by data-mining molecular dynamics and density functional theory.

    PubMed

    Chen, Chi; Baiyee, Zarah Medina; Ciucci, Francesco

    2015-10-07

    BaFeO3 (BFO) is a promising parent material for high-temperature oxygen catalysis. The effects of La substitution on the oxygen ion diffusion and oxygen catalysis in A-site La-substituted BFO are studied by combining data-driven molecular dynamics (MD) simulations and density functional theory (DFT) calculations. The data-driven MD simulations are capable of providing atomic level information regarding oxygen jumps at different sites, bridging the resolution gap of analysis between MD and DFT. The simulations identify several effects due to the introduction of La. First, according to simple electroneutrality considerations and DFT calculations, La tends to decrease the concentration of oxygen vacancies in BFO. Second, La substitution lowers the activation energy of local oxygen migration, providing faster paths for oxygen diffusion. The MD analysis predicts a higher hopping rate through La-containing bottlenecks as well as easier oxygen jumps from the La-rich cages and lower dwell times of oxygen in those cages. DFT calculations confirm a lower migration energy through La-containing bottlenecks. Third, the electrocatalytic activity of the material decreases with La, as indicated by a lower O p-band center and higher oxygen vacancy formation energies.

  8. In situ formation of oxygen vacancy in perovskite Sr0.95Ti0.8Nb0.1M0.1O3 (M = Mn, Cr) toward efficient carbon dioxide electrolysis

    PubMed Central

    Zhang, Jun; Xie, Kui; Wei, Haoshan; Qin, Qingqing; Qi, Wentao; Yang, Liming; Ruan, Cong; Wu, Yucheng

    2014-01-01

    In this work, redox-active Mn or Cr is introduced to the B site of redox stable perovskite Sr0.95Ti0.9Nb0.1O3.00 to create oxygen vacancies in situ after reduction for high-temperature CO2 electrolysis. Combined analysis using X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy and thermogravimetric analysis confirms the change of the chemical formula from oxidized Sr0.95Ti0.9Nb0.1O3.00 to reduced Sr0.95Ti0.9Nb0.1O2.90 for the bare sample. By contrast, a significant concentration of oxygen vacancy is additionally formed in situ for Mn- or Cr-doped samples by reducing the oxidized Sr0.95Ti0.8Nb0.1M0.1O3.00 (M = Mn, Cr) to Sr0.95Ti0.8Nb0.1M0.1O2.85. The ionic conductivities of the Mn- and Cr-doped titanate improve by approximately 2 times higher than bare titanate in an oxidizing atmosphere and 3–6 times higher in a reducing atmosphere at intermediate temperatures. A remarkable chemical accommodation of CO2 molecules is achieved on the surface of the reduced and doped titanate, and the chemical desorption temperature reaches a common carbonate decomposition temperature. The electrical properties of the cathode materials are investigated and correlated with the electrochemical performance of the composite electrodes. Direct CO2 electrolysis at composite cathodes is investigated in solid-oxide electrolyzers. The electrode polarizations and current efficiencies are observed to be significantly improved with the Mn- or Cr-doped titanate cathodes. PMID:25403738

  9. Cardiac failure in very long chain acyl-CoA dehydrogenase deficiency requiring extracorporeal membrane oxygenation (ECMO) treatment: A case report and review of the literature.

    PubMed

    Katz, Sharon; Landau, Yuval; Pode-Shakked, Ben; Pessach, Itai M; Rubinshtein, Marina; Anikster, Yair; Salem, Yishay; Paret, Gideon

    2017-03-01

    Fatty acid oxidation (FAO) defects often present with multi-system involvement, including several life-threatening cardiac manifestations, such as cardiomyopathy, pericardial effusion and arrhythmias. We report herein a fatal case of cardiac dysfunction and rapid-onset tamponade following an acute illness in a neonate with molecularly proven very long chain acyl-CoA dehydrogenase (VLCAD) deficiency (harboring the known del799_802 mutation), requiring 15 days of extracorporeal membrane oxygenation (ECMO) treatment. As data regarding the use of ECMO in FAO defects in general, and VLCAD in particular, are scarce, we review the literature and discuss insights from in vitro models and several successful reported cases.

  10. Tunable thermodynamic activity of LaxSr1–xMnyAl1–yO3–δ (0 ≤ x ≤ 1, 0 ≤ y ≤ 1) perovskites for solar thermochemical fuel synthesis† †Electronic supplementary information (ESI) available: Computational details, comprehensive XRD analyses, oxygen nonstoichiometry measurements and thermodynamic characterization of the perovskites. See DOI: 10.1039/c6ta06644e Click here for additional data file.

    PubMed Central

    Ezbiri, M.; Takacs, M.; Theiler, D.; Steinfeld, A.

    2017-01-01

    Nonstoichiometric metal oxides with variable valence are attractive redox materials for thermochemical and electrochemical fuel processing. To guide the design of advanced redox materials for solar-driven splitting of CO2 and/or H2O to produce CO and/or H2 (syngas), we investigate the equilibrium thermodynamics of the LaxSr1–xMnyAl1–yO3–δ perovskite family (0 ≤ x ≤ 1, 0 ≤ y ≤ 1) and La0.6Ca0.4Mn0.8Al0.2O3–δ, and compare them to those of CeO2 as the baseline. Oxygen nonstoichiometry measurements from 1573 to 1773 K and from 0.206 to 180 mbar O2 show a tunable reduction extent, increasing with increasing Sr content. Maximal nonstoichiometry of 0.32 is established with La0.2Sr0.8Mn0.8Al0.2O3–δ at 1773 K and 2.37 mbar O2. As a trend, we find that oxygen capacities are most sensitive to the A-cation composition. Partial molar enthalpy, entropy and Gibbs free energy changes for oxide reduction are extracted from the experimental data using defect models for Mn4+/Mn3+ and Mn3+/Mn2+ redox couples. We find that perovskites exhibit typically decreasing enthalpy changes with increasing nonstoichiometries. This desirable characteristic is most pronounced by La0.6Sr0.4Mn0.4Al0.6O3–δ, rendering it attractive for CO2 and H2O splitting. Generally, perovskites show lower enthalpy and entropy changes than ceria, resulting in more favorable reduction but less favorable oxidation equilibria. The energy penalties due to larger temperature swings and excess oxidants are discussed in particular. Using electronic structure theory, we conclude with a practical methodology estimating thermodynamic activity to rationally design perovskites with variable stoichiometry and valence. PMID:28580143

  11. Preparation of N-doped and oxygen-deficient TiO2 microspheres via a novel electron beam-assisted method

    NASA Astrophysics Data System (ADS)

    Pu, Xianjuan; Hu, Yiyang; Cui, Shicong; Cheng, Lingli; Jiao, Zheng

    2017-08-01

    Nitrogen-doped and oxygen-deficient TiO2 microspheres (NT) with large specific surface were prepared by a solvothermal method and following with electron beam (EB) irradiation under various doses (140-500 kGy). XPS results show that under the EB irradiation, nitrogen ions have been doped into the TiO2 lattice successfully, as well as part of Ti4+ on the surface of the samples changed to Ti3+. Photocatalytic performance was tested by decomposing Rhodamine B in the aqueous phase under visible light irradiation. The prepared materials under the EB irradiation at dose of 140 kGy (NT-140) exhibit the best visible light photocatalytic activity. It is attributed to the large specific surface (138.4 m2/g) and a synergistic effect between substitutional nitrogen dopants and oxygen defects in NT-140. The results obtained may provide a new sight for the application of EB-assisted preparation of nanomaterials.

  12. Interaction between water flow and oxygen deficiency on growth in the infaunal brittle star Amphiura filiformis (Echinodermata: Ophiuroidea)

    NASA Astrophysics Data System (ADS)

    Nilsson, H. C.

    2000-12-01

    Interactions between 'oxygen concentration' (normoxia: >80% oxygen saturation, and hypoxia: 18% oxygen saturation) and 'water flow velocity' (low: 0.1 cm s -1, and moderate: 0.5 cm s -1) were studied on growth rates in the brittle star Amphiura filiformis in a flow-through aquaria system. Effects of 'sublethal predation' on growth rates were investigated as 'number of amputated arms' (1 and 3 arms) and 'amputation of the disk'. A significant interaction between oxygen concentration and water flow velocity was observed in mean arm regeneration rate, but in both flow velocities higher mean arm regeneration rates were observed in normoxia compared to hypoxia. In hypoxia a positive response in arm regeneration rate was observed in moderate flow compared to low flow velocity. In normoxia, however, no response to flow velocity was observed. The latter observation indicates that Amphiura filiformis is able to maintain the ventilation of the burrow at low flow velocities, but in low oxygen concentrations hydrodynamic forces seem to affect growth. A significant interaction between oxygen concentration and disk amputation was observed in both arm and disk regeneration rates, indicating that the disk is the major organ for gas exchange in this species. The number of arms amputated, however, did not affect mean arm regeneration rate. The results obtained in this study suggest that the secondary production in subtidal infaunal populations could be negatively affected by low oxygen concentrations and that this response is even more negative in combination with low flow velocities in the near-bottom water.

  13. Orbital-selective charge transfer at oxygen-deficient LaAlO3/SrTiO3(001) interfaces

    NASA Astrophysics Data System (ADS)

    Ong, P. V.; Lee, Jaichan

    2013-05-01

    Density-functional theory within the local density approximation + Hubbard U approach was used to study interface electronic structures in stoichiometric and oxygen-deficient LaAlO3/SrTiO3 (LAO/STO) superlattices with regularly spaced n-type and p-type interfaces. Asymmetric behaviors between complementary n-type and p-type interfaces were revealed in terms of orbital-selective charge transfer. Extra electrons induced by oxygen vacancies at the p-type interface easily spread to the n-type interface and occupy the Ti 3dxyorbitals, while those induced by the vacancies at the n-type interface are strictly confined and reside in Ti 3dx2-y2 and/or 3d3z2-r2 orbtials. The electronic behavior of oxygen vacancies at the LAO/STO interfaces and the possibility of distinguishing between intrinsic electronic states, which are induced by the polar catastrophe, and extrinsic states due to oxygen vacancies are discussed in detail.

  14. Spin-texture induced by oxygen vacancies in Strontium perovskites (001) surfaces: A theoretical comparison between SrTiO3 and SrHfO3

    NASA Astrophysics Data System (ADS)

    Vergniory, Maia; García-Castro, Andrés-Camilo; Bousquet, Eric; Romero, Aldo Humberto

    The electronic structure of SrTiO3 and SrHfO3 (001) surfaces with oxygen vacancies is studied by means of first-principles calculations. We reveal how oxygen vacancies within the first atomic layer of the SrTiO3 surface (i) induce a large antiferrodistortive motion of the oxygen octahedra at the surface, (ii) drive localized magnetic moments on the Ti-3 d orbitals close to the vacancies and (iii) form a two-dimensional electron gas localized within the first layers. The analysis of the spin-texture of this system exhibits a splitting of the energy bands according to the Zeeman interaction, lowering of the Ti-3dxy level in comparison with dxz and dyz and also an in-plane precession of the spins. No Rashba-like splitting for the ground state neither for ab initio molecular dynamics trajectory at 400K is recognized as suggested recently by A. F. Santander-Syro et al.). Instead, a sizeable Rashba-like splitting is observed when the Ti atom is replaced by a heavier Hf atom with a much larger spin-orbit interaction. However, we observe the disappearance of the magnetism and the surface two-dimensional electron gas when full structural optimization of the SrHfO3 surface is performed. Our results uncove

  15. The hybrid-DFT study on bandgap estimation for the perovskite-type titanium oxide of SrTiO3

    NASA Astrophysics Data System (ADS)

    Onishi, Taku

    When we estimate the proper bandgap for the perovskite-type titanium oxide of SrTiO3 by the use of hybrid-density functional theory (DFT) method, it is important to choose the exchange and correlation functionals. Especially, Hartree-Fock (HF) exchange functional plays the major role in inclusion of the localization effect. In this study, we empirically determined the proper HF exchange functional coefficient for SrTiO3. Though the blue-light emission process in SrTiO3 has attracted much interest, the mechanism is still unclear. To elucidate the mechanism of the blue-light emission process, we performed hybrid-DFT calculations for the oxygen deficient cluster models. It was concluded that oxygen deficiency is irrelevant to the process, because of the strong chemical bond between titaniums.

  16. Magnetoresistance Versus Oxygen Deficiency in Epi-stabilized SrRu1 - x Fe x O3 - δ Thin Films

    NASA Astrophysics Data System (ADS)

    Dash, Umasankar; Acharya, Susant Kumar; Lee, Bo Wha; Jung, Chang Uk

    2017-03-01

    Oxygen vacancies have a profound effect on the magnetic, electronic, and transport properties of transition metal oxide materials. Here, we studied the influence of oxygen vacancies on the magnetoresistance (MR) properties of SrRu1 - x Fe x O3 - δ epitaxial thin films ( x = 0.10, 0.20, and 0.30). For this purpose, we synthesized highly strained epitaxial SrRu1 - x Fe x O3 - δ thin films with atomically flat surfaces containing different amounts of oxygen vacancies using pulsed laser deposition. Without an applied magnetic field, the films with x = 0.10 and 0.20 showed a metal-insulator transition, while the x = 0.30 thin film showed insulating behavior over the entire temperature range of 2-300 K. Both Fe doping and the concentration of oxygen vacancies had large effects on the negative MR contributions. For the low Fe doping case of x = 0.10, in which both films exhibited metallic behavior, MR was more prominent in the film with fewer oxygen vacancies or equivalently a more metallic film. For semiconducting films, higher MR was observed for more semiconducting films having more oxygen vacancies. A relatively large negative MR ( 36.4%) was observed for the x = 0.30 thin film with a high concentration of oxygen vacancies ( δ = 0.12). The obtained results were compared with MR studies for a polycrystal of (Sr1 - x La x )(Ru1 - x Fe x )O3. These results highlight the crucial role of oxygen stoichiometry in determining the magneto-transport properties in SrRu1 - x Fe x O3 - δ thin films.

  17. Synthesis, crystal structure and charge distribution of Na{sub 7}As{sub 11}O{sub 31}: An oxygen-deficient layered sodium arsenate

    SciTech Connect

    Guesmi, Abderrahmen . E-mail: abderrahmen.guesmi@ipeim.mu.tn; Nespolo, Massimo; Driss, Ahmed

    2006-08-15

    A new sodium arsenate with layer structure has been synthesized and its crystal structure solved and refined by single-crystal X-ray diffraction. The crystal is trigonal, space group P3-bar m1, a=11.199(3)A, c=5.411(2)A, V=587.80(3)A{sup 3}, Z=1; the refinement converged to R=0.0282 and wR=0.0751 for 590 reflections with (I)>2sigma(I). The structural model gives the formula Na{sub 7}As{sub 11}O{sub 32}, which would be non-neutral; besides, the structural model is not validated by the charge distribution (CD) analysis, which gives an unsatisfactory agreement on the computed charges of the cations. The CD analysis suggest incomplete (5/6) occupation of the O5 site, which leads to the deficiency of an oxygen atom per unit cell and to formula Na{sub 7}As{sub 11}O{sub 31}: this new structural model corresponds to a neutral compound, is validated by the CD analysis, and results in better displacement parameters for O5 than its non neutral counterpart. The (001) anionic layers are built up from corner and edge sharing of As1 and As2 distorted octahedra and As3 distorted tetrahedra, the sodium cations playing the role of interlayer cations. The effects of the oxygen deficiency on the crystal structure are discussed.

  18. Efficient Suppression of Electron–Hole Recombination in Oxygen-Deficient Hydrogen-Treated TiO2 Nanowires for Photoelectrochemical Water Splitting

    PubMed Central

    2013-01-01

    There is an increasing level of interest in the use of black TiO2 prepared by thermal hydrogen treatments (H:TiO2) due to the potential to enhance both the photocatalytic and the light-harvesting properties of TiO2. Here, we examine oxygen-deficient H:TiO2 nanotube arrays that have previously achieved very high solar-to-hydrogen (STH) efficiencies due to incident photon-to-current efficiency (IPCE) values of >90% for photoelectrochemical water splitting at only 0.4 V vs RHE under UV illumination. Our transient absorption (TA) mechanistic study provides strong evidence that the improved electrical properties of oxygen-deficient TiO2 enables remarkably efficient spatial separation of electron–hole pairs on the submicrosecond time scale at moderate applied bias, and this coupled to effective suppression of microsecond to seconds charge carrier recombination is the primary factor behind the dramatically improved photoelectrochemical activity. PMID:24376902

  19. Characteristics of Alpha-1 Antitrypsin-Deficient Individuals in the Long-term Oxygen Treatment Trial and Comparison with Other Subjects with Chronic Obstructive Pulmonary Disease.

    PubMed

    Stoller, James K; Aboussouan, Loutfi S; Kanner, Richard E; Wilson, Laura A; Diaz, Phil; Wise, Robert

    2015-12-01

    Alpha-1 antitrypsin deficiency (AATD) predisposes to chronic obstructive pulmonary disease, but is underrecognized. Oxygenation and exercise desaturation in individuals with AATD-associated chronic obstructive pulmonary disease has been sparsely studied. The Long-term Oxygen Treatment Trial (LOTT) permits comparing these features of individuals with AATD with alpha-1 antitrypsin-replete (called "usual chronic obstructive pulmonary disease") LOTT participants. Compare demographic, clinical, baseline oxygenation, and exercise desaturation features in participating AATD subjects with those of other LOTT subjects. LOTT is a multicenter randomized controlled trial comparing use of supplemental oxygen versus not in subjects with chronic obstructive pulmonary disease and moderate hypoxemia (resting oxygen saturation as measured by pulse oximetry, 89-93%) or normal oxygen saturation at rest and significant exercise desaturation. Among the 597 LOTT participants with nonmissing alpha-1 antitrypsin levels, 11 (1.8%) had severe AATD and 44 (7.4%) had mild/moderate AATD. Comparison of the 11 severely AAT-deficient individuals with the 542 LOTT participants with usual chronic obstructive pulmonary disease showed that the AATD subjects were younger and despite less smoking, had lower FEV1/FVC (mean post-bronchodilator FEV1/FVC, 0.38 ± 0.06 vs. 0.46 ± 0.13; P = 0.002). Comparison with 27 age-, sex-, and FEV1-matched alpha-1 antitrypsin-normal LOTT participants showed no baseline difference in resting room air pulse oximetry saturation (AATD, 93.6% ± 2.3% vs. 92.7% ± 2.2%; P = 0.64). Exercise-related desaturation was more severe in the individuals with AATD based on desaturation to 88% or less sooner during a 6-minute-walk test, having a higher percentage of desaturation points (e.g., <90%) during exercise, and having a higher distance-saturation product (defined as the distance walked in 6 min multiplied by the nadir saturation achieved during the 6-minute-walk test). These

  20. Characteristics of Alpha-1 Antitrypsin–Deficient Individuals in the Long-term Oxygen Treatment Trial and Comparison with Other Subjects with Chronic Obstructive Pulmonary Disease

    PubMed Central

    Aboussouan, Loutfi S.; Kanner, Richard E.; Wilson, Laura A.; Diaz, Phil; Wise, Robert

    2015-01-01

    Rationale: Alpha-1 antitrypsin deficiency (AATD) predisposes to chronic obstructive pulmonary disease, but is underrecognized. Oxygenation and exercise desaturation in individuals with AATD-associated chronic obstructive pulmonary disease has been sparsely studied. The Long-term Oxygen Treatment Trial (LOTT) permits comparing these features of individuals with AATD with alpha-1 antitrypsin–replete (called “usual chronic obstructive pulmonary disease”) LOTT participants. Objectives: Compare demographic, clinical, baseline oxygenation, and exercise desaturation features in participating AATD subjects with those of other LOTT subjects. Methods: LOTT is a multicenter randomized controlled trial comparing use of supplemental oxygen versus not in subjects with chronic obstructive pulmonary disease and moderate hypoxemia (resting oxygen saturation as measured by pulse oximetry, 89–93%) or normal oxygen saturation at rest and significant exercise desaturation. Measurement and Main Results: Among the 597 LOTT participants with nonmissing alpha-1 antitrypsin levels, 11 (1.8%) had severe AATD and 44 (7.4%) had mild/moderate AATD. Comparison of the 11 severely AAT-deficient individuals with the 542 LOTT participants with usual chronic obstructive pulmonary disease showed that the AATD subjects were younger and despite less smoking, had lower FEV1/FVC (mean post-bronchodilator FEV1/FVC, 0.38 ± 0.06 vs. 0.46 ± 0.13; P = 0.002). Comparison with 27 age-, sex-, and FEV1-matched alpha-1 antitrypsin–normal LOTT participants showed no baseline difference in resting room air pulse oximetry saturation (AATD, 93.6% ± 2.3% vs. 92.7% ± 2.2%; P = 0.64). Exercise-related desaturation was more severe in the individuals with AATD based on desaturation to 88% or less sooner during a 6-minute-walk test, having a higher percentage of desaturation points (e.g., <90%) during exercise, and having a higher distance-saturation product (defined as the distance

  1. Sudden Deaths Among Oil and Gas Extraction Workers Resulting from Oxygen Deficiency and Inhalation of Hydrocarbon Gases and Vapors - United States, January 2010-March 2015.

    PubMed

    Harrison, Robert J; Retzer, Kyla; Kosnett, Michael J; Hodgson, Michael; Jordan, Todd; Ridl, Sophia; Kiefer, Max

    2016-01-15

    In 2013, an occupational medicine physician from the University of California, San Francisco, contacted CDC's National Institute for Occupational Safety and Health (NIOSH), and the Occupational Safety and Health Administration (OSHA) about two oil and gas extraction worker deaths in the western United States. The suspected cause of these deaths was exposure to hydrocarbon gases and vapors (HGVs) and oxygen (O2)-deficient atmospheres after opening the hatches of hydrocarbon storage tanks. The physician and experts from NIOSH and OSHA reviewed available fatality reports from January 2010 to March 2015, and identified seven additional deaths with similar characteristics (nine total deaths). Recommendations were made to industry and regulators regarding the hazards associated with opening hatches of tanks, and controls to reduce or eliminate the potential for HGV exposure were proposed. Health care professionals who treat or evaluate oil and gas workers need to be aware that workers might report symptoms of exposure to high concentrations of HGVs and possible O2 deficiency; employers and workers need to be aware of this hazard and know how to limit exposure. Medical examiners investigating the death of oil and gas workers who open tank hatches should consider the contribution of O2 deficiency and HGV exposure.

  2. Chalcogenide perovskites for photovoltaics.

    PubMed

    Sun, Yi-Yang; Agiorgousis, Michael L; Zhang, Peihong; Zhang, Shengbai

    2015-01-14

    Chalcogenide perovskites are proposed for photovoltaic applications. The predicted band gaps of CaTiS3, BaZrS3, CaZrSe3, and CaHfSe3 with the distorted perovskite structure are within the optimal range for making single-junction solar cells. The predicted optical absorption properties of these materials are superior compared with other high-efficiency solar-cell materials. Possible replacement of the alkaline-earth cations by molecular cations, e.g., (NH3NH3)(2+), as in the organic-inorganic halide perovskites (e.g., CH3NH3PbI3), are also proposed and found to be stable. The chalcogenide perovskites provide promising candidates for addressing the challenging issues regarding halide perovskites such as instability in the presence of moisture and containing the toxic element Pb.

  3. Solid state oxygen sensor

    DOEpatents

    Garzon, Fernando H.; Chung, Brandon W.; Raistrick, Ian D.; Brosha, Eric L.

    1996-01-01

    Solid state oxygen sensors are provided with a yttria-doped zirconia as an electrolyte and use the electrochemical oxygen pumping of the zirconia electrolyte. A linear relationship between oxygen concentration and the voltage arising at a current plateau occurs when oxygen accessing the electrolyte is limited by a diffusion barrier. A diffusion barrier is formed herein with a mixed electronic and oxygen ion-conducting membrane of lanthanum-containing perovskite or zirconia-containing fluorite. A heater may be used to maintain an adequate oxygen diffusion coefficient in the mixed conducting layer.

  4. Solid state oxygen sensor

    DOEpatents

    Garzon, F.H.; Chung, B.W.; Raistrick, I.D.; Brosha, E.L.

    1996-08-06

    Solid state oxygen sensors are provided with a yttria-doped zirconia as an electrolyte and use the electrochemical oxygen pumping of the zirconia electrolyte. A linear relationship between oxygen concentration and the voltage arising at a current plateau occurs when oxygen accessing the electrolyte is limited by a diffusion barrier. A diffusion barrier is formed herein with a mixed electronic and oxygen ion-conducting membrane of lanthanum-containing perovskite or zirconia-containing fluorite. A heater may be used to maintain an adequate oxygen diffusion coefficient in the mixed conducting layer. 4 figs.

  5. High Rate and Stable Li-Ion Insertion in Oxygen-Deficient LiV3O8 Nanosheets as a Cathode Material for Lithium-Ion Battery.

    PubMed

    Song, Huanqiao; Luo, Mingsheng; Wang, Aimei

    2017-01-25

    Low performance of cathode materials has become one of the major obstacles to the application of lithium-ion battery (LIB) in advanced portable electronic devices, hybrid electric vehicles, and electric vehicles. The present work reports a versatile oxygen-deficient LiV3O8 (D-LVO) nanosheet that was synthesized successfully via a facile oxygen-deficient hydrothermal reaction followed by thermal annealing in Ar. When used as a cathode material for LIB, the prepared D-LVO nanosheets display remarkable capacity properties at various current densities (a capacity of 335, 317, 278, 246, 209, 167, and 133 mA h g(-1) at 50, 100, 200, 500, 1000, 2000, and 4000 mA g(-1), respectively) and excellent lithium-ion storage stability, maintaining more than 88% of the initial reversible capacity after 200 cycles at 1000 mA g(-1). The outstanding electrochemical properties are believed to arise largely from the introduction of tetravalent V (∼15% V(4+)) and the attendant oxygen vacancies into LiV3O8 nanosheets, leading to intrinsic electrical conductivity more than 1 order of magnitude higher and lithium-ion diffusion coefficient nearly 2 orders of magnitude higher than those of LiV3O8 without detectable V(4+) (N-LVO) and thus contributing to the easy lithium-ion diffusion, rapid phase transition, and the excellent electrochemical reversibility. Furthermore, the more uniform nanostructure, as well as the larger specific surface area of D-LVO than N-LVO nanosheets may also improve the electrolyte penetration and provide more reaction sites for fast lithium-ion diffusion during the discharge/charge processes.

  6. Sr(4 + n)Mn(3+)(4)Mn(4+)(n)O(10 + 3n): a new homologous series of oxygen-vacancy-ordered perovskites built from Mn(3+)O(5) pyramids and Mn(4+)O(6) octahedra.

    PubMed

    Suescun, Leopoldo; Dabrowski, Bogdan

    2008-04-01

    A new homologous series of oxygen-vacancy-ordered perovskites with the formula Sr_{4+n}Mn;{3+}_4Mn;{4+}_nO_{10+3n} is proposed based on the structural trends found for the recently described Sr(4)Mn(4)O(10), Sr(5)Mn(5)O(13) and Sr(7)Mn(7)O(19) compounds. These compounds correspond to n = 0 (Sr(4)Mn;{3+}_4O(10)), n = 1 (Sr(5)Mn;{3+}_4Mn(4+)O(13)) and n = 3 (Sr(7)Mn;{3+}_4Mn;{4+}_3O(19)) members of the series. A linear set of four Mn(3+)O(5) pyramids placed on the ab plane and pointing along the +x, -y, +y, -x directions defines the n = 0 building block for the series. The nth members can be constructed from blocks containing four pyramids and n Mn(4+)O(6) octahedra with 2/m symmetry. Compounds in the related systems CaMnO(x) and LaCuO(x), containing Mn(3+) and Cu(2+) pyramids and Mn(4+) and Cu(3+) octahedra have also been found to be members of the series. The size and charge of the A-site cation and the apical distortion of the pyramidally coordinated B-site cation are shown to be important factors in the stabilization of certain members of the series. A qualitative explanation for the absence of some of the possible members of the series is presented based on these factors.

  7. Molecular diversity of denitrifying genes in continental margin sediments within the oxygen-deficient zone off the Pacific coast of Mexico.

    PubMed

    Liu, Xueduan; Tiquia, Sonia M; Holguin, Gina; Wu, Liyou; Nold, Stephen C; Devol, Allan H; Luo, Kuan; Palumbo, Anthony V; Tiedje, James M; Zhou, Jizhong

    2003-06-01

    To understand the composition and structure of denitrifying communities in the oxygen-deficient zone off the Pacific coast of Mexico, the molecular diversity of nir genes from sediments obtained at four stations was examined by using a PCR-based cloning approach. A total of 50 operational taxonomic units (OTUs) for nirK and 82 OTUs for nirS were obtained from all samples. Forty-four of the nirS clones and 31 of the nirK clones were sequenced; the levels of similarity of the nirS clones were 52 to 92%, and the levels of similarity of the nirS clones were 50 to 99%. The percentages of overlapping OTUs between stations were 18 to 30% for nirS and 5 to 8% for nirK. Sequence analysis revealed that 26% of the nirS clones were related to the nirS genes of Alcaligenes faecalis (80 to 94% similar) and Pseudomonas stutzeri (80 to 99%), whereas 3 to 31% of the nirK clones were closely related to the nirK genes of Pseudomonas sp. strain G-179 (98 to 99%), Bradyrhizobium japonicum (91%), Blastobacter denitrificans (83%), and Alcaligenes xylosoxidans (96%). The rest of the clones, however, were less than 80% similar to nirS and nirK sequences available in sequence databases. The results of a principal-component analysis (PCA) based on the percentage of OTUs and biogeochemical data indicated that the nitrate concentration and oxygen have an effect on the denitrifying communities. The communities at the stations in oxygen-deficient zones were more similar than the communities at the stations in the oxygenated zone. The denitrifying communities were more similar at the stations that were closer together and had similar nitrate levels. Also, the results of PCA based on biogeochemical properties suggest that geographic location and biogeochemical conditions, especially the nitrate and oxygen levels, appear to be the key factors that control the structure of denitrifying communities.

  8. Magnetism, Spin Texture, and In-Gap States: Atomic Specialization at the Surface of Oxygen-Deficient SrTiO_{3}.

    PubMed

    Altmeyer, Michaela; Jeschke, Harald O; Hijano-Cubelos, Oliver; Martins, Cyril; Lechermann, Frank; Koepernik, Klaus; Santander-Syro, Andrés F; Rozenberg, Marcelo J; Valentí, Roser; Gabay, Marc

    2016-04-15

    Motivated by recent spin- and angular-resolved photoemission (SARPES) measurements of the two-dimensional electronic states confined near the (001) surface of oxygen-deficient SrTiO_{3}, we explore their spin structure by means of ab initio density functional theory (DFT) calculations of slabs. Relativistic nonmagnetic DFT calculations display Rashba-like spin winding with a splitting of a few meV and when surface magnetism on the Ti ions is included, bands become spin-split with an energy difference ∼100  meV at the Γ point, consistent with SARPES findings. While magnetism tends to suppress the effects of the relativistic Rashba interaction, signatures of it are still clearly visible in terms of complex spin textures. Furthermore, we observe an atomic specialization phenomenon, namely, two types of electronic contributions: one is from Ti atoms neighboring the oxygen vacancies that acquire rather large magnetic moments and mostly create in-gap states; another comes from the partly polarized t_{2g} itinerant electrons of Ti atoms lying further away from the oxygen vacancy, which form the two-dimensional electron system and are responsible for the Rashba spin winding and the spin splitting at the Fermi surface.

  9. Magnetism, Spin Texture, and In-Gap States: Atomic Specialization at the Surface of Oxygen-Deficient SrTiO3

    NASA Astrophysics Data System (ADS)

    Altmeyer, Michaela; Jeschke, Harald O.; Hijano-Cubelos, Oliver; Martins, Cyril; Lechermann, Frank; Koepernik, Klaus; Santander-Syro, Andrés F.; Rozenberg, Marcelo J.; Valentí, Roser; Gabay, Marc

    2016-04-01

    Motivated by recent spin- and angular-resolved photoemission (SARPES) measurements of the two-dimensional electronic states confined near the (001) surface of oxygen-deficient SrTiO3, we explore their spin structure by means of ab initio density functional theory (DFT) calculations of slabs. Relativistic nonmagnetic DFT calculations display Rashba-like spin winding with a splitting of a few meV and when surface magnetism on the Ti ions is included, bands become spin-split with an energy difference ˜100 meV at the Γ point, consistent with SARPES findings. While magnetism tends to suppress the effects of the relativistic Rashba interaction, signatures of it are still clearly visible in terms of complex spin textures. Furthermore, we observe an atomic specialization phenomenon, namely, two types of electronic contributions: one is from Ti atoms neighboring the oxygen vacancies that acquire rather large magnetic moments and mostly create in-gap states; another comes from the partly polarized t2 g itinerant electrons of Ti atoms lying further away from the oxygen vacancy, which form the two-dimensional electron system and are responsible for the Rashba spin winding and the spin splitting at the Fermi surface.

  10. Synergetic effect of Sn addition and oxygen-deficient atmosphere to design active hematite photoelectrodes for light-induced water splitting.

    PubMed

    de Freitas, Andre Luiz Martins; Souza, Flavio L

    2017-09-08

    This work describes a microwave-assisted hydrothermal conditions method to design pure and Sn-hematite photoelectrodes at different synthesis time with additional thermal treatment under air and N2 atmosphere. The hematite photoelectrode designed under N2 atmosphere and Sn deposited on its surface, which is represented by material synthesized at 4 hours exhibit the highest performance. Hence, the Sn-addition followed by high annealing temperature conducted at oxygen-deficient atmosphere seems to create of oxygen vacancies and have prevented the dopant segregation to form SnO2 phase at the hematite crystal reducing its energy and suppressing the grain growth. The increased number of donor density provided by the oxygen vacancies (confirmed by X-ray photoelectron data) and a possible reduction in the grain boundary energy or hematite crystal interface might favor the charge separation and increase the electron transfer through the hematite into the back contact (FTO substrate). As consequence, the light-induced water oxidation reaction efficiency of Sn-hematite photoelectrode was significantly increased in comparison with pure ones, even though the vertical rod morphology was not preserved. This finding provides a novel insight on the intentional Sn-addition revealing that the dopant segregation at the hematite crystal surface (or at the grain boundaries) could be the more relevant factor for developing active hematite photoelectrodes by increasing the electron mobility than the columnar morphology control. © 2017 IOP Publishing Ltd.

  11. Quasiparticle Interference on Cubic Perovskite Oxide Surfaces

    NASA Astrophysics Data System (ADS)

    Okada, Yoshinori; Shiau, Shiue-Yuan; Chang, Tay-Rong; Chang, Guoqing; Kobayashi, Masaki; Shimizu, Ryota; Jeng, Horng-Tay; Shiraki, Susumu; Kumigashira, Hiroshi; Bansil, Arun; Lin, Hsin; Hitosugi, Taro

    2017-08-01

    We report the observation of coherent surface states on cubic perovskite oxide SrVO3(001 ) thin films through spectroscopic-imaging scanning tunneling microscopy. A direct link between the observed quasiparticle interference patterns and the formation of a dx y -derived surface state is supported by first-principles calculations. We show that the apical oxygens on the topmost VO2 plane play a critical role in controlling the coherent surface state via modulating orbital state.

  12. Slicing the perovskite structure with crystallographic shear planes: the A(n)B(n)O(3n-2) homologous series.

    PubMed

    Abakumov, Artem M; Hadermann, Joke; Batuk, Maria; D'Hondt, Hans; Tyablikov, Oleg A; Rozova, Marina G; Pokholok, Konstantin V; Filimonov, Dmitry S; Sheptyakov, Denis V; Tsirlin, Alexander A; Niermann, Daniel; Hemberger, Joachim; Van Tendeloo, Gustaaf; Antipov, Evgeny V

    2010-10-18

    A new A(n)B(n)O(3n-2) homologous series of anion-deficient perovskites has been evidenced by preparation of the members with n = 5 (Pb(2.9)Ba(2.1)Fe(4)TiO(13)) and n = 6 (Pb(3.8)Bi(0.2)Ba(2)Fe(4.2)Ti(1.8)O(16)) in a single phase form. The crystal structures of these compounds were determined using a combination of transmission electron microscopy and X-ray and neutron powder diffraction (S.G. Ammm, a = 5.74313(7), b = 3.98402(4), c = 26.8378(4) Å, R(I) = 0.035, R(P) = 0.042 for Pb(2.9)Ba(2.1)Fe(4)TiO(13) and S.G. Imma, a = 5.7199(1), b = 3.97066(7), c = 32.5245(8) Å, R(I) = 0.032, R(P) = 0.037 for Pb(3.8)Bi(0.2)Ba(2)Fe(4.2)Ti(1.8)O(16)). The crystal structures of the A(n)B(n)O(3n-2) homologues are formed by slicing the perovskite structure with (101)(p) crystallographic shear (CS) planes. The shear planes remove a layer of oxygen atoms and displace the perovskite blocks with respect to each other by the 1/2[110](p) vector. The CS planes introduce edge-sharing connections of the transition metal-oxygen polyhedra at the interface between the perovskite blocks. This results in intrinsically frustrated magnetic couplings between the perovskite blocks due to a competition of the exchange interactions between the edge- and the corner-sharing metal-oxygen polyhedra. Despite the magnetic frustration, neutron powder diffraction and Mössbauer spectroscopy reveal that Pb(2.9)Ba(2.1)Fe(4)TiO(13) and Pb(3.8)Bi(0.2)Ba(2)Fe(4.2)Ti(1.8)O(16) are antiferromagnetically ordered below T(N) = 407 and 343 K, respectively. The Pb(2.9)Ba(2.1)Fe(4)TiO(13) and Pb(3.8)Bi(0.2)Ba(2)Fe(4.2)Ti(1.8)O(16) compounds are in a paraelectric state in the 5-300 K temperature range.

  13. Recent advances of lanthanum-based perovskite oxides for catalysis

    DOE PAGES

    Zhu, Huiyuan; Zhang, Pengfei; Dai, Sheng

    2015-09-21

    There is a need to reduce the use of noble metal elements especially in the field of catalysis, where noble metals are ubiquitously applied. To this end, perovskite oxides, an important class of mixed oxide, have been attracting increasing attention for decades as potential replacements. Benefiting from the extraordinary tunability of their compositions and structures, perovskite oxides can be rationally tailored and equipped with targeted physical and chemical properties e.g. redox behavior, oxygen mobility, and ion conductivity for enhanced catalysis. Recently, the development of highly efficient perovskite oxide catalysts has been extensively studied. This review article summarizes the recent developmentmore » of lanthanum-based perovskite oxides as advanced catalysts for both energy conversion applications and traditional heterogeneous reactions.« less

  14. Recent advances of lanthanum-based perovskite oxides for catalysis

    SciTech Connect

    Zhu, Huiyuan; Zhang, Pengfei; Dai, Sheng

    2015-09-21

    There is a need to reduce the use of noble metal elements especially in the field of catalysis, where noble metals are ubiquitously applied. To this end, perovskite oxides, an important class of mixed oxide, have been attracting increasing attention for decades as potential replacements. Benefiting from the extraordinary tunability of their compositions and structures, perovskite oxides can be rationally tailored and equipped with targeted physical and chemical properties e.g. redox behavior, oxygen mobility, and ion conductivity for enhanced catalysis. Recently, the development of highly efficient perovskite oxide catalysts has been extensively studied. This review article summarizes the recent development of lanthanum-based perovskite oxides as advanced catalysts for both energy conversion applications and traditional heterogeneous reactions.

  15. Trapped charge-driven degradation of perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Ahn, Namyoung; Kwak, Kwisung; Jang, Min Seok; Yoon, Heetae; Lee, Byung Yang; Lee, Jong-Kwon; Pikhitsa, Peter V.; Byun, Junseop; Choi, Mansoo

    2016-11-01

    Perovskite solar cells have shown unprecedent performance increase up to 22% efficiency. However, their photovoltaic performance has shown fast deterioration under light illumination in the presence of humid air even with encapulation. The stability of perovskite materials has been unsolved and its mechanism has been elusive. Here we uncover a mechanism for irreversible degradation of perovskite materials in which trapped charges, regardless of the polarity, play a decisive role. An experimental setup using different polarity ions revealed that the moisture-induced irreversible dissociation of perovskite materials is triggered by charges trapped along grain boundaries. We also identified the synergetic effect of oxygen on the process of moisture-induced degradation. The deprotonation of organic cations by trapped charge-induced local electric field would be attributed to the initiation of irreversible decomposition.

  16. Trapped charge-driven degradation of perovskite solar cells

    PubMed Central

    Ahn, Namyoung; Kwak, Kwisung; Jang, Min Seok; Yoon, Heetae; Lee, Byung Yang; Lee, Jong-Kwon; Pikhitsa, Peter V.; Byun, Junseop; Choi, Mansoo

    2016-01-01

    Perovskite solar cells have shown unprecedent performance increase up to 22% efficiency. However, their photovoltaic performance has shown fast deterioration under light illumination in the presence of humid air even with encapulation. The stability of perovskite materials has been unsolved and its mechanism has been elusive. Here we uncover a mechanism for irreversible degradation of perovskite materials in which trapped charges, regardless of the polarity, play a decisive role. An experimental setup using different polarity ions revealed that the moisture-induced irreversible dissociation of perovskite materials is triggered by charges trapped along grain boundaries. We also identified the synergetic effect of oxygen on the process of moisture-induced degradation. The deprotonation of organic cations by trapped charge-induced local electric field would be attributed to the initiation of irreversible decomposition. PMID:27830709

  17. Ferroelectric-field-effect-enhanced resistance performance of TiN/Si:HfO2/oxygen-deficient HfO2/TiN resistive switching memory cells

    NASA Astrophysics Data System (ADS)

    Jiang, Ran; Wu, Zhengran; Du, Xianghao; Han, Zuyin; Sun, Weideng

    2015-07-01

    Greatly improved resistance performance, including high resistance ratio between the high resistance state and the low resistance state, long-time retention, and reliable endurance, was observed in TiN/Si:HfO2/oxygen-deficient HfO2/TiN memory cells. The enhanced resistance ratio is ascribed to the creation/elimination of an extra barrier in oxygen-deficient HfO2 layer in response to the polarization reversal in the ferroelectric Si:HfO2 layer. Along with the enhanced resistance ratio, the long retention and good endurance make the proposed device a promising candidate for non-volatile resistive memories.

  18. Magnetism and Faraday Rotation in Oxygen-Deficient Polycrystalline and Single-Crystal Iron-Substituted Strontium Titanate

    NASA Astrophysics Data System (ADS)

    Goto, Taichi; Kim, Dong Hun; Sun, Xueyin; Onbasli, Mehmet C.; Florez, Juan M.; Ong, Shyue Ping; Vargas, Patricio; Ackland, Karl; Stamenov, Plamen; Aimon, Nicolas M.; Inoue, Mitsuteru; Tuller, Harry L.; Dionne, Gerald F.; Coey, J. Michael D.; Ross, Caroline A.

    2017-02-01

    Both polycrystalline and single-crystal films of iron-substituted strontium titanate, Sr (Ti0.65Fe0.35)O3 -δ , prepared by pulsed laser deposition, show room-temperature magnetism and Faraday rotation, with the polycrystalline films exhibiting higher saturation magnetization and Faraday rotation. The magnetic properties vary with the oxygen pressure at which the films are grown, showing a maximum at pressures of approximately 4 μ Torr at which the unit-cell volume is largest. The results are discussed in terms of the oxygen stoichiometry and corresponding Fe valence states, the structure and strain state, and the presence of small-volume fractions of metallic Fe in single-crystal films grown at the optimum deposition pressure. Integration of magneto-optical polycrystalline films on an optical-waveguide device demonstrates a nonreciprocal phase shift.

  19. Senescence marker protein-30 (SMP30) deficiency impairs myocardium-induced dilation of coronary arterioles associated with reactive oxygen species.

    PubMed

    Mizukami, Hiroyuki; Saitoh, Shu-Ichi; Machii, Hirofumi; Yamada, Shinya; Hoshino, Yasuto; Misaka, Tomofumi; Ishigami, Akihito; Takeishi, Yasuchika

    2013-04-29

    Senescence marker protein-30 (SMP30) decreases with aging. Mice with SMP30 deficiency, a model of aging, have a short lifespan with increased oxidant stress. To elucidate SMP30's effect on coronary circulation derived from myocytes, we measured the changes in the diameter of isolated coronary arterioles in wild-type (WT) mice exposed to supernatant collected from isolated paced cardiac myocytes from SMP30 KO or WT mice. Pacing increased hydrogen peroxide in myocytes, and hydrogen peroxide was greater in SMP30 KO myocytes compared to WT myocytes. Antimycin enhanced and FCCP (oxidative phosphorylation uncoupler in mitochondria) decreased superoxide production in both groups. Addition of supernatant from stimulated myocytes, either SMP30 KO or WT, caused vasodilation. The degree of the vasodilation response to supernatant was smaller in SMP30 KO mice compared to WT mice. Administration of catalase to arterioles eliminated vasodilation in myocyte supernatant of WT mice and converted vasodilation to vasoconstriction in myocyte supernatant of SMP30 KO mice. This vasoconstriction was eliminated by olmesartan, an angiotensin II receptor antagonist. Thus, SMP30 deficiency combined with oxidant stress increases angiotensin and hydrogen peroxide release from cardiac myocytes. SMP30 plays an important role in the regulation of coronary vascular tone by myocardium.

  20. Magnetic studies of current conduction and flux pinning in high-T(sub c) cuprates: Virgin, irradiated, and oxygen deficient materials

    NASA Astrophysics Data System (ADS)

    Thompson, J. R.; Sun, Yang Ren; Ossandon, J. G.; Christen, D. K.; Kerchner, H. R.; Sles, B. C.; Chakoumakos, B. C.; Civale, L.; Marwick, A. D.; Holtzberg, F.

    1992-09-01

    To increase the current density and pinning of magnetic flux in high temperature superconductors, defects with point-like and line-like geometries were created in controlled numbers using ion irradiation methods. Single crystals of Y1Ba2Cu3O7 and Bi2Sr2Ca1Cu2O8 superconductors were studied using dc magnetic methods. These studies showed greatly increased irreversibility in the vortex state magnetization and enhanced intragrain current density J(sub c) following irradiation. Linear defects, created by irradiation with energetic heavy ions, are particularly effective in pinning vortices at higher temperatures and magnetic fields. Further investigations of 'flux creep' (the time dependence of magnetization) are well described by recent vortex glass and collective pinning theories. Complementary investigations have delineated the role of oxygen deficiency (delta) on pinning in aligned Y1Ba2Cu3O(7-delta) materials.

  1. Synthesis and thermoelectric properties of oxygen deficient fluorite derivative Ga3-xIn5+xSn2O16

    NASA Astrophysics Data System (ADS)

    Bhame, S. D.; Zhou, T.; Guilmeau, E.; Kinemuchi, Y.; Delorme, F.; Raveau, B.

    2010-11-01

    Exploring the possibility to obtain n-type oxide thermoelectrics, the transparent conducting oxide Ga3-xIn5+xSn2O16 (0.3oxygen-deficient fluorite structure.

  2. Detection and imaging of the oxygen deficiency in single crystalline YBa2Cu3O7-δ thin films using a scanning positron beam

    NASA Astrophysics Data System (ADS)

    Reiner, M.; Gigl, T.; Jany, R.; Hammerl, G.; Hugenschmidt, C.

    2015-03-01

    Single crystalline YBa2Cu3O7-δ (YBCO) thin films were grown by pulsed laser deposition in order to probe the oxygen deficiency δ using a mono-energetic positron beam. The sample set covered a large range of δ (0.191 < δ < 0.791) yielding a variation of the critical temperature Tc between 25 and 90 K. We found a linear correlation between the Doppler broadening of the positron electron annihilation line and δ determined by X-ray diffraction. Ab-initio calculations have been performed in order to exclude the presence of Y vacancies and to ensure the negligible influence of potentially present Ba or Cu vacancies to the found correlation. Moreover, scanning with the positron beam allowed us to analyze the spatial variation of δ, which was found to fluctuate with a standard deviation of up to 0.079(5) within a single YBCO film.

  3. Griffiths phase and colossal magnetoresistance in Nd0.5Sr0.5MnO3 oxygen-deficient thin films

    NASA Astrophysics Data System (ADS)

    Solin, N. I.; Korolyov, A. V.; Medvedev, Yu. V.; Nikolaenko, Yu. M.; Khokhlov, V. A.; Prokhorov, A. Yu.; Levchenko, G. G.

    2013-05-01

    This work is devoted to study the influence of the Griffiths phase in colossal magnetoresistance manganites. Griffiths-phase-like behavior of the paramagnetic susceptibility χ0 is observed in Nd0.5Sr0.5MnO3 oxygen-deficient thin films fabricated by magnetron sputtering deposition. In Nd0.5Sr0.5MnO3-δ films with oxygen deficiency for ТG≈260-280 K>T>TC=138 K (ТG and ТС—Griffiths and Curie temperatures, respectively), paramagnetic matrix consists of a magnetic phase with short-range order (˜1-1.5 nm) (which is responsible for the colossal magnetoresistance (CMR) above ТС), and is embedded in this matrix region with long-range ferromagnetic order (≫10 nm), responsible for the Griffiths phase-like behavior of the paramagnetic susceptibility. Electrical resistivity is caused by carrier tunneling between the localized states and obeys the Efros-Shklovskii law. Magnetic resistivity is caused by change of the localized state sizes under the magnetic field. The temperature and magnetic field dependencies of size of the phase inhomogeneity inclusions, found from measurements of magneto-transport properties, can be satisfactorily described by the model of thermodynamic phase separation into metallic droplets of small radius in a paramagnetic matrix. Intrinsic nanoscale inhomogeneities caused by thermodynamic phase separation, rather than the Griffiths phase, determine the electrical resistivity and colossal magnetoresistance of the films. In half-doped manganites, the nature of long-range ordered magnetic phases may be related, besides the chemical heterogeneity, to proximity to a ferromagnetic-antiferromagnetic boundary at the phase diagram as well. The results are in good agreement with the model of existence of an analog of Griffiths phase temperature in half-doped manganites.

  4. Structural evolution across the insulator-metal transition in oxygen-deficient BaTiO3-δ studied using neutron total scattering and Rietveld analysis

    SciTech Connect

    Jeong, I.-K.; Lee, Seunghun; Jeong, Se-Young; Won, C. J.; Hur, N.; Llobet, A.

    2011-08-29

    Oxygen-deficient BaTiO3-δ exhibits an insulator-metal transition with increasing δ. We performed neutron total scattering measurements to study structural evolution across an insulator-metal transition in BaTiO3-δ. Despite its significant impact on resistivity, slight oxygen reduction (δ=0.09) caused only a small disturbance on the local doublet splitting of Ti-O bond. This finding implies that local polarization is well preserved under marginal electric conduction. In the highly oxygen-deficient metallic state (δ=0.25), however, doublet splitting of the Ti-O bond became smeared. The smearing of the local Ti-O doublet is complemented with long-range structural analysis and demonstrates that the metallic conduction in the highly oxygen-reduced BaTiO3-δ is due to the appearance of nonferroelectric cubic lattice.

  5. Ferroelectric ultrathin perovskite films

    DOEpatents

    Rappe, Andrew M; Kolpak, Alexie Michelle

    2013-12-10

    Disclosed herein are perovskite ferroelectric thin-film. Also disclosed are methods of controlling the properties of ferroelectric thin films. These films can be used in a variety materials and devices, such as catalysts and storage media, respectively.

  6. Water conditions and geochemistry in northern Adriatic anoxia-prone areas and response of benthic faunas to oxygen deficiencies

    NASA Astrophysics Data System (ADS)

    Zuschin, Martin; Riedel, Bettina; Stachowitsch, Michael; Cermelj, Branko

    2010-05-01

    One predicted effect of global climate change, specifically global warming, is the increase in the temperatures and stratification of shallow coastal and estuarine systems. This, coupled with ongoing anthropogenic eutrophication, will exacerbate hypoxia and benthic mortalities, significantly damaging these critical marine ecosystems. These phenomena are particularly severe on sublitoral soft-bottoms such as the poorly sorted silty sands at the study site in the northern Adriatic Sea. We deployed a specially developed underwater chamber to artificially induce anoxia in situ. Our Experimental Anoxia Generating Unit (EAGU) is a large plexiglass chamber that combines a digital camera with oxygen/hydrogen sulphide/pH sensors along with flashes and battery packs. The unit can be deployed for up to five days to autonomously generate oxygen crises and quantify both physico-chemical parameters and benthic responses. The system is initially positioned in an "open" configuration (open-sided aluminium frame) over the benthic fauna ("control" experiment). After 24 h the EAGU is switched to its "closed" configuration (plexiglass enclosure) and repositioned over the same assemblage. In this contribution, we focus on the natural oxygen content, temperature and pH of bottom waters during summer, the course of oxygen decrease during our experiments and the onset of H2S development. Oxygen content of the bottom water, a few centimetres above the sediment-water interface, ranges from ~3.5-8 but is mostly between 4-6 ml l-1 during July to September of the study periods (2005 and 2006) and decreases to zero within ~1-3 days after initiation of our experiments. In parallel, H2S starts to develop at the onset of anoxia. Water temperatures at the bottom were stable during experiments and ranged from 18.5°C to 21.4°C, but pH decreased from 8.3 to 8.1 at the beginning to 7.9 to 7.7 at the end of the experiments. Sediment profiling indicates that the diffusive benthic boundary layer is

  7. Combined Increases in Mitochondrial Cooperation and Oxygen Photoreduction Compensate for Deficiency in Cyclic Electron Flow in Chlamydomonas reinhardtii[W][OPEN

    PubMed Central

    Dang, Kieu-Van; Plet, Julie; Tolleter, Dimitri; Jokel, Martina; Cuiné, Stéphan; Carrier, Patrick; Auroy, Pascaline; Richaud, Pierre; Johnson, Xenie; Alric, Jean; Allahverdiyeva, Yagut; Peltier, Gilles

    2014-01-01

    During oxygenic photosynthesis, metabolic reactions of CO2 fixation require more ATP than is supplied by the linear electron flow operating from photosystem II to photosystem I (PSI). Different mechanisms, such as cyclic electron flow (CEF) around PSI, have been proposed to participate in reequilibrating the ATP/NADPH balance. To determine the contribution of CEF to microalgal biomass productivity, here, we studied photosynthesis and growth performances of a knockout Chlamydomonas reinhardtii mutant (pgrl1) deficient in PROTON GRADIENT REGULATION LIKE1 (PGRL1)–mediated CEF. Steady state biomass productivity of the pgrl1 mutant, measured in photobioreactors operated as turbidostats, was similar to its wild-type progenitor under a wide range of illumination and CO2 concentrations. Several changes were observed in pgrl1, including higher sensitivity of photosynthesis to mitochondrial inhibitors, increased light-dependent O2 uptake, and increased amounts of flavodiiron (FLV) proteins. We conclude that a combination of mitochondrial cooperation and oxygen photoreduction downstream of PSI (Mehler reactions) supplies extra ATP for photosynthesis in the pgrl1 mutant, resulting in normal biomass productivity under steady state conditions. The lower biomass productivity observed in the pgrl1 mutant in fluctuating light is attributed to an inability of compensation mechanisms to respond to a rapid increase in ATP demand. PMID:24989042

  8. Diverse Mechanisms of Sp1-Dependent Transcriptional Regulation Potentially Involved in the Adaptive Response of Cancer Cells to Oxygen-Deficient Conditions

    PubMed Central

    Koizume, Shiro; Miyagi, Yohei

    2015-01-01

    The inside of a tumor often contains a hypoxic area caused by a limited supply of molecular oxygen due to aberrant vasculature. Hypoxia-inducible factors (HIFs) are major transcription factors that are required for cancer cells to adapt to such stress conditions. HIFs, complexed with the aryl hydrocarbon receptor nuclear translocator, bind to and activate target genes as enhancers of transcription. In addition to this common mechanism, the induction of the unfolded protein response and mTOR signaling in response to endoplasmic reticulum stress is also known to be involved in the adaptation to hypoxia conditions. Sp1 is a ubiquitously-expressed transcription factor that plays a vital role in the regulation of numerous genes required for normal cell function. In addition to the well-characterized stress response mechanisms described above, increasing experimental evidence suggests that Sp1 and HIFs collaborate to drive gene expression in cancer cells in response to hypoxia, thereby regulating additional adaptive responses to cellular oxygen deficiency. However, these characteristics of Sp1 and their biological merits have not been summarized. In this review, we will discuss the diverse mechanisms of transcriptional regulation by Sp1 and their potential involvement in the adaptive response of cancer cells to hypoxic tumor microenvironments. PMID:26703734

  9. Partaking of Archaea to biogeochemical cycling in oxygen-deficient zones of meromictic saline Lake Faro (Messina, Italy).

    PubMed

    La Cono, Violetta; La Spada, Gina; Arcadi, Erika; Placenti, Francesco; Smedile, Francesco; Ruggeri, Gioacchino; Michaud, Luigi; Raffa, Carmen; De Domenico, Emilio; Sprovieri, Mario; Mazzola, Salvatore; Genovese, Lucrezia; Giuliano, Laura; Slepak, Vladlen Z; Yakimov, Michail M

    2013-06-01

    We used a combination of molecular and microbiological approaches to determine the activity, abundance and diversity of archaeal populations inhabiting meromictic saline Lake Faro (Messina, Italy). Analysis of archaeal 16S rRNA, amoA, accA and hbd genes and transcripts revealed that sub- and anoxic layers of Lake Faro are primarily inhabited by the organisms related to the clusters of Marine Group I.1a of Thaumarchaeota frequently recovered from oxygen-depleted marine ecosystems. These organisms dominated the metabolically active archaea down to the bottom of the lake, indicating their adaptation to recurrent changes in the levels of water column hypoxia. The upper microaerobic layer of Lake Faro redoxcline has the maximal rates of dark primary production much lower than those of other previously studied pelagic redoxclines, but comparable to the values of meso- and bathypelagic areas of Mediterranean Sea. Application of bacterial inhibitors, especially azide, significantly declined the CO2 fixation rates in the low interface and monimolimnion, whereas archaea-specific inhibitor had effect only in upper part of the redoxcline. Based on these findings, we hypothesize that dark bicarbonate fixation in suboxic zone of Lake Faro results mainly from archaeal activity which is affected by the predicted lack in oxygen in lower layers. © 2012 Society for Applied Microbiology and Blackwell Publishing Ltd.

  10. The Chaoborus pump: Migrating phantom midge larvae sustain hypolimnetic oxygen deficiency and nutrient internal loading in lakes.

    PubMed

    Tang, Kam W; Flury, Sabine; Grossart, Hans-Peter; McGinnis, Daniel F

    2017-10-01

    Hypolimnetic oxygen demand in lakes is often assumed to be driven mainly by sediment microbial processes, while the role of Chaoborus larvae, which are prevalent in eutrophic lakes with hypoxic to anoxic bottoms, has been overlooked. We experimentally measured the respiration rates of C. flavicans at different temperatures yielding a Q10 of 1.44-1.71 and a respiratory quotient of 0.84-0.98. Applying the experimental data in a system analytical approach, we showed that migrating Chaoborus larvae can significantly add to the water column and sediment oxygen demand, and contribute to the observed linear relationship between water column respiration and depth. The estimated phosphorus excretion by Chaoborus in sediment is comparable in magnitude to the required phosphorus loading for eutrophication. Migrating Chaoborus larvae thereby essentially trap nutrients between the water column and the sediment, and this continuous internal loading of nutrients would delay lake remediation even when external inputs are stopped. Copyright © 2017 Elsevier Ltd. All rights reserved.

  11. Mechanisms of photodoping in oxygen-deficient YBa2Cu3Ox films studied by in situ transport measurements

    NASA Astrophysics Data System (ADS)

    Stockinger, C.; Markowitsch, W.; Lang, W.; Kula, W.; Sobolewski, Roman

    1998-04-01

    In situ studies of the superconducting and normal-state transport properties in partially oxygen-depleted, metallic YBa2Cu3Ox (Tc,mid~52 K) thin films exposed to long-term white-light illumination (photodoping) are reported. We observed that the effects of photoexcitation strongly depended on the temperature at which the photodoping was performed. The Hall number increased during the illumination in the entire tested temperature range from 70 to 290 K, with the strongest increase near room temperature, whereas, the Hall mobility increased steadily only upon low-temperature illumination. At temperatures above 250 K, it showed an abrupt initial increase followed by a long-term decrease. At high temperatures, the Hall quantities react on the impact of light excitation independently from each other, which strongly suggests that both the photoassisted oxygen ordering and charge-transfer mechanisms contribute to photodoping, the former acting mainly on the mobility, while the latter on the density of charge carriers. The photoinduced enhancement of the superconducting transition temperature Tc exhibited essentially the same temperature dependence as the enhancement of the Hall number, being largest (ΔTc~2.6 K) for the illumination performed at high temperatures. Thus, the Tc enhancement results from the change of the density more likely than of the mobility of the charge carriers.

  12. A multiproxy approach to understanding the "enhanced" flux of organic matter through the oxygen-deficient waters of the Arabian Sea

    NASA Astrophysics Data System (ADS)

    Keil, Richard G.; Neibauer, Jacquelyn A.; Biladeau, Christina; van der Elst, Kelsey; Devol, Allan H.

    2016-04-01

    Free-drifting sediment net traps were deployed 14 times at depths between 80 and 500 m for 1-3 days each during the late monsoon-intermonsoon transition in the central Arabian Sea. Two locations (19.5 and 15.5° N) were within the permanently oxygen-deficient zone (ODZ), and a third (11° N) had a shallow and thin oxygen minimum. The secondary nitrite maximum, which serves as a tracer of the ODZ, thinned from ˜ 250 m thick at stations 19.5 and 15.5° N to ˜ 50 m thick at station 11° N. Overall, organic carbon fluxes ranged from 13.2 g m2 yr-1 at 80 m to a minimum of 1.1 g m2 yr-1 at 500 m. Fluxes at the more oxygenated 11° N station attenuate faster than within the permanent ODZ. Martin curve attenuation coefficients for 19.5 and 15.5° N are respectively 0.59 and 0.63 and for 11° N it is 0.98. At least six potential mechanisms might explain why particles sinking through the ODZ are more effectively transferred to depth: (M1) oxygen effects, (M2) microbial loop efficiencies and chemoautotrophy, (M3) changes in zooplankton dynamics, (M4) additions of ballast that might sorb and protect organic matter from decay (M4a) or change sinking speeds (M4b), (M5) inputs of refractory organic matter and (M6) temperature effects. These mechanisms are intertwined, and they were explored using a combination of mineral (XPS) and organic matter characterizations of the sinking material, shipboard incubation experiments, and evaluations of existing literature. Direct evidence was found supporting an oxygen effect and/or changes in the efficiency of the microbial loop including the addition of chemoautotrophic carbon to the sinking flux in the upper 500 m. Less direct evidence was found for the other potential mechanisms. A simple conceptual model consistent with our and other recent data suggests that the upper ODZ microbial community determines the initial flux attenuation, and that zooplankton and sinking speed become more important deeper in the water column. The exact

  13. OXYGEN TRANSPORT CERAMIC MEMBRANES

    SciTech Connect

    Dr. Sukumar Bandopadhyay; Dr. Nagendra Nagabhushana

    2002-07-01

    In the present quarter, oxygen transport perovskite ceramic membranes are evaluated for strength and fracture in oxygen gradient conditions. Oxygen gradients are created in tubular membranes by insulating the inner surface from the reducing environment by platinum foils. Fracture in these test conditions is observed to have a gradient in trans and inter-granular fracture as opposed to pure trans-granular fracture observed in homogeneous conditions. Fracture gradients are reasoned to be due to oxygen gradient set up in the membrane, variation in stoichiometry across the thickness and due to varying decomposition of the parent perovskite. The studies are useful in predicting fracture criterion in actual reactor conditions and in understanding the initial evolution of fracture processes.

  14. Density functional study on redox energetics of LaMO3-δ (M=Sc-Cu) perovskite-type oxides

    NASA Astrophysics Data System (ADS)

    Pishahang, Mehdi; Erik Mohn, Chris; Stølen, Svein

    2016-01-01

    This study evaluates the redox energetics of LaMO3-δ (M=Sc-Cu) perovskite-type oxides via generalized gradient approximation (GGA) to DFT. Two different approaches to redox energetics of oxygen deficient perovskites of strongly non-stoichiometric (δ=0.5) and dilute defect limits (δ→0) are studied. In the first approach the enthalpies of oxidation are calculated using the stoichiometric end-compounds of LaMO3 and LaMO2.5. The most common structures for the reduced lanthanides and strontides similar to the ones experimentally reported for SrMnO2.5, SrFeO2.5, and LaNiO2.5 are considered. The second approach to the oxidation enthalpies termed (δ→0) follow the trend observed experimentally. This approach represents the experimental conditions of the measured oxygen enthalpies, and is hampered less by the artificial features due to spurious self-interaction errors in GGA.

  15. Synthesis of a polar ordered oxynitride perovskite

    NASA Astrophysics Data System (ADS)

    Vadapoo, Rajasekarakumar; Ahart, Muhtar; Somayazulu, Maddury; Holtgrewe, Nicholas; Meng, Yue; Konopkova, Zuzana; Hemley, Russell J.; Cohen, R. E.

    2017-06-01

    For decades, numerous attempts have been made to produce polar oxynitride perovskites, where some of the oxygen is replaced by nitrogen, but a polar ordered oxynitride has never been demonstrated. Caracas and Cohen [Appl. Phys. Lett. 91, 092902 (2007), 10.1063/1.2776370] studied possible ordered polar oxynitrides within density-functional theory (DFT) and found a few candidates that were predicted to be insulating and at least metastable. YSi O2N stood out with huge predicted polarization and nonlinear optic coefficients. In this study, we demonstrate the synthesis of perovskite-structured YSi O2N by using a combination of a diamond-anvil cell and in situ laser-heating techniques. Subsequent in situ x-ray diffraction, second-harmonic generation, and Raman-scattering measurements confirm that it is polar and a strong nonlinear optical material, with structure and properties similar to those predicted by DFT.

  16. Nanogranular metallic Fe oxygen deficient TiO2-δ composite films: a room temperature, highly carrier polarized magnetic semiconductor

    NASA Astrophysics Data System (ADS)

    Yoon, S. D.; Widom, A.; Miller, K. E.; McHenry, M. E.; Vittoria, C.; Harris, V. G.

    2008-05-01

    Nanogranular metallic iron (Fe) and titanium dioxide (TiO2-δ) were sequentially deposited on (100) lanthanum aluminate (LaAlO3) substrates in a low oxygen chamber pressure using a pulsed laser ablation deposition (PLD) technique. By sequential deposition, ≈10 nm diameter metallic Fe spherical grains were suspended within a TiO2-δ matrix. The films show ferromagnetic behavior with a saturation magnetization of 3100 G at room temperature. Our estimate of the saturation magnetization based on the size and distribution of the Fe spheres agreed with the measured value. The film composite structure was characterized as a p-type magnetic semiconductor at 300 K with a carrier density of the order of ≈1022 cm-3. The hole carriers were excited at the interface between the nanogranular Fe and TiO2-δ matrix, similar to holes excited in the metal/n-type semiconductor interface commonly observed in metal-oxide-semiconductor (MOS) devices. From the large anomalous Hall effect measured in these films, we observed that the holes at the interface were strongly spin polarized. Structure and magnetotransport properties suggested that these PLD films have potential spintronics applications.

  17. Oxygen deficient α-Fe2O3 photoelectrodes: a balance between enhanced electrical properties and trap-mediated losses.

    PubMed

    Forster, Mark; Potter, Richard J; Ling, Yichuan; Yang, Yi; Klug, David R; Li, Yat; Cowan, Alexander J

    2015-07-15

    Intrinsic doping of hematite through the inclusion of oxygen vacancies (VO) is being increasingly explored as a simple, low temperature route to preparing active water splitting α-Fe2O3-x photoelectrodes. Whilst it is widely accepted that the introduction of VO leads to improved conductivities, little else is verified regarding the actual mechanism of enhancement. Here we employ transient absorption (TA) spectroscopy to build a comprehensive kinetic model for water oxidation on α-Fe2O3-x . In contrast to previous suggestions, the primary effect of introducing VO is to block very slow (ms) surface hole - bulk electron recombination pathways. In light of our mechanistic research we are also able to identify and address a cause of the high photocurrent onset potential, a common issue with this class of electrodes. Atomic layer deposition (ALD) of Al2O3 is found to be particularly effective with α-Fe2O3-x , leading to the photocurrent onset potential shifting by ca. 200 mV. Significantly TA measurements on these ALD passivated electrodes also provide important insights into the role of passivating layers, that are relevant to the wider development of α-Fe2O3 photoelectrodes.

  18. Spin polarized electronic states and spin textures at the surface of oxygen-deficient SrTiO3

    NASA Astrophysics Data System (ADS)

    Jeschke, Harald O.; Altmeyer, Michaela; Rozenberg, Marcelo; Gabay, Marc; Valenti, Roser

    We investigate the electronic structure and spin texture at the (001) surface of SrTiO3 in the presence of oxygen vacancies by means of ab initio density functional theory (DFT) calculations of slabs. Relativistic non-magnetic DFT calculations exhibit Rashba-like spin winding with a characteristic energy scale ~ 10 meV. However, when surface magnetism on the Ti ions is included, bands become spin-split with an energy difference ~ 100 meV at the Γ point. This energy scale is comparable to the observations in SARPES experiments performed on the two-dimensional electronic states confined near the (001) surface of SrTiO3. We find the spin polarized state to be the ground state of the system, and while magnetism tends to suppress the effects of the relativistic Rashba interaction, signatures of it are still clearly visible in terms of complex spin textures. We gratefully acknowledge financial support from the Deutsche Forschungsgemeinschaft through grants SFB/TR 49 and FOR 1346.

  19. Rapid Synthesis of Thin and Long Mo17O47 Nanowire-Arrays in an Oxygen Deficient Flame

    PubMed Central

    Allen, Patrick; Cai, Lili; Zhou, Lite; Zhao, Chenqi; Rao, Pratap M.

    2016-01-01

    Mo17O47 nanowire-arrays are promising active materials and electrically-conductive supports for batteries and other devices. While high surface area resulting from long, thin, densely packed nanowires generally leads to improved performance in a wide variety of applications, the Mo17O47 nanowire-arrays synthesized previously by electrically-heated chemical vapor deposition under vacuum conditions were relatively thick and short. Here, we demonstrate a method to grow significantly thinner and longer, densely packed, high-purity Mo17O47 nanowire-arrays with diameters of 20–60 nm and lengths of 4–6 μm on metal foil substrates using rapid atmospheric flame vapor deposition without any chamber or walls. The atmospheric pressure and 1000 °C evaporation temperature resulted in smaller diameters, longer lengths and order-of-magnitude faster growth rate than previously demonstrated. As explained by kinetic and thermodynamic calculations, the selective synthesis of high-purity Mo17O47 nanowires is achieved due to low oxygen partial pressure in the flame products as a result of the high ratio of fuel to oxidizer supplied to the flame, which enables the correct ratio of MoO2 and MoO3 vapor concentrations for the growth of Mo17O47. This flame synthesis method is therefore a promising route for the growth of composition-controlled one-dimensional metal oxide nanomaterials for many applications. PMID:27271194

  20. Rapid Synthesis of Thin and Long Mo17O47 Nanowire-Arrays in an Oxygen Deficient Flame

    NASA Astrophysics Data System (ADS)

    Allen, Patrick; Cai, Lili; Zhou, Lite; Zhao, Chenqi; Rao, Pratap M.

    2016-06-01

    Mo17O47 nanowire-arrays are promising active materials and electrically-conductive supports for batteries and other devices. While high surface area resulting from long, thin, densely packed nanowires generally leads to improved performance in a wide variety of applications, the Mo17O47 nanowire-arrays synthesized previously by electrically-heated chemical vapor deposition under vacuum conditions were relatively thick and short. Here, we demonstrate a method to grow significantly thinner and longer, densely packed, high-purity Mo17O47 nanowire-arrays with diameters of 20-60 nm and lengths of 4-6 μm on metal foil substrates using rapid atmospheric flame vapor deposition without any chamber or walls. The atmospheric pressure and 1000 °C evaporation temperature resulted in smaller diameters, longer lengths and order-of-magnitude faster growth rate than previously demonstrated. As explained by kinetic and thermodynamic calculations, the selective synthesis of high-purity Mo17O47 nanowires is achieved due to low oxygen partial pressure in the flame products as a result of the high ratio of fuel to oxidizer supplied to the flame, which enables the correct ratio of MoO2 and MoO3 vapor concentrations for the growth of Mo17O47. This flame synthesis method is therefore a promising route for the growth of composition-controlled one-dimensional metal oxide nanomaterials for many applications.

  1. Highly Oriented Low-Dimensional Tin Halide Perovskites with Enhanced Stability and Photovoltaic Performance.

    PubMed

    Liao, Yuqin; Liu, Hefei; Zhou, Wenjia; Yang, Dongwen; Shang, Yuequn; Shi, Zhifang; Li, Binghan; Jiang, Xianyuan; Zhang, Lijun; Quan, Li Na; Quintero-Bermudez, Rafael; Sutherland, Brandon R; Mi, Qixi; Sargent, Edward H; Ning, Zhijun

    2017-05-17

    The low toxicity and a near-ideal choice of bandgap make tin perovskite an attractive alternative to lead perovskite in low cost solar cells. However, the development of Sn perovskite solar cells has been impeded by their extremely poor stability when exposed to oxygen. We report low-dimensional Sn perovskites that exhibit markedly enhanced air stability in comparison with their 3D counterparts. The reduced degradation under air exposure is attributed to the improved thermodynamic stability after dimensional reduction, the encapsulating organic ligands, and the compact perovskite film preventing oxygen ingress. We then explore these highly oriented low-dimensional Sn perovskite films in solar cells. The perpendicular growth of the perovskite domains between electrodes allows efficient charge carrier transport, leading to power conversion efficiencies of 5.94% without the requirement of further device structure engineering. We tracked the performance of unencapsulated devices over 100 h and found no appreciable decay in efficiency. These findings raise the prospects of pure Sn perovskites for solar cells application.

  2. Perovskite-type catalytic materials for environmental applications

    NASA Astrophysics Data System (ADS)

    Labhasetwar, Nitin; Saravanan, Govindachetty; Megarajan, Suresh Kumar; Manwar, Nilesh; Khobragade, Rohini; Doggali, Pradeep; Grasset, Fabien

    2015-06-01

    Perovskites are mixed-metal oxides that are attracting much scientific and application interest owing to their low price, adaptability, and thermal stability, which often depend on bulk and surface characteristics. These materials have been extensively explored for their catalytic, electrical, magnetic, and optical properties. They are promising candidates for the photocatalytic splitting of water and have also been extensively studied for environmental catalysis applications. Oxygen and cation non-stoichiometry can be tailored in a large number of perovskite compositions to achieve the desired catalytic activity, including multifunctional catalytic properties. Despite the extensive uses, the commercial success for this class of perovskite-based catalytic materials has not been achieved for vehicle exhaust emission control or for many other environmental applications. With recent advances in synthesis techniques, including the preparation of supported perovskites, and increasing understanding of promoted substitute perovskite-type materials, there is a growing interest in applied studies of perovskite-type catalytic materials. We have studied a number of perovskites based on Co, Mn, Ru, and Fe and their substituted compositions for their catalytic activity in terms of diesel soot oxidation, three-way catalysis, N2O decomposition, low-temperature CO oxidation, oxidation of volatile organic compounds, etc. The enhanced catalytic activity of these materials is attributed mainly to their altered redox properties, the promotional effect of co-ions, and the increased exposure of catalytically active transition metals in certain preparations. The recent lowering of sulfur content in fuel and concerns over the cost and availability of precious metals are responsible for renewed interest in perovskite-type catalysts for environmental applications.

  3. Perovskite-type catalytic materials for environmental applications

    PubMed Central

    Labhasetwar, Nitin; Saravanan, Govindachetty; Kumar Megarajan, Suresh; Manwar, Nilesh; Khobragade, Rohini; Doggali, Pradeep; Grasset, Fabien

    2015-01-01

    Perovskites are mixed-metal oxides that are attracting much scientific and application interest owing to their low price, adaptability, and thermal stability, which often depend on bulk and surface characteristics. These materials have been extensively explored for their catalytic, electrical, magnetic, and optical properties. They are promising candidates for the photocatalytic splitting of water and have also been extensively studied for environmental catalysis applications. Oxygen and cation non-stoichiometry can be tailored in a large number of perovskite compositions to achieve the desired catalytic activity, including multifunctional catalytic properties. Despite the extensive uses, the commercial success for this class of perovskite-based catalytic materials has not been achieved for vehicle exhaust emission control or for many other environmental applications. With recent advances in synthesis techniques, including the preparation of supported perovskites, and increasing understanding of promoted substitute perovskite-type materials, there is a growing interest in applied studies of perovskite-type catalytic materials. We have studied a number of perovskites based on Co, Mn, Ru, and Fe and their substituted compositions for their catalytic activity in terms of diesel soot oxidation, three-way catalysis, N2O decomposition, low-temperature CO oxidation, oxidation of volatile organic compounds, etc. The enhanced catalytic activity of these materials is attributed mainly to their altered redox properties, the promotional effect of co-ions, and the increased exposure of catalytically active transition metals in certain preparations. The recent lowering of sulfur content in fuel and concerns over the cost and availability of precious metals are responsible for renewed interest in perovskite-type catalysts for environmental applications. PMID:27877813

  4. Isolation of two-dimensional 2:1 cation-ordered perovskite units by anion vacancy ordering in Ba6Na2Nb2P2O17.

    PubMed

    Kuang, Xiaojun; Claridge, John B; Price, Tim; Iddles, David M; Rosseinsky, Matthew J

    2008-10-06

    A new six-layer perovskite-related structure Ba 6Na 2Nb 2M 2O 17 (M = P, V), which consists of cubic (c) BaO 3 layers and oxygen-deficient pseudocubic (c') BaO 2 layers stacked in the sequence c'ccccc, is presented. In Ba 6Na 2Nb 2M 2O 17, two-dimensional slabs of the well-known 2:1 octahedral cation-ordered perovskite motif are isolated between layers of tetrahedral units formed by anion vacancy ordering: two consecutive NbO 6 octahedral layers are sandwiched by two single NaO 6 octahedral layers, which, in turn, connect with two isolated MO 4 tetrahedral layers. Both oxides are derived from the 2:1 ordered perovskite structure (e.g., Ba 3ZnTa 2O 9) by ordered removal of O atoms in every sixth BaO 3 layer. Both materials exhibit a relative permittivity of approximately 20-23, Q x f 0 values of approximately 7800-10600 GHz, and negative temperature coefficients of the resonant frequency of approximately -23 to -7 ppm/ degrees C.

  5. Effect of basic additives on Pt/Al{sub 2}O{sub 3} for CO and propylene oxidation under oxygen-deficient conditions

    SciTech Connect

    Lee, C.H.; Chen, Y.W.

    1997-05-01

    Pt catalysts supported on Al{sub 2}O{sub 3}, CeO{sub 2}/Al{sub 2}O{sub 3}, Na{sub 2}O/Al{sub 2}O{sub 3}, and K{sub 2}O/Al{sub 2}O{sub 3} were prepared and characterized with respect to surface area, CO chemisorption, temperature-programmed desorption (TPD) of CO{sub 2}, and temperature-programmed reduction (TPR) of H{sub 2}. The effects of basic additives on Pt/Al{sub 2}O{sub 3} for CO and propylene oxidation were investigated. The addition of basic additives slightly decreases the surface area of the catalyst and does not significantly change Pt dispersion. The basicity of the catalyst is in the order Pt-K{sub 2}O/Al{sub 2}O{sub 3} > Pt-Na{sub 2}O/Al{sub 2}O{sub 3} > Pt-CeO{sub 2}/Al{sub 2}O{sub 3} > Pt/Al{sub 2}O{sub 3}. The promoted Pt/Al{sub 2}O{sub 3} catalysts are much more active than the unpromoted one for CO and propylene oxidation under the stoichiometric point. Under oxygen-deficient conditions and in the absence of water, propylene conversions on all catalysts studied herein increase with increasing reaction temperature. Pt/Al{sub 2}O{sub 3} exhibits the highest propylene conversion and the lowest CO conversion among these catalysts, and the addition of CeO{sub 2}, Na{sub 2}O, and K{sub 2}O on Pt/Al{sub 2}O{sub 3} can promote the CO conversion. Under oxygen-deficient conditions and in the presence of water, the water-gas shift and steam re-forming reactions can take place and result in increases of CO and propylene conversions. Pt/Al{sub 2}O{sub 3} is the most active catalyst for the steam reforming reaction and the least active catalyst for the water-gas shift reaction among these catalysts. However, the addition of basic additives on Pt/Al{sub 2}O{sub 3} catalyst can significantly enhance the water-gas shift reaction that can reduce CO emission. The promotional effect is in the order K{sub 2}O > Na{sub 2}O > CeO{sub 2}. K{sub 2}O could be a promising additive to a catalytic converter of a two-stroke motorcycle since it can enhance CO conversion.

  6. The chemical composition of TS 01, the most oxygen-deficient planetary nebula. AGB nucleosynthesis in a metal-poor binary star

    NASA Astrophysics Data System (ADS)

    Stasińska, G.; Morisset, C.; Tovmassian, G.; Rauch, T.; Richer, M. G.; Peña, M.; Szczerba, R.; Decressin, T.; Charbonnel, C.; Yungelson, L.; Napiwotzki, R.; Simón-Díaz, S.; Jamet, L.

    2010-02-01

    The planetary nebula TS 01 (also called PN G 135.9+55.9 or SBS 1150+599A) with its record-holding low oxygen abundance and its double degenerate close binary core (period 3.9 h) is an exceptional object located in the Galactic halo. We have secured observational data in a complete wavelength range to pin down the abundances of half a dozen elements in the nebula. The abundances are obtained via detailed photoionization modelling which takes into account all the observational constraints (including geometry and aperture effects) using the pseudo-3D photoionization code Cloudy_3D. The spectral energy distribution of the ionizing radiation is taken from appropriate model atmospheres. Incidentally we find from the new observational constraints that both stellar components contribute to the ionization: the “cool” one provides the bulk of hydrogen ionization, while the “hot” one is responsible for the presence of the most highly charged ions, which explains why previous attempts to model the nebula experienced difficulties. The nebular abundances of C, N, O, and Ne are found to be 1/3.5, 1/4.2, 1/70, and 1/11 of the solar value respectively, with uncertainties of a factor 2. Thus the extreme O deficiency of this object is confirmed. The abundances of S and Ar are less than 1/30 of solar. The abundance of He relative to H is 0.089 ± 0.009. Standard models of stellar evolution and nucleosynthesis cannot explain the abundance pattern observed in the nebula. To obtain an extreme oxygen deficiency in a star whose progenitor has an initial mass of about 1 M⊙ requires an additional mixing process, which can be induced by stellar rotation and/or by the presence of the close companion. We have computed a stellar model with an initial mass of 1 M⊙, appropriate metallicity, and initial rotation of 100 km s-1, and find that rotation greatly improves the agreement between the predicted and observed abundances. Based on observations obtained at the Canada

  7. Perovskite photonic sources

    NASA Astrophysics Data System (ADS)

    Sutherland, Brandon R.; Sargent, Edward H.

    2016-05-01

    The field of solution-processed semiconductors has made great strides; however, it has yet to enable electrically driven lasers. To achieve this goal, improved materials are required that combine efficient (>50% quantum yield) radiative recombination under high injection, large and balanced charge-carrier mobilities in excess of 10 cm2 V-1 s-1, free-carrier densities greater than 1017 cm-3 and gain coefficients exceeding 104 cm-1. Solid-state perovskites are -- in addition to galvanizing the field of solar electricity -- showing great promise in photonic sources, and may be the answer to realizing solution-cast laser diodes. Here, we discuss the properties of perovskites that benefit light emission, review recent progress in perovskite electroluminescent diodes and optically pumped lasers, and examine the remaining challenges in achieving continuous-wave and electrically driven lasing.

  8. Los Alamos Discovers Super Efficient Solar Using Perovskite Crystals

    SciTech Connect

    Mohite, Aditya; Nie, Wanyi

    2015-01-29

    State-of-the-art photovoltaics using high-purity, large-area, wafer-scale single-crystalline semiconductors grown by sophisticated, high temperature crystal-growth processes offer promising routes for developing low-cost, solar-based clean global energy solutions for the future. Solar cells composed of the recently discovered material organic-inorganic perovskites offer the efficiency of silicon, yet suffer from a variety of deficiencies limiting the commercial viability of perovskite photovoltaic technology. In research to appear in Science, Los Alamos National Laboratory researchers reveal a new solution-based hot-casting technique that eliminates these limitations, one that allows for the growth of high-quality, large-area, millimeter-scale perovskite crystals and demonstrates that highly efficient and reproducible solar cells with reduced trap assisted recombination can be realized.

  9. Los Alamos Discovers Super Efficient Solar Using Perovskite Crystals

    ScienceCinema

    Mohite, Aditya; Nie, Wanyi

    2016-07-12

    State-of-the-art photovoltaics using high-purity, large-area, wafer-scale single-crystalline semiconductors grown by sophisticated, high temperature crystal-growth processes offer promising routes for developing low-cost, solar-based clean global energy solutions for the future. Solar cells composed of the recently discovered material organic-inorganic perovskites offer the efficiency of silicon, yet suffer from a variety of deficiencies limiting the commercial viability of perovskite photovoltaic technology. In research to appear in Science, Los Alamos National Laboratory researchers reveal a new solution-based hot-casting technique that eliminates these limitations, one that allows for the growth of high-quality, large-area, millimeter-scale perovskite crystals and demonstrates that highly efficient and reproducible solar cells with reduced trap assisted recombination can be realized.

  10. A High-Performing Sulfur-Tolerant and Redox-Stable Layered Perovskite Anode for Direct Hydrocarbon Solid Oxide Fuel Cells.

    PubMed

    Ding, Hanping; Tao, Zetian; Liu, Shun; Zhang, Jiujun

    2015-12-09

    Development of alternative ceramic oxide anode materials is a key step for direct hydrocarbon solid oxide fuel cells (SOFCs). Several lanthanide based layered perovskite-structured oxides demonstrate outstanding oxygen diffusion rate, favorable electronic conductivity, and good oxygen surface exchange kinetics, owing to A-site ordered structure in which lanthanide and alkali-earth ions occupy alternate (001) layers and oxygen vacancies are mainly located in [LnOx] planes. Here we report a nickel-free cation deficient layered perovskite, (PrBa)0.95(Fe0.9Mo0.1)2O5 + δ (PBFM), for SOFC anode, and this anode shows an outstanding performance with high resistance against both carbon build-up and sulfur poisoning in hydrocarbon fuels. At 800 °C, the layered PBFM showed high electrical conductivity of 59.2 S cm(-1) in 5% H2 and peak power densities of 1.72 and 0.54 W cm(-2) using H2 and CH4 as fuel, respectively. The cell exhibits a very stable performance under a constant current load of 1.0 A cm(-2). To our best knowledge, this is the highest performance of ceramic anodes operated in methane. In addition, the anode is structurally stable at various fuel and temperature conditions, suggesting that it is a feasible material candidate for high-performing SOFC anode.

  11. A High-Performing Sulfur-Tolerant and Redox-Stable Layered Perovskite Anode for Direct Hydrocarbon Solid Oxide Fuel Cells

    NASA Astrophysics Data System (ADS)

    Ding, Hanping; Tao, Zetian; Liu, Shun; Zhang, Jiujun

    2015-12-01

    Development of alternative ceramic oxide anode materials is a key step for direct hydrocarbon solid oxide fuel cells (SOFCs). Several lanthanide based layered perovskite-structured oxides demonstrate outstanding oxygen diffusion rate, favorable electronic conductivity, and good oxygen surface exchange kinetics, owing to A-site ordered structure in which lanthanide and alkali-earth ions occupy alternate (001) layers and oxygen vacancies are mainly located in [LnOx] planes. Here we report a nickel-free cation deficient layered perovskite, (PrBa)0.95(Fe0.9Mo0.1)2O5 + δ (PBFM), for SOFC anode, and this anode shows an outstanding performance with high resistance against both carbon build-up and sulfur poisoning in hydrocarbon fuels. At 800 °C, the layered PBFM showed high electrical conductivity of 59.2 S cm-1 in 5% H2 and peak power densities of 1.72 and 0.54 W cm-2 using H2 and CH4 as fuel, respectively. The cell exhibits a very stable performance under a constant current load of 1.0 A cm-2. To our best knowledge, this is the highest performance of ceramic anodes operated in methane. In addition, the anode is structurally stable at various fuel and temperature conditions, suggesting that it is a feasible material candidate for high-performing SOFC anode.

  12. A High-Performing Sulfur-Tolerant and Redox-Stable Layered Perovskite Anode for Direct Hydrocarbon Solid Oxide Fuel Cells

    PubMed Central

    Ding, Hanping; Tao, Zetian; Liu, Shun; Zhang, Jiujun

    2015-01-01

    Development of alternative ceramic oxide anode materials is a key step for direct hydrocarbon solid oxide fuel cells (SOFCs). Several lanthanide based layered perovskite-structured oxides demonstrate outstanding oxygen diffusion rate, favorable electronic conductivity, and good oxygen surface exchange kinetics, owing to A-site ordered structure in which lanthanide and alkali-earth ions occupy alternate (001) layers and oxygen vacancies are mainly located in [LnOx] planes. Here we report a nickel-free cation deficient layered perovskite, (PrBa)0.95(Fe0.9Mo0.1)2O5 + δ (PBFM), for SOFC anode, and this anode shows an outstanding performance with high resistance against both carbon build-up and sulfur poisoning in hydrocarbon fuels. At 800 °C, the layered PBFM showed high electrical conductivity of 59.2 S cm−1 in 5% H2 and peak power densities of 1.72 and 0.54 W cm−2 using H2 and CH4 as fuel, respectively. The cell exhibits a very stable performance under a constant current load of 1.0 A cm−2. To our best knowledge, this is the highest performance of ceramic anodes operated in methane. In addition, the anode is structurally stable at various fuel and temperature conditions, suggesting that it is a feasible material candidate for high-performing SOFC anode. PMID:26648509

  13. Oxygen deficiency in Ti O2 : Similarities and differences between the Ti self-interstitial and the O vacancy in bulk rutile and anatase

    NASA Astrophysics Data System (ADS)

    Deák, Peter; Aradi, Bálint; Frauenheim, Thomas

    2015-07-01

    Ti O2 is an oxygen-deficient, intrinsically n -type material, but it is often debated whether the electrons are donated by oxygen vacancies (VO) or titanium interstitials (T ii) . Investigating this issue is complicated by the fact that rutile can self-trap electrons in intrinsic small polaron states, while bulk anatase cannot. The screened hybrid functional HSE06 was proven to account for this phenomenon and has provided quantitatively correct results for VO in our earlier study. Here, we use it for T ii in both rutile and anatase, allowing full spin and symmetry freedom, to shed light on the similarities and differences to VO. We find that these two defects give rise to very similar fingerprints in electron paramagnetic resonance, infrared absorption, or photoelectron spectra. In weakly reduced rutile, the ground state of both defects is (2 +) , with two electrons in polaronic traps, bound loosely to the defect. Most of the time, only these latter states (crudely resembling a hydrogenic series, with increasing distance from the defect) are likely to be detected. In anatase, both VO and T ii can be expected to be ionized at room temperature (singly and doubly, respectively), and the next vertical ionization energy is similar in the two defects—and very close to the ionization energy of the bound polarons in rutile. Most signals in paramagnetic resonance experiments on rutile must also be related to the polaron states, and, in general, very special conditions have to be fulfilled to detect electrons localized to VO or T ii itself. We show that, in thermal equilibrium, the dominant defect in intrinsic samples is VO, and T ii can be the majority defect only in strongly reduced anatase, or in case of p -type doping.

  14. K{sub 2}NaOsO{sub 5.5} and K{sub 3}NaOs{sub 2}O{sub 9}: The first osmium perovskites containing alkali cations at the 'A' site

    SciTech Connect

    Mogare, Kailash M.; Klein, Wilhelm; Jansen, Martin

    2012-07-15

    K{sub 2}NaOsO{sub 5.5} and K{sub 3}NaOs{sub 2}O{sub 9} were obtained from solid-state reactions of potassium superoxide, sodium peroxide and osmium metal at elevated oxygen pressures. K{sub 2}NaOsO{sub 5.5} crystallizes as an oxygen-deficient cubic double perovskite in space group Fm3{sup Macron }m with a=8.4184(5) A and contains isolated OsO{sub 6} octahedra. K{sub 3}NaOs{sub 2}O{sub 9} crystallizes hexagonally in P6{sub 3}/mmc with a=5.9998(4) A and c=14.3053(14) A. K{sub 3}NaOs{sub 2}O{sub 9} consists of face sharing Os{sub 2}O{sub 9} pairs of octahedra. According to magnetic measurements K{sub 2}NaOsO{sub 5.5} is diamagnetic, whereas K{sub 3}NaOs{sub 2}O{sub 9} displays strong antiferromagnetic coupling (T{sub N}=140 K), indicating enhanced magnetic interactions within the octahedral pair. - Graphical abstract: High oxidation states of Os, obtained by high oxygen pressure synthesis, are accommodated in double and triple perovskite matrices. K{sub 3}NaOs{sub 2}O{sub 9} displays enhanced magnetic interactions. Highlights: Black-Right-Pointing-Pointer New osmates containing highly oxidized Os were obtained by high O{sub 2} pressure synthesis. Black-Right-Pointing-Pointer High oxidation states of Os are accommodated in double and triple perovskite matrices. Black-Right-Pointing-Pointer Both compounds represent the first Os perovskites with an alkali metal at the A site. Black-Right-Pointing-Pointer K{sub 3}NaOs{sub 2}O{sub 9} displays enhanced magnetic interactions within the octahedral pair.

  15. Crystal structure, thermal expansion and high-temperature electrical conductivity of A-site deficient La{sub 2−z}Co{sub 1+y}(Mg{sub x}Nb{sub 1−x}){sub 1−y}O{sub 6} double perovskites

    SciTech Connect

    Shafeie, S.; Dreyer, B.; Awater, R.H.P; Golod, T.; Grins, J.; Biendicho, J.J.; Istomin, S.Ya.; Svensson, G.

    2015-09-15

    New La-deficient double perovskites with P2{sub 1}/n symmetry, La{sub ∼1.90}(Co{sup 2+}{sub 1−x}Mg{sup 2+}{sub x})(Co{sup 3+}{sub 1/3}Nb{sup 5+}{sub 2/3})O{sub 6} with x=0, 0.13 and 0.33, and La{sub 2}(Co{sup 2+}{sub 1/2}Mg{sup 2+}{sub 1/2}) (Co{sup 3+}{sub 1/2}Nb{sup 5+}{sub 1/2})O{sub 6} were prepared by solid state reaction at 1450 °C. Their crystal structures were refined using time-of-flight neutron powder diffraction data. Our results show that certain cations such as Nb{sup 5+}, with very strong B–O bonds in the perovskite structure, can induce A-site vacancies in double perovskites. Upon heating in N{sub 2} gas atmosphere at 1200 °C ∼1% O atom vacancies are formed together with a partial reduction of the Co{sup 3+} content. The average thermal expansion coefficient between 25 and 900 °C of La{sub 1.90}(Co{sup 2+}{sub 2/3}Mg{sup 2+}{sub 1/3})(Co{sup 3+}{sub 1/3}Nb{sup 5+}{sub 2/3})O{sub 6} was determined to be 17.4 ppm K{sup −1}. Four-point electronic conductivity measurements showed that the compounds are semiconductors, with conductivities varying between 3.7·10{sup −2} and 7.7·10{sup −2} S cm{sup −1} at 600 °C and activation energies between 0.77 and 0.81 eV. Partial replacement of La{sup 3+} with Sr{sup 2+} does not lead to any increase of conductivity, while replacement of Mg{sup 2+} with Cu{sup 2+} in La{sub 1.9}CoCu{sub 1/3}Nb{sub 2/3}O{sub 6} and La{sub 1.8}CoCu{sub 1/2}Nb{sub 1/2}O{sub 6} leads to ∼100 times larger conductivities at 600 °C, 0.35 and 1.0 S cm{sup −1}, respectively, and lower activation energies, 0.57 and 0.73 eV, respectively. - Highlights: • Double perovskites, P2{sub 1}/n, La{sub 2−z}(Co{sup 2+}{sub 1−x}Mg{sup 2+}{sub x})(Co{sup 3+}{sub 1/3}Nb{sup 5+}{sub 2/3})O{sub 6} have been synthesized. • Crystal structures have been refined using neutron powder diffraction data. • Strong Nb–O bond and size ordering of Mg{sup 2+}/Co{sup 2+} and Nb{sup 5+}/Co{sup ~3+} leads to La-deficiency. • The

  16. Electrospun Perovskite Nanofibers

    NASA Astrophysics Data System (ADS)

    Chen, Dongsheng; Zhu, Yanyan

    2017-02-01

    CH3NH3PbI3 perovskite nanofibers were synthesized by versatile electrospinning techniques. The synthetic CH3NH3PbI3 nanofibers were characterized by X-ray diffraction, scanning electron microscopy, thermogravimetric analysis, and photoluminescence. As counter electrodes, the synthesized nanofibers increased the performance of the dye-sensitized solar cells from 1.58 to 2.09%. This improvement was attributed to the enhanced smoothness and efficiency of the electron transport path. Thus, CH3NH3PbI3 perovskites nanofibers are potential alternative to platinum counter electrodes in dye-sensitized solar cells.

  17. Electric transport coefficients in highly epitaxial LaBaCo{sub 2}O{sub 5 + δ} films with “p-to-n” transition induced by oxygen deficiency

    SciTech Connect

    Shaibo, J.; Zhang, Q. Y. Hu, H. C.; Li, X. N.; Pan, L. J.; Wang, Y. Q.

    2016-08-14

    Electric transport coefficients such as carrier type, density, and mobility are the important physical parameters in designing functional devices. In this work, we report the study on the electric transport coefficients of the highly epitaxial LaBaCo{sub 2}O{sub 5 + δ} (LBCO) films, which were discussed as a function of electric conductivity for the first time and compared with the results calculated by the theory for mixed conduction. The mobility in the LBCO films was determined to be ∼0.85 and ∼40 cm{sup 2}/V s for holes and electrons, respectively, and the density of p-type carriers strongly depends on the oxygen deficiency. Solid evidence is presented to demonstrate that the oxygen deficiency cannot make LBCO materials changed from p- to n-type. The n-type conduction observed in experiment is a counterfeit phenomenon caused by the deficiency in Hall measurement, rather than a realistic transition induced by oxygen deficiency. In addition, the temperature-dependent conductivity was discussed using the differential coefficients, which might be useful in the study of the samples with magnetic transition.

  18. Atomic and electronic structures of single-layer FeSe on SrTiO3(001): The role of oxygen deficiency

    DOE PAGES

    Bang, Junhyeok; Li, Zhi; Sun, Y. Y.; ...

    2013-06-06

    Using first-principles calculation, we propose an interface structure for single triple-layer FeSe on the SrTiO3(001) surface, a high-Tc superconductor found recently. The key component of this structure is the oxygen deficiency on the top layer of the SrTiO3 substrate, as a result of Se etching used in preparing the high-Tc samples. The O vacancies strongly bind the FeSe triple layer to the substrate giving rise to a (2×1) reconstruction, as observed by scanning tunneling microscopy. The enhanced binding correlates to the significant increase of Tc observed in experiment. The O vacancies also serve as the source of electron doping, whichmore » modifies the Fermi surface of the first FeSe layer by filling the hole pocket near the center of the surface Brillouin zone, as suggested from angle-resolved photoemission spectroscopy measurement.« less

  19. Atomic and electronic structures of single-layer FeSe on SrTiO3(001): The role of oxygen deficiency

    SciTech Connect

    Bang, Junhyeok; Li, Zhi; Sun, Y. Y.; Samanta, Amit; Zhang, Y. Y.; Zhang, Wenhao; Wang, Lili; Chen, X.; Ma, Xucun; Xue, Q.-K.; Zhang, S. B.

    2013-06-06

    Using first-principles calculation, we propose an interface structure for single triple-layer FeSe on the SrTiO3(001) surface, a high-Tc superconductor found recently. The key component of this structure is the oxygen deficiency on the top layer of the SrTiO3 substrate, as a result of Se etching used in preparing the high-Tc samples. The O vacancies strongly bind the FeSe triple layer to the substrate giving rise to a (2×1) reconstruction, as observed by scanning tunneling microscopy. The enhanced binding correlates to the significant increase of Tc observed in experiment. The O vacancies also serve as the source of electron doping, which modifies the Fermi surface of the first FeSe layer by filling the hole pocket near the center of the surface Brillouin zone, as suggested from angle-resolved photoemission spectroscopy measurement.

  20. Oxygen deficiency induced deterioration in microstructure and magnetic properties at Y{sub 3}Fe{sub 5}O{sub 12}/Pt interface

    SciTech Connect

    Song, Dongsheng; Zhu, Jing; Ma, Li; Zhou, Shiming

    2015-07-27

    Transport efficiency of pure spin current across the ferromagnetic films adjacent with a nonmagnetic metal is strongly dependent on the spin mixing conductance, which is very sensitive to atomic-level interface conditions. Here, by the means of advanced electron microscopy techniques, atomic structure, electronic structure, and magnetic properties at Y{sub 3}Fe{sub 5}O{sub 12} (YIG)/Pt interface are detailed characterized to correlate the microstructure and magnetic properties with interfacial transport properties. It is found that the order-disorder structure transformation at the interface is accompanied with oxygen deficiency, thus the reduced iron valence and the break of magnetic atom-O-magnetic atom bridges, which is responsible for superexchange interaction and magnetic order. It is also found that the magnetic moment of interfacial iron ions is decreased. The disorder interfacial layer with suppressed magnetism finally contributes to the declined spin transport efficiency. Our results provide the knowledge to control and manipulate the interfacial structure and properties in order to obtain higher spin transport efficiency.

  1. TRPC3-mediated Ca2+ influx contributes to Rac1-mediated production of reactive oxygen species in MLP-deficient mouse hearts.

    PubMed

    Kitajima, Naoyuki; Watanabe, Kunihiro; Morimoto, Sachio; Sato, Yoji; Kiyonaka, Shigeki; Hoshijima, Masahiko; Ikeda, Yasuhiro; Nakaya, Michio; Ide, Tomomi; Mori, Yasuo; Kurose, Hitoshi; Nishida, Motohiro

    2011-05-27

    Dilated cardiomyopathy (DCM) is a myocardial disorder that is characterized by dilation and dysfunction of the left ventricle (LV). Accumulating evidence has implicated aberrant Ca(2+) signaling and oxidative stress in the progression of DCM, but the molecular details are unknown. In the present study, we report that inhibition of the transient receptor potential canonical 3 (TRPC3) channels partially prevents LV dilation and dysfunction in muscle LIM protein-deficient (MLP (-/-)) mice, a murine model of DCM. The expression level of TRPC3 and the activity of Ca(2+)/calmodulin-dependent kinase II (CaMKII) were increased in MLP (-/-) mouse hearts. Acitivity of Rac1, a small GTP-binding protein that participates in NADPH oxidase (Nox) activation, and the production of reactive oxygen species (ROS) were also increased in MLP (-/-) mouse hearts. Treatment with pyrazole-3, a TRPC3 selective inhibitor, strongly suppressed the increased activities of CaMKII and Rac1, as well as ROS production. In contrast, activation of TRPC3 by 1-oleoyl-2-acetyl-sn-glycerol (OAG), or by mechanical stretch, induced ROS production in rat neonatal cardiomyocytes. These results suggest that up-regulation of TRPC3 is responsible for the increase in CaMKII activity and the Nox-mediated ROS production in MLP (-/-) mouse cardiomyocytes, and that inhibition of TRPC3 is an effective therapeutic strategy to prevent the progression of DCM. Copyright © 2011 Elsevier Inc. All rights reserved.

  2. Highly nonlinear varistors from oxygen-deficient zinc oxide thin films by hot-dipping in Bi2O3: Influence of temperature

    NASA Astrophysics Data System (ADS)

    Wang, Yang; Peng, Zhijian; Wang, Qi; Fu, Xiuli

    2016-12-01

    Highly nonlinear varistors were fabricated by hot-dipping oxygen-deficient zinc oxide (ZnO1-x, x < 1) thin films in Bi2O3. The ZnO1-x films were deposited on conducting silicon chips by radio frequency magnetron sputtering of a sintered zinc oxide ceramic target. Then the films were hot-dipped at a temperature from 200 to 600 °C in Bi2O3. With the increase in hot-dipping temperature, the nonlinear coefficient (α) of the film varistors increases first and then decreases, and the leakage current (IL) correspondingly decreases initially and then increases, owing mainly to the formation and destroying of complete ZnO1-x/Bi2O3 grain boundaries and the roundness change of the ZnO1-x grains; and the varistor voltage (E1mA) decreases from 0.0268 to 0.0137 V/nm, due to the decreased number of effective grain boundaries in the materials. The film varistors prepared by hot-dipping at 400 °C exhibit the optimum nonlinear properties with the highest α = 15.1, lowest IL = 0.0223 mA/cm2, and E1mA = 0.0176 V/nm. Such nanoscaled film varistors will be very promising in electrical/electronic devices working in low-voltage.

  3. PHYTOALEXIN DEFICIENT 4 affects reactive oxygen species metabolism, cell wall and wood properties in hybrid aspen (Populus tremula L. × tremuloides).

    PubMed

    Ślesak, Ireneusz; Szechyńska-Hebda, Magdalena; Fedak, Halina; Sidoruk, Natalia; Dąbrowska-Bronk, Joanna; Witoń, Damian; Rusaczonek, Anna; Antczak, Andrzej; Drożdżek, Michał; Karpińska, Barbara; Karpiński, Stanisław

    2015-07-01

    The phytoalexin deficient 4 (PAD4) gene in Arabidopsis thaliana (AtPAD4) is involved in the regulation of plant--pathogen interactions. The role of PAD4 in woody plants is not known; therefore, we characterized its function in hybrid aspen and its role in reactive oxygen species (ROS)-dependent signalling and wood development. Three independent transgenic lines with different suppression levels of poplar PAD expression were generated. All these lines displayed deregulated ROS metabolism, which was manifested by an increased H2O2 level in the leaves and shoots, and higher activities of manganese superoxide dismutase (MnSOD) and catalase (CAT) in the leaves in comparison to the wild-type plants. However, no changes in non-photochemical quenching (NPQ) between the transgenic lines and wild type were observed in the leaves. Moreover, changes in the ROS metabolism in the pad4 transgenic lines positively correlated with wood formation. A higher rate of cell division, decreased tracheid average size and numbers, and increased cell wall thickness were observed. The results presented here suggest that the Populus tremula × tremuloides PAD gene might be involved in the regulation of cellular ROS homeostasis and in the cell division--cell death balance that is associated with wood development.

  4. The excellent performance of nest-like oxygen-deficient Cu1.5Mn1.5O4 applied in activated carbon air-cathode microbial fuel cell.

    PubMed

    Wang, Junjie; Tian, Pei; Li, Kexun; Ge, Baochao; Liu, Di; Liu, Yi; Yang, Tingting; Ren, Rong

    2016-12-01

    This study investigated the performance of nano spinel nest-like oxygen-deficient Cu1.5Mn1.5O4 doping activated carbon (AC) as air cathode in microbial fuel cell (MFC). The Cu1.5Mn1.5O4 was synthesized via hydrothermal method and subsequent annealed. The maximum power density (MPD) of MFC with oxygen-deficient Cu1.5Mn1.5O4 modified cathode was 1928±18mWm(-2), which was 1.53 times higher than the bare cathode. The electrochemical studies showed that Cu1.5Mn1.5O4 doping AC exhibited higher kinetic activity and lower resistance. The mechanism of oxygen reduction for the catalyst was a four electron pathway. The oxygen deficient of Cu1.5Mn1.5O4 played an important role in catalytic activity. So Cu1.5Mn1.5O4 would be an excellent promising catalyst for ORR in MFC.

  5. Artificial oxygen transport protein

    DOEpatents

    Dutton, P. Leslie

    2014-09-30

    This invention provides heme-containing peptides capable of binding molecular oxygen at room temperature. These compounds may be useful in the absorption of molecular oxygen from molecular oxygen-containing atmospheres. Also included in the invention are methods for treating an oxygen transport deficiency in a mammal.

  6. Resistance switching memory in perovskite oxides

    SciTech Connect

    Yan, Z.B. Liu, J.-M.

    2015-07-15

    The resistance switching behavior has recently attracted great attentions for its application as resistive random access memories (RRAMs) due to a variety of advantages such as simple structure, high-density, high-speed and low-power. As a leading storage media, the transition metal perovskite oxide owns the strong correlation of electrons and the stable crystal structure, which brings out multifunctionality such as ferroelectric, multiferroic, superconductor, and colossal magnetoresistance/electroresistance effect, etc. The existence of rich electronic phases, metal–insulator transition and the nonstoichiometric oxygen in perovskite oxide provides good platforms to insight into the resistive switching mechanisms. In this review, we first introduce the general characteristics of the resistance switching effects, the operation methods and the storage media. Then, the experimental evidences of conductive filaments, the transport and switching mechanisms, and the memory performances and enhancing methods of perovskite oxide based filamentary RRAM cells have been summarized and discussed. Subsequently, the switching mechanisms and the performances of the uniform RRAM cells associating with the carrier trapping/detrapping and the ferroelectric polarization switching have been discussed. Finally, the advices and outlook for further investigating the resistance switching and enhancing the memory performances are given.

  7. Perovskite Nanowire Extrusion.

    PubMed

    Oener, Sebastian Z; Khoram, Parisa; Brittman, Sarah; Mann, Sander A; Zhang, Qianpeng; Fan, Zhiyong; Boettcher, Shannon W; Garnett, Erik C

    2017-10-10

    The defect tolerance of halide perovskite materials has led to efficient optoelectronic devices based on thin-film geometries with unprecedented speed. Moreover, it has motivated research on perovskite nanowires because surface recombination continues to be a major obstacle in realizing efficient nanowire devices. Recently, ordered vertical arrays of perovskite nanowires have been realized, which can benefit from nanophotonic design strategies allowing precise control over light propagation, absorption, and emission. An anodized aluminum oxide template is used to confine the crystallization process, either in the solution or in the vapor phase. This approach, however, results in an unavoidable drawback: only nanowires embedded inside the AAO are obtainable, since the AAO cannot be etched selectively. The requirement for a support matrix originates from the intrinsic difficulty of controlling precise placement, sizes, and shapes of free-standing nanostructures during crystallization, especially in solution. Here we introduce a method to fabricate free-standing solution-based vertical nanowires with arbitrary dimensions. Our scheme also utilizes AAO; however, in contrast to embedding the perovskite inside the matrix, we apply a pressure gradient to extrude the solution from the free-standing templates. The exit profile of the template is subsequently translated into the final semiconductor geometry. The free-standing nanowires are single crystalline and show a PLQY up to ∼29%. In principle, this rapid method is not limited to nanowires but can be extended to uniform and ordered high PLQY single crystalline perovskite nanostructures of different shapes and sizes by fabricating additional masking layers or using specifically shaped nanopore endings.

  8. Electric transport and oxygen permeation properties of lanthanum cobaltite membranes synthesized by different methods

    SciTech Connect

    Qi, X.; Lin, Y.S.; Swartz, S.L.

    2000-03-01

    Dense perovskite-structured membranes with desired composition of La{sub 0.8}Sr{sub 0.2}Co{sub 0.6}Fe{sub 0.4}O{sub 3{minus}{delta}} (LSCF) were prepared from powders produced by four different methods. LSCF powders prepared by citrate, solid-state, and spray-pyrolysis methods had compositions close to the desired stoichiometry with a slight difference in cobalt concentration, whereas coprecipitated powders had a large strontium deficiency. The membrane composition was a determining factor that affected the electronic conductivity and therefore oxygen permeability. The membrane with a large strontium deficiency had much lower electronic conductivity and oxygen permeability (ionic conductivity) than the other three membranes with compositions close to the desired stoichiometry. The electronic conductivity of membranes prepared from citrate, solid-state, and spray-pyrolysis methods increases with the cobalt concentration of the membrane. For the three membranes with similar composition, the activation energy of oxygen flux decreases with increasing grain size. Oxygen pressure dependency of oxygen vacancy concentration is also influenced by the membrane microstructure and composition. LSCF membranes with same composition and similar microstructure should have similar electric and oxygen transport properties.

  9. High Performance Perovskite Solar Cells.

    PubMed

    Tong, Xin; Lin, Feng; Wu, Jiang; Wang, Zhiming M

    2016-05-01

    Perovskite solar cells fabricated from organometal halide light harvesters have captured significant attention due to their tremendously low device costs as well as unprecedented rapid progress on power conversion efficiency (PCE). A certified PCE of 20.1% was achieved in late 2014 following the first study of long-term stable all-solid-state perovskite solar cell with a PCE of 9.7% in 2012, showing their promising potential towards future cost-effective and high performance solar cells. Here, notable achievements of primary device configuration involving perovskite layer, hole-transporting materials (HTMs) and electron-transporting materials (ETMs) are reviewed. Numerous strategies for enhancing photovoltaic parameters of perovskite solar cells, including morphology and crystallization control of perovskite layer, HTMs design and ETMs modifications are discussed in detail. In addition, perovskite solar cells outside of HTMs and ETMs are mentioned as well, providing guidelines for further simplification of device processing and hence cost reduction.

  10. High Performance Perovskite Solar Cells

    PubMed Central

    Tong, Xin; Lin, Feng; Wu, Jiang

    2015-01-01

    Perovskite solar cells fabricated from organometal halide light harvesters have captured significant attention due to their tremendously low device costs as well as unprecedented rapid progress on power conversion efficiency (PCE). A certified PCE of 20.1% was achieved in late 2014 following the first study of long‐term stable all‐solid‐state perovskite solar cell with a PCE of 9.7% in 2012, showing their promising potential towards future cost‐effective and high performance solar cells. Here, notable achievements of primary device configuration involving perovskite layer, hole‐transporting materials (HTMs) and electron‐transporting materials (ETMs) are reviewed. Numerous strategies for enhancing photovoltaic parameters of perovskite solar cells, including morphology and crystallization control of perovskite layer, HTMs design and ETMs modifications are discussed in detail. In addition, perovskite solar cells outside of HTMs and ETMs are mentioned as well, providing guidelines for further simplification of device processing and hence cost reduction. PMID:27774402

  11. Temperature-independent sensors based on perovskite-type oxides

    NASA Astrophysics Data System (ADS)

    Zaza, F.; Frangini, S.; Leoncini, J.; Luisetto, I.; Masci, A.; Pasquali, M.; Tuti, S.

    2014-06-01

    The need of energy security and environment sustainability drives toward the development of energy technology in order to enhance the performance of internal combustion engines. Gas sensors play a key role for controlling the fuel oxygen ratio and monitoring the pollution emissions. The perovskite-type oxides can be synthesized for an extremely wide variety of combinations of chemical elements, allowing to design materials with suitable properties for sensing application. Lanthanum strontium ferrites, such as La0.7Sr0.3FeO3, are suitable oxygen sensing materials with temperature-independence conductivity, but they have low chemical stability under reducing conditions. The addition of aluminum into the perovskite structure improves the material properties in order to develop suitable oxygen sensing probes for lean burn engine control systems. Perovskite-type oxides with formula (La0.7Sr0.3)(AlxFe1-x)O3 was synthesized by the citrate-nitrate combustion synthesis method. XRD analyses, show that it was synthesized a phase-pure powder belonging to the perovskite structure. Aluminum affects both the unit cell parameters, by shrinking the unit cell, and the powder morphology, by promoting the synthesis of particles with small crystallite size and large specific surface area. The partial substitution of iron with aluminum improves the chemical stability under reducing gas conditions and modulates the oxygen sensitivity by affecting the relative amount of Fe4+ and Fe3+, as confirmed from TPR profiles. In the same time, the addition of aluminum does not affects the temperature-independent properties of lanthanum strontium ferrites. Indeed, the electrical measurements show that (La0.7Sr0.3)(AlxFe1-x)O3 perovskites have temperature-independence conductivity from 900 K.

  12. Temperature-independent sensors based on perovskite-type oxides

    SciTech Connect

    Zaza, F.; Frangini, S.; Masci, A.; Leoncini, J.; Pasquali, M.; Luisetto, I.; Tuti, S.

    2014-06-19

    The need of energy security and environment sustainability drives toward the development of energy technology in order to enhance the performance of internal combustion engines. Gas sensors play a key role for controlling the fuel oxygen ratio and monitoring the pollution emissions. The perovskite-type oxides can be synthesized for an extremely wide variety of combinations of chemical elements, allowing to design materials with suitable properties for sensing application. Lanthanum strontium ferrites, such as La{sub 0.7}Sr{sub 0.3}FeO{sub 3}, are suitable oxygen sensing materials with temperature-independence conductivity, but they have low chemical stability under reducing conditions. The addition of aluminum into the perovskite structure improves the material properties in order to develop suitable oxygen sensing probes for lean burn engine control systems. Perovskite-type oxides with formula (La{sub 0.7}Sr{sub 0.3})(Al{sub x}Fe{sub 1−x})O{sub 3} was synthesized by the citrate-nitrate combustion synthesis method. XRD analyses, show that it was synthesized a phase-pure powder belonging to the perovskite structure. Aluminum affects both the unit cell parameters, by shrinking the unit cell, and the powder morphology, by promoting the synthesis of particles with small crystallite size and large specific surface area. The partial substitution of iron with aluminum improves the chemical stability under reducing gas conditions and modulates the oxygen sensitivity by affecting the relative amount of Fe{sup 4+} and Fe{sup 3+}, as confirmed from TPR profiles. In the same time, the addition of aluminum does not affects the temperature-independent properties of lanthanum strontium ferrites. Indeed, the electrical measurements show that (La{sub 0.7}Sr{sub 0.3})(Al{sub x}Fe{sub 1−x})O{sub 3} perovskites have temperature-independence conductivity from 900 K.

  13. Structural transformations in cubic structure of Mn/Co perovskites in reducing and oxidizing atmospheres

    NASA Astrophysics Data System (ADS)

    Koponen, Markus J.; Suvanto, Mika; Kallinen, Kauko; Kinnunen, Toni-J. J.; Härkönen, Matti; Pakkanen, Tapani A.

    2006-05-01

    ABO ( A=La, Pr; B=Mn, Co), ABBx'O ( A=La, Pr; B=Mn, Co; B=Co, Pd), and ABCoPdO ( A=La, Pr; B=Fe, Mn) ( x=0.05, 0.37; y=0.38) perovskites were synthesized via malic acid complexation. O 2-TPD, O 2-TPO, and H 2-TPR treatments were carried out to study the oxidation and reduction behavior of the synthesized perovskites. LaCo 0.95Pd 0.05O 3, PrCo 0.95Pd 0.05O 3, and PrCoO 3 perovskites had the highest desorption, oxidation, and reduction activity within the studied perovskite series. Powder XRD studies revealed structural transformation of the cubic structure of all synthesized perovskites except LaFe 0.57Co 0.38Pd 0.05O 3 in H 2/Ar atmosphere when the temperature was over 400 °C. The decomposed structure reverted to the original perovskite structure under oxidizing atmosphere. This reversion was accompanied by increased oxygen desorption activity. It was noticed that the Co and Mn combinations in the B-site of the perovskites structure decreased the thermal stability of the synthesized perovskites.

  14. Theoretical evaluation of the surface electrochemistry of perovskites with promising photon absorption properties for solar water splitting

    SciTech Connect

    Montoya, Joseph H.; Garcia-Mota, Monica; Nørskov, Jens K.; Vojvodic, Aleksandra

    2015-01-01

    Density functional theory results describing the theoretical electrocatalytic properties of perovskite oxides and oxynitrides suggest that the water splitting reaction will require cocatalysts due to high theoretical oxygen evolution and hydrogen evolution overpotentials.

  15. Enhancing photocatalytic CO2 reduction by coating an ultrathin Al2O3 layer on oxygen deficient TiO2 nanorods through atomic layer deposition

    NASA Astrophysics Data System (ADS)

    Zhao, Huilei; Chen, Jiatang; Rao, Guiying; Deng, Wei; Li, Ying

    2017-05-01

    In this work, anatase nanorods (ANR) of TiO2 with active facet {100} as the major facet were successfully synthesized, and reducing the ANR by NaBH4 led to the formation of gray colored oxygen deficient TiO2-x (ReANR). On the surface of ReANR, a thin layer of Al2O3 was deposited using atomic layer deposition (ALD), and the thickness of Al2O3 varied by the number of ALD cycles (1, 2, 5, 10, 50, 100, or 200). The growth rate of Al2O3 was determined to be 0.25 Å per cycle based on high-resolution TEM analysis, and the XRD result showed the amorphous structure of Al2O3. All the synthesized photocatalysts (ANR, ReANR, and Al2O3 coated ReANR) were tested for CO2 photocatalytic reduction in the presence of water vapor, with CO detected as the major reduction product and CH4 as the minor product. Compared with ANR, ReANR had more than 50% higher CO production and more than ten times higher CH4 production due to the oxygen vacancies that possibly enhanced CO2 adsorption and activation. By applying less than 5 cycles of ALD, the Al2O3 coated ReANR had enhanced overall production of CO and CH4 than uncoated ReANR, with 2 cycles being the optimum, about 40% higher overall production than ReANR. Whereas, both CO and CH4 production decreased with increasing number of ALD cycles when more than 5 cycles were applied. Photoluminescence (PL) analysis showed an ultrathin layer of Al2O3 (2 cycles of ALD) coating on the ReANR was able to reduce the charge carrier recombination rate, likely because of the passivation of surface states. On the other hand, a relatively thick layer of Al2O3 may act as an insulation layer to prohibit electron migration to the catalyst surface. This work gives valuable insights on the application of ALD coating on photocatalysts to promote CO2 photoreduction to fuels.

  16. A Comparison of the Nitrogen Gas Excess Versus the Fixed Nitrogen Deficit in Two Major Oxygen Deficient Zones of the World

    NASA Astrophysics Data System (ADS)

    Devol, A. H.; Chang, B. X.

    2006-12-01

    This study compares the nitrogen gas excesses in the oxygen deficient zones (ODZs) of the Eastern Tropical South Pacific (ETSP) and the Arabian Sea. These are two of the three largest ODZs in the world. In the near absence of oxygen, heterotrophic denitrification is the dominant form of respiration in these regions which, coupled to the sheer vastness of the ODZs, makes them a globally significant sink of marine fixed nitrogen. Thus, understanding how nitrogen is cycled in the ODZs is important to understanding the global nitrogen cycle. We measured profiles of nitrogen gas and argon concentrations through the ODZs of the ETSP and the Arabian Sea in the fall of 2005 and 2004, respectively. Nitrogen gas concentrations were normalized to argon concentrations to eliminate variations due to physical changes in the water mass. Any nitrogen gas in excess of the background nitrogen gas concentration was interpreted to be from denitrification. In the Arabian Sea ODZ, we found the nitrogen gas excess up to 18 uM N. Using stoichiometric relationships of nitrate and phosphate specific to the Arabian Sea, previous workers have estimated the nitrate deficit in the Arabian Sea ODZ to be no more than 12 uM N, which is only two-thirds of the nitrogen gas excess. In the ODZ of the ETSP, we found the nitrogen gas excess to be 15 uM N and the estimated nitrate deficit to be comparable, which suggests that in the ETSP, the nitrogen gas excess may be accounted for by the nitrate deficit. In the Arabian Sea ODZ, however, there is 50% more nitrogen in the excess than can be accounted for by the nitrate deficit. Several explanations are possible for this discrepancy, but probably the most significant is the likely greater contribution of nitrogen fixation to the overall productivity of the Arabian Sea compared to the ETSP. Nitrogen fixing bacteria are known to have an elevated N:P relative to the assumed near-Redfieldian organic matter falling into the ODZ. Nitrogen fixation has been

  17. The Role of Oxygen Partial Pressure in Controlling the Phase Composition of La1- x Sr x Co y Fe1- y O3- δ Oxygen Transport Membranes Manufactured by Means of Plasma Spray-Physical Vapor Deposition

    NASA Astrophysics Data System (ADS)

    Marcano, D.; Mauer, G.; Sohn, Y. J.; Vaßen, R.; Garcia-Fayos, J.; Serra, J. M.

    2016-04-01

    La0.58Sr0.4Co0.2Fe0.8O3 - δ (LSCF) deposited on a metallic porous support by plasma spray-physical vapor deposition is a promising candidate for oxygen-permeation membranes. Ionic transport properties are regarded to depend on the fraction of perovskite phase present in the membrane. However, during processing, the LSCF powder decomposes into perovskite and secondary phases. In order to improve the ionic transport properties of the membranes, spraying was carried out at different oxygen partial pressures p(O2). It was found that coatings deposited at lower and higher oxygen partial pressures consist of 70% cubic/26% rhombohedral and 61% cubic/35% rhombohedral perovskite phases, respectively. During annealing, the formation of non-perovskite phases is driven by oxygen non-stoichiometry. The amount of oxygen added during spraying can be used to increase the perovskite phase fraction and suppress the formation of non-perovskite phases.

  18. Effect of oxygen deficiency on the magnetic, electrical, magnetoelectric, and magnetoelastic properties of La1 - x Sr x MnO3 - δ manganites

    NASA Astrophysics Data System (ADS)

    Koroleva, L. I.; Zashchirinskiĭ, D. M.; Khapaeva, T. M.; Gurskiĭ, L. I.; Kalanda, N. A.; Trukhan, V. M.; Szymczak, R.; Krzumanska, B.

    2008-12-01

    This paper reports on a study of the effect of oxygen deficiency on the magnetic and electrical properties of the La1 - x Sr x MnO3 - δ manganites ( x = 0, 0.2, 0.4; δ = 0, 0.13, 0.2). In compositions with x = 0 and δ = 0.13 and 0.2, the temperature dependence of the magnetization M ( T) can be approximated by the Langevin function with the moment of superparamagnetic clusters μ = 77μB (δ = 0.13) and 86μB (δ = 0.2) at temperatures of 25 K ≤ T ≤ 250 K, with the exception of a small temperature range near 132 K in which a maximum characteristic of the LaMnO3 antiferromagnet is seen. These compositions, as well as Sr-doped compositions with δ ≠ 0, reveal a difference between the magnetizations of the sample cooled in a weak magnetic field and in zero field. At T = 6 K in a magnetic field of 16 kOe, the compositions with x = 0.2 and 0.4, δ = 0.13 possess a magnetic moment per formula unit lower than that with δ = 0, as well as reveal an anomalous relation between the Curie temperature T C and the Curie paramagnetic point gJ, namely, T C > gJ. The magnetization of compositions with x = 0.2 and 0.4, δ = 0.2 follows the Langevin function with μ = 40μB and 130μB, respectively. The electrical resistivity of samples with x = 0.4 and δ = 0.13 and 0.2 is one to two orders of magnitude larger than that of the composition with x = 0.4, δ = 0, which evidences partial or complete compensation of acceptor defects (Sr2+ ions) by donor defects (doubly charged O2- vacancies). The above properties of oxygen-deficient compositions suggest that they contain an insulating ferro-antiferromagnetic magnetically double-phase state. The magnetoresistance and volume magnetostriction in samples with x = 0.4 and δ = 0, 0.13, and 0.2 are small; indeed, in a magnetic field of 8 kOe, they do not exceed 1.4% and 6 × 10-6, respectively. On this basis, it is concluded that the unbalanced doubly charged donors (O vacancies) are in the state with antiparallel spins and, thus, do

  19. Corrosion of copper in oxygen-deficient groundwater with and without deep bedrock micro-organisms: Characterisation of microbial communities and surface processes

    NASA Astrophysics Data System (ADS)

    Huttunen-Saarivirta, E.; Rajala, P.; Bomberg, M.; Carpén, L.

    2017-02-01

    Copper specimens were exposed to oxygen-deficient artificial groundwater in the presence and absence of micro-organisms enriched from the deep bedrock of the planned nuclear waste repository site at Olkiluoto island on the western coast of Finland. During the exposure periods of 4 and 10 months, the copper specimens were subjected to electrochemical measurements. The biofilm developed on the specimens and the water used in the exposures were subjected to microbiological analyses. Changes in the water chemistry were also determined and surfaces of the copper specimens were characterized with respect to the morphology and composition of the formed corrosion products. The results showed that under biotic conditions, redox of the water and open circuit potential (OCP) of the copper specimens were generally negative and resulted in the build-up of a copper sulphide, Cu2S, layer due to the activity of sulphate-reducing bacteria (SRB) that were included in the system. In the 4-month test, the electrochemical behaviour of the specimens changed during the exposure and alphaproteobactria Rhizobiales were the dominant bacterial group in the biofilm where the highest corrosion rate was observed. In the 10-month test, however, deltaproteobacteria SRB flourished and the initial electrochemical behaviour and the low corrosion rate of the copper were retained until the end of the test period. Under abiotic conditions, the positive water redox potential and specimen OCP correlated with the formation of copper oxide, Cu2O. Furthermore, in the absence of SRB, Cu2O provided slightly inferior protection against corrosion compared to that by Cu2S in the presence of SRB. The obtained results show that the presence of microorganisms may enhance the passivity of copper. In addition, the identification of key microbial species, such as SRB thriving on copper for long time periods, is important for successful prediction of the behaviour of copper.

  20. Vertical modeling of the nitrogen cycle in the eastern tropical South Pacific oxygen deficient zone using high-resolution concentration and isotope measurements

    NASA Astrophysics Data System (ADS)

    Peters, Brian D.; Babbin, Andrew R.; Lettmann, Karsten A.; Mordy, Calvin W.; Ulloa, Osvaldo; Ward, Bess B.; Casciotti, Karen L.

    2016-11-01

    Marine oxygen deficient zones (ODZs) have long been identified as sites of fixed nitrogen (N) loss. However, the mechanisms and rates of N loss have been debated, and traditional methods for measuring these rates are labor-intensive and may miss hot spots in spatially and temporally variable environments. Here we estimate rates of heterotrophic nitrate reduction, heterotrophic nitrite reduction (denitrification), nitrite oxidation, and anaerobic ammonium oxidation (anammox) at a coastal site in the eastern tropical South Pacific (ETSP) ODZ based on high-resolution concentration and natural abundance stable isotope measurements of nitrate (NO3-) and nitrite (NO2-). These measurements were used to estimate process rates using a two-step inverse modeling approach. The modeled rates were sensitive to assumed isotope effects for NO3- reduction and NO2- oxidation. Nevertheless, we addressed two questions surrounding the fates of NO2- in the ODZ: (1) Is NO2- being primarily reduced to N2 or oxidized to NO3- in the ODZ? and (2) what are the contributions of anammox and denitrification to NO2- removal? Depth-integrated rates from the model suggest that 72-88% of the NO2- produced in the ODZ was oxidized back to NO3-, while 12-28% of NO2- was reduced to N2. Furthermore, our model suggested that 36-74% of NO2- loss was due to anammox, with the remainder due to denitrification. These model results generally agreed with previously measured rates, though with a large range of uncertainty, and they provide a long-term integrated view that compliments incubation experiments to obtain a broader picture of N cycling in ODZs.

  1. Linkage of oxygen deficiency defects and rare earth concentrations in silica glass optical fiber probed by ultraviolet absorption and laser excitation spectroscopy.

    PubMed

    Liu, Y-S; Galvin, T C; Hawkins, T; Ballato, J; Dong, L; Foy, P R; Dragic, P D; Eden, J G

    2012-06-18

    Ultraviolet absorption measurements and laser excitation spectroscopy in the vicinity of 248 nm provide compelling evidence for linkages between the oxygen deficiency center (ODC) and rare earth concentrations in Yb and Er-doped glass optical fibers. Investigations of YAG-derived and solution-doped glass fibers are described. For both Yb and Er-doped fibers, the dependence of Type II ODC absorption on the rare earth number density is approximately linear, but the magnitude of the effect is greater for Yb-doped fibers. Furthermore, laser excitation spectra demonstrate unambiguously the existence of an energy transfer mechanism coupling an ODC with Yb(3+). Photopumping glass fibers with a Ti:sapphire laser/optical parametric amplifier system, tunable over the 225-265 nm region, or with a KrF laser at 248.4 nm show: 1) emission features in the 200-1100 nm interval attributable only to the ODC (Type II) defect or Yb(3+), and 2) the excitation spectra for ODC (II) emission at ~280 nm and Yb(3+) fluorescence (λ ~1.03 μm) to be, within experimental uncertainty, identical. The latter demonstrates that, when irradiating Yb-doped silica fibers between ~240 and 255 nm, the ODC (II) defect is at least the primary precursor to Yb(3+) emission. Consistent with previous reports in the literature, the data show the ODC (II) absorption spectrum to have a peak wavelength and breadth of ~246 nm and ~19 nm (FWHM). Experiments also reveal that, in the absence of Yb, incorporating either Al(2)O(3) or Y(2)O(3) into glass fibers has a negligible impact on the ODC concentration. Not only do the data reported here demonstrate the relationship between the ODC (II) number density and the Yb doping concentration, but they also suggest that the appearance of ODC defects in the fiber is associated with the introduction of Yb and the process by which the fiber is formed.

  2. Metal halide perovskite light emitters

    PubMed Central

    Kim, Young-Hoon; Cho, Himchan; Lee, Tae-Woo

    2016-01-01

    Twenty years after layer-type metal halide perovskites were successfully developed, 3D metal halide perovskites (shortly, perovskites) were recently rediscovered and are attracting multidisciplinary interest from physicists, chemists, and material engineers. Perovskites have a crystal structure composed of five atoms per unit cell (ABX3) with cation A positioned at a corner, metal cation B at the center, and halide anion X at the center of six planes and unique optoelectronic properties determined by the crystal structure. Because of very narrow spectra (full width at half-maximum ≤20 nm), which are insensitive to the crystallite/grain/particle dimension and wide wavelength range (400 nm ≤ λ ≤ 780 nm), perovskites are expected to be promising high-color purity light emitters that overcome inherent problems of conventional organic and inorganic quantum dot emitters. Within the last 2 y, perovskites have already demonstrated their great potential in light-emitting diodes by showing high electroluminescence efficiency comparable to those of organic and quantum dot light-emitting diodes. This article reviews the progress of perovskite emitters in two directions of bulk perovskite polycrystalline films and perovskite nanoparticles, describes current challenges, and suggests future research directions for researchers to encourage them to collaborate and to make a synergetic effect in this rapidly emerging multidisciplinary field. PMID:27679844

  3. Oxygen ion conducting materials

    DOEpatents

    Carter, J. David; Wang, Xiaoping; Vaughey, John; Krumpelt, Michael

    2004-11-23

    An oxygen ion conducting ceramic oxide that has applications in industry including fuel cells, oxygen pumps, oxygen sensors, and separation membranes. The material is based on the idea that substituting a dopant into the host perovskite lattice of (La,Sr)MnO.sub.3 that prefers a coordination number lower than 6 will induce oxygen ion vacancies to form in the lattice. Because the oxygen ion conductivity of (La,Sr)MnO.sub.3 is low over a very large temperature range, the material exhibits a high overpotential when used. The inclusion of oxygen vacancies into the lattice by doping the material has been found to maintain the desirable properties of (La,Sr)MnO.sub.3, while significantly decreasing the experimentally observed overpotential.

  4. Oxygen ion conducting materials

    DOEpatents

    Vaughey, John; Krumpelt, Michael; Wang, Xiaoping; Carter, J. David

    2005-07-12

    An oxygen ion conducting ceramic oxide that has applications in industry including fuel cells, oxygen pumps, oxygen sensors, and separation membranes. The material is based on the idea that substituting a dopant into the host perovskite lattice of (La,Sr)MnO.sub.3 that prefers a coordination number lower than 6 will induce oxygen ion vacancies to form in the lattice. Because the oxygen ion conductivity of (La,Sr)MnO.sub.3 is low over a very large temperature range, the material exhibits a high overpotential when used. The inclusion of oxygen vacancies into the lattice by doping the material has been found to maintain the desirable properties of (La,Sr)MnO.sub.3, while significantly decreasing the experimentally observed overpotential.

  5. Oxygen ion conducting materials

    DOEpatents

    Vaughey, John; Krumpelt, Michael; Wang, Xiaoping; Carter, J. David

    2003-01-01

    An oxygen ion conducting ceramic oxide that has applications in industry including fuel cells, oxygen pumps, oxygen sensors, and separation membranes. The material is based on the idea that substituting a dopant into the host perovskite lattice of (La,Sr)MnO.sub.3 that prefers a coordination number lower than 6 will induce oxygen ion vacancies to form in the lattice. Because the oxygen ion conductivity of (La,Sr)MnO.sub.3 is low over a very large temperature range, the material exhibits a high overpotential when used. The inclusion of oxygen vacancies into the lattice by doping the material has been found to maintain the desirable properties of (La,Sr)MnO.sub.3, while significantly decreasing the experimentally observed overpotential.

  6. A comparative ab initio study of bulk and surface oxygen vacancies in PbTiO 3, PbZrO 3 and SrTiO 3 perovskites

    NASA Astrophysics Data System (ADS)

    Zhukovskii, Yu. F.; Kotomin, E. A.; Piskunov, S.; Ellis, D. E.

    Using the DFT-HF hybrid LCAO approach as implemented in the CRYSTAL computer code, we have performed large supercell comparative calculations of neutral O vacancies ( F centers) in the bulk and on the (001) surface of three cubic perovskite crystals (SrTiO 3, PbTiO 3, and PbZrO 3). The local lattice relaxation, charge redistribution, and positions of defect energy levels within the band gap are compared. It is shown that the difference in the chemical composition of host materials leads to quite different defect properties.

  7. Density functional study on redox energetics of LaMO{sub 3−δ} (M=Sc–Cu) perovskite-type oxides

    SciTech Connect

    Pishahang, Mehdi; Erik Mohn, Chris; Stølen, Svein

    2016-01-15

    This study evaluates the redox energetics of LaMO{sub 3−δ} (M=Sc–Cu) perovskite-type oxides via generalized gradient approximation (GGA) to DFT. Two different approaches to redox energetics of oxygen deficient perovskites of strongly non-stoichiometric (δ=0.5) and dilute defect limits (δ→0) are studied. In the first approach the enthalpies of oxidation are calculated using the stoichiometric end-compounds of LaMO{sub 3} and LaMO{sub 2.5}. The most common structures for the reduced lanthanides and strontides similar to the ones experimentally reported for SrMnO{sub 2.5}, SrFeO{sub 2.5}, and LaNiO{sub 2.5} are considered. The second approach to the oxidation enthalpies termed (δ→0) follow the trend observed experimentally. This approach represents the experimental conditions of the measured oxygen enthalpies, and is hampered less by the artificial features due to spurious self-interaction errors in GGA.

  8. Tunable perovskite microdisk lasers.

    PubMed

    Sun, Wenzhao; Wang, Kaiyang; Gu, Zhiyuan; Xiao, Shumin; Song, Qinghai

    2016-04-28

    Perovskite microdisk lasers have been intensively studied recently. But their lasing properties are usually fixed once the devices are synthesized. Here, for the first time, we demonstrated the switchable and tunable perovskite microdisk lasers by surrounding them with 5CB liquid crystals. With the increase of the environmental temperature from 24 °C to 34 °C, the lasing wavelength slightly changed from 552.91 nm to 552.11 nm at the beginning and suddenly shifted to around 552.54 nm at T = 32 °C, where the phase transition of liquid crystals occurs. Our numerical calculation shows that the wavelength shift is caused by the changes of the refractive index of liquid crystals. More than tuning of the wavelength, a more dramatic wavelength transition from ∼554 nm to 550 nm has also been observed. This sudden transition is mainly induced by the reduction of scattering rather than the change in the refractive index when the liquid crystals are changed from the nematic phase to the isotropic phase. We believe that our research can shed light on the applications of perovskite optoelectronics.

  9. Novel Properties of Atomically Arranged Perovskites

    NASA Astrophysics Data System (ADS)

    Dabrowski, B.; Kolesnik, S.; Chmaissem, O.; Suescun, L.; Mais, J.

    2007-01-01

    Perovskites AMO3-δ attain unique electronic, magnetic, ferroelectric, thermoelectric, mixed-conducting, and other functional properties through selection of the A- and M-site ions, their fractions, ionic sizes and valences, spin states, and orbital orderings, as well as the oxygen content and vacancy ordering. We illustrate here our systematic exploration of the effects of composition, temperature, pressure, and oxygen content on the thermodynamic stability and magnetic properties for La1-x-ySrxBayMnO3 manganites. Parameters controlling magnetic transitions are identified through examples of single-valent compounds of RMnO3 (the Mn-O-Mn bond angles that can be equivalently described in terms of the tolerance factor) and Sr1-xCaxMnO3 (the tolerance factor and disorder described in terms of the variance of A-site ion sizes), and the mixed-valent La0.5Sr0.5-yBayMnO3 (the tolerance factor, variance of sizes, and the local strains described in terms of the elongated Mn-O bonds). By using an example of kinetically stable, atomically-ordered layered-perovskites we show that improved useful properties, such as the increase in the Curie temperature TC and enhancement of colossal magneto-resistive effect at room temperature, can be achieved through decreases in structural distortions such as variance of sizes and local strains.

  10. Organometal Halide Perovskite Artificial Synapses.

    PubMed

    Xu, Wentao; Cho, Himchan; Kim, Young-Hoon; Kim, Young-Tae; Wolf, Christoph; Park, Chan-Gyung; Lee, Tae-Woo

    2016-07-01

    Organometal halide perovskite synaptic devices are fabricated; they emulate important working principles of a biological synapse, including excitatory postsynaptic current, paired-pulse facilitation, short-term plasticity, long-term plasticity, and spike-timing dependent plasticity. These properties originate from possible ion migration in the ion-rich perovskite matrix. This work has extensive applicability and practical significance in neuromorphic electronics.

  11. Advances in Perovskite Solar Cells.

    PubMed

    Zuo, Chuantian; Bolink, Henk J; Han, Hongwei; Huang, Jinsong; Cahen, David; Ding, Liming

    2016-07-01

    Organolead halide perovskite materials possess a combination of remarkable optoelectronic properties, such as steep optical absorption edge and high absorption coefficients, long charge carrier diffusion lengths and lifetimes. Taken together with the ability for low temperature preparation, also from solution, perovskite-based devices, especially photovoltaic (PV) cells have been studied intensively, with remarkable progress in performance, over the past few years. The combination of high efficiency, low cost and additional (non-PV) applications provides great potential for commercialization. Performance and applications of perovskite solar cells often correlate with their device structures. Many innovative device structures were developed, aiming at large-scale fabrication, reducing fabrication cost, enhancing the power conversion efficiency and thus broadening potential future applications. This review summarizes typical structures of perovskite solar cells and comments on novel device structures. The applications of perovskite solar cells are discussed.

  12. Garden-like perovskite superstructures with enhanced photocatalytic activity.

    PubMed

    Ye, Meidan; Wang, Mengye; Zheng, Dajiang; Zhang, Nan; Lin, Changjian; Lin, Zhiqun

    2014-04-07

    By subjecting amorphous flower-like TiO2 to a facile hydrothermal synthesis in the presence of Sr(2+), garden-like perovskite SrTiO3 superstructures were achieved. The amorphous TiO2 was preformed using ZnO flowers as templates. Different three-dimensional SrTiO3 architectures were coexisted in the garden, including SrTiO3 flowers composed of several hollow sword-shaped petals, many sheet-shaped petals or numerous flake-shaped petals, and SrTiO3 grass consisting of a number of long blades. These SrTiO3 superstructures were simultaneously grown on fluorine-doped tin oxide (FTO) substrates. On the basis of a comprehensive study on the effects of growth time, temperature, initial concentrations of precursor, and pH, the formation of these various hierarchical architectures was attributed primarily to the dissolution of amorphous TiO2 and precipitation of perovskite crystals, followed by the Ostwald ripening process of perovskite nanocrystals and self-organization of perovskite building blocks. Interestingly, this approach can be readily extended to create other perovskite structures, including dendritic BaTiO3 and nest-like CaTiO3, as well as PbTiO3 transformed from plate-like pyrochlore Pb2Ti2O6 after post-thermal treatment. Garden-like SrTiO3 superstructures showed a superior photocatalytic performance when compared to other as-prepared semiconductors and perovskite materials (i.e., ZnO, TiO2, BaTiO3, CaTiO3 and PbTiO3), probably due to their intrinsic photocatalytic activity and special garden-like features with a coexistence of various structures that significantly facilitated the adsorption and diffusion of methyl blue (MB) molecules and oxygen species in the photochemical reaction of MB degradation.

  13. Phase stability study of Bi{sub 0.15}Sr{sub 0.85-x}Ae{sub x}CoO{sub 3-{delta}} (x = 0 and Ae = Ba{sub 0.28}; Ca{sub 0.17}) perovskites by in-situ neutron diffraction

    SciTech Connect

    Eriksson, A.K.; Eriksson, S.G.; Chapon, L.C.; Knee, C.S.

    2010-12-15

    The oxygen deficient perovskites, Bi{sub 0.15}Sr{sub 0.85-x}Ae{sub x}CoO{sub 3-{delta}}, x = 0 and Ae{sub x} = Ba{sub 0.28}, Ca{sub 0.17}, were studied with in-situ neutron powder diffraction and combined TGA/DSC in order to investigate their behaviour at elevated temperatures in oxidising conditions. The phase stability of the I4/mmm supercell structure adopted by Bi{sub 0.15}Sr{sub 0.85}CoO{sub 3-{delta}} is shown to be dependent on temperature and the oxygen content of the phase, with three structural events, at T {approx} 250, 590 and 880 {sup o}C, detected. The first transition occurs as the perovskite supercell vanishes due to oxygen absorption; the second transition is also associated with oxidation and involves the decomposition of the perovskite phase via an exothermic process to yield a dominant hexagonal phase. Finally, at T {approx} 900 {sup o}C the perovskite phase re-forms. For the Ba and Ca containing materials the decomposition to the hexagonal phase occurs at T {approx} 600 {sup o}C and {approx} 650 {sup o}C respectively. The presence of Ca at the A-site is found to stabilise the I4/mmm supercell structure in the range RT - 650 {sup o}C. The antiferromagnetic to paramagnetic transitions occur at T{sub N} {approx} 250 {sup o}C, T{sub N} {approx} 175 {sup o}C and T{sub N} {approx} 145 {sup o}C for the samples with Ae{sub x} = Ba{sub 0.28}, x = 0 and Ae{sub x} = Ca{sub 0.17}, respectively.

  14. Stable and durable CH3NH3PbI3 perovskite solar cells at ambient conditions.

    PubMed

    Rajamanickam, Nagalingam; Kumari, Sudesh; Vendra, Venkat Kalyan; Lavery, Brandon W; Spurgeon, Joshua; Druffel, Thad; Sunkara, Mahendra K

    2016-06-10

    Degradation of metal-organic halide perovskites when exposed to ambient conditions is a crucial issue that needs to be addressed for commercial viability of perovskite solar cells (PSCs). Here, a concept of encapsulating CH3NH3PbI3 perovskite crystals with a multi-functional graphene-polyaniline (PANI) composite coating to protect the perovskite against degradation from moisture, oxygen and UV light is presented. Hole-conducting polymers containing 2D layered sheet materials are presented here as multi-functional materials with oxygen and moisture impermeability. Specific studies involving PANI and graphene composites as coatings for perovskite crystals exhibited resistance to moisture and oxygen under continued exposure to UV and visible light. Most importantly, no perovskite degradation was observed even after 96 h of exposure of the PSCs to extremely high humidity (99% relative humidity). Our observations and results on perovskite protection with graphene/conducting polymer composites open up opportunities for glove-box-free and atmospheric processing of PSCs.

  15. Stable and durable CH3NH3PbI3 perovskite solar cells at ambient conditions

    NASA Astrophysics Data System (ADS)

    Rajamanickam, Nagalingam; Kumari, Sudesh; Kalyan Vendra, Venkat; Lavery, Brandon W.; Spurgeon, Joshua; Druffel, Thad; Sunkara, Mahendra K.

    2016-06-01

    Degradation of metal-organic halide perovskites when exposed to ambient conditions is a crucial issue that needs to be addressed for commercial viability of perovskite solar cells (PSCs). Here, a concept of encapsulating CH3NH3PbI3 perovskite crystals with a multi-functional graphene-polyaniline (PANI) composite coating to protect the perovskite against degradation from moisture, oxygen and UV light is presented. Hole-conducting polymers containing 2D layered sheet materials are presented here as multi-functional materials with oxygen and moisture impermeability. Specific studies involving PANI and graphene composites as coatings for perovskite crystals exhibited resistance to moisture and oxygen under continued exposure to UV and visible light. Most importantly, no perovskite degradation was observed even after 96 h of exposure of the PSCs to extremely high humidity (99% relative humidity). Our observations and results on perovskite protection with graphene/conducting polymer composites open up opportunities for glove-box-free and atmospheric processing of PSCs.

  16. Glory of piezoelectric perovskites

    PubMed Central

    Uchino, Kenji

    2015-01-01

    This article reviews the history of piezoelectric perovskites and forecasts future development trends, including Uchino’s discoveries such as the Pb(Mg1/3Nb2/3)O3–PbTiO3 electrostrictor, Pb(Zn1/3Nb2/3)O3–PbTiO3 single crystal, (Pb, La)(Zr, Ti)O3 photostriction, and Pb(Zr, Ti)O3–Terfenol magnetoelectric composites. We discuss five key trends in the development of piezomaterials: performance to reliability, hard to soft, macro to nano, homo to hetero, and single to multi-functional. PMID:27877827

  17. Perovskite electrodes and method of making the same

    DOEpatents

    Seabaugh, Matthew M.; Swartz, Scott L.

    2009-09-22

    The invention relates to perovskite oxide electrode materials in which one or more of the elements Mg, Ni, Cu, and Zn are present as minority components that enhance electrochemical performance, as well as electrode products with these compositions and methods of making the electrode materials. Such electrodes are useful in electrochemical system applications such as solid oxide fuel cells, ceramic oxygen generation systems, gas sensors, ceramic membrane reactors, and ceramic electrochemical gas separation systems.

  18. Perovskite electrodes and method of making the same

    DOEpatents

    Seabaugh, Matthew M.; Swartz, Scott L.

    2005-09-20

    The invention relates to perovskite oxide electrode materials in which one or more of the elements Mg, Ni, Cu, and Zn are present as minority components that enhance electrochemical performance, as well as electrode products with these compositions and methods of making the electrode materials. Such electrodes are useful in electrochemical system applications such as solid oxide fuel cells, ceramic oxygen generation systems, gas sensors, ceramic membrane reactors, and ceramic electrochemical gas separation systems.

  19. Multidimensional Perovskites: A Mixed Cation Approach Towards Ambient Stable and Tunable Perovskite Photovoltaics.

    PubMed

    Koh, Teck Ming; Thirumal, Krishnamoorthy; Soo, Han Sen; Mathews, Nripan

    2016-09-22

    Although halide perovskites are able to deliver high power conversion efficiencies, their ambient stability still remains an obstacle for commercialization. Thus, promoting the ambient stability of perovskites has become a key research focus. In this review, we highlight the sources of instability in conventional 3 D perovskites, including water intercalation, ion migration, and thermal decomposition. Recently, the multidimensional perovskites approach has become one of the most promising strategies to enhance the stability of perovskites. As compared to pure 2 D perovskites, multidimensional perovskites typically possess more ideal band gaps, better charge transport, and lower exciton binding energy, which are essential for photovoltaic applications. The larger organic cations in multidimensional perovskites could also be more chemically stable at higher temperatures than the commonly used methylammonium cation. By combining 3 D and 2 D perovskites to form multidimensional perovskites, halide perovskite photovoltaics can attain both high efficiency and increased stability.

  20. Stability of Perovskite Solar Cells: A Prospective on the Substitution of the A Cation and X Anion.

    PubMed

    Wang, Ze; Shi, Zejiao; Li, Taotao; Chen, Yonghua; Huang, Wei

    2017-01-24

    In recent years, organometal trihalide perovskites have emerged as promising materials for low-cost, flexible, and highly efficient solar cells. Despite their processing advantages, before the technology can be commercialized the poor stability of the organic-inorganic hybrid perovskite materials with regard to humidity, heat, light, and oxygen has be to overcome. Herein, we distill the current state-of-the-art and highlight recent advances in improving the chemical stability of perovskite materials by substitution of the A-cation and X-anion. Our hope is to pave the way for the rational design of perovskite materials to realize perovskite solar cells with unprecedented improvement in stability. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Methodologies for high efficiency perovskite solar cells.

    PubMed

    Park, Nam-Gyu

    2016-01-01

    Since the report on long-term durable solid-state perovskite solar cell in 2012, perovskite solar cells based on lead halide perovskites having organic cations such as methylammonium CH3NH3PbI3 or formamidinium HC(NH2)2PbI3 have received great attention because of superb photovoltaic performance with power conversion efficiency exceeding 22 %. In this review, emergence of perovskite solar cell is briefly introduced. Since understanding fundamentals of light absorbers is directly related to their photovoltaic performance, opto-electronic properties of organo lead halide perovskites are investigated in order to provide insight into design of higher efficiency perovskite solar cells. Since the conversion efficiency of perovskite solar cell is found to depend significantly on perovskite film quality, methodologies for fabricating high quality perovskite films are particularly emphasized, including various solution-processes and vacuum deposition method.

  2. Methodologies for high efficiency perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Park, Nam-Gyu

    2016-06-01

    Since the report on long-term durable solid-state perovskite solar cell in 2012, perovskite solar cells based on lead halide perovskites having organic cations such as methylammonium CH3NH3PbI3 or formamidinium HC(NH2)2PbI3 have received great attention because of superb photovoltaic performance with power conversion efficiency exceeding 22 %. In this review, emergence of perovskite solar cell is briefly introduced. Since understanding fundamentals of light absorbers is directly related to their photovoltaic performance, opto-electronic properties of organo lead halide perovskites are investigated in order to provide insight into design of higher efficiency perovskite solar cells. Since the conversion efficiency of perovskite solar cell is found to depend significantly on perovskite film quality, methodologies for fabricating high quality perovskite films are particularly emphasized, including various solution-processes and vacuum deposition method.

  3. Oxygen Transport Ceramic Membranes

    SciTech Connect

    S. Bandopadhyay; N. Nagabhushana; X.-D Zhou; Q. Cai; J. Yang; W.B. Yelon; W.J. James; H.U. Anderson; Alan Jacobson; C.A. Mims

    2004-10-01

    The present quarterly report describes some of the investigations on the structural properties of dense OTM bars provided by Praxair and studies on newer composition of Ti doped LSF. In this report, Moessbauer spectroscopy was used to study the local environmentals of LSFT with various level of oxygen deficiency. Ionic valence state, magnetic interaction and influence of Ti on superexchange are discussed Stable crack growth studies on Dense OTM bars provided by Praxair were done at elevated temperature, pressure and elevated conditions. Post-fracture X-ray data of the OTM fractured at 1000 C in environment were refined by FullProf code and results indicate a distortion of the parent cubic perovskite to orthorhombic structure with reduced symmetry. TGA-DTA studies on the post-fracture samples also indicated residual effect arising from the thermal and stress history of the samples. An electrochemical cell has been designed and built for measurements of the Seebeck coefficient as a function of temperature and pressure. The initial measurements on La{sub 0.2}Sr{sub 0.8}Fe{sub 0.55}Ti{sub 0.45}O{sub 3-{delta}} are reported. Neutron diffraction measurements of the same composition are in agreement with both the stoichiometry and the kinetic behavior observed in coulometric titration measurements. A series of isotope transients under air separation mode (small gradient) were completed on the membrane of LSCrF-2828 at 900 C. Low pO{sub 2} atmospheres based on with CO-CO{sub 2} mixtures have also been admitted to the delivery side of the LSCrF-2828 membrane to produce the gradients which exist under syngas generation conditions. The COCO{sub 2} mixtures have normal isotopic {sup 18}O abundances. The evolution of {sup 18}O on the delivery side in these experiments after an {sup 18}O pulse on the air side reveals a wealth of information about the oxygen transport processes.

  4. Covalent dependence of octahedral rotations in orthorhombic perovskite oxides.

    PubMed

    Cammarata, Antonio; Rondinelli, James M

    2014-09-21

    The compositional dependence of metal-oxygen BO6 octahedral distortions, including bond elongations and rotations, is frequently discussed in the ABO3 perovskite literature; structural distortions alleviate internal stresses driven by under- or over-coordinated bond environments. Here we identify the dependence of octahedral rotations from changes in metal-oxygen bond covalency in orthorhombic perovskites. Using density functional theory we formulate a covalency metric, which captures both the real and k-space interactions between the magnitude and sense, i.e., in-phase or out-of-phase, octahedral rotations, to explore the link between the ionic-covalent Fe-O bond and the interoctahedral Fe-O-Fe bond angles in Pbnm ferrates. Our survey finds that the covalency of the metal-oxygen bond is correlated with the rotation amplitude: We find the more covalent the Fe-O bond, the less distorted is the structure and the more important the long-range inter-octahedral (Fe-O-Fe bond angle) interactions. Finally, we show how to indirectly tune the B-O bond covalency by A-cation induced BO6 rotations independent of ionic size, facilitating design of targeted bonding interactions in complex perovskites.

  5. Oxidation Reactions of Ethane over Ba-Ce-O Based Perovskites

    SciTech Connect

    Miller, James E.; Sault, Allen G.; Trudell, Daniel E.; Nenoff, Tina M.; Thoma, Steven G.; Jackson, Nancy B.

    1999-08-18

    Ethane oxidation reactions were studied over pure and Ca-, Mg-, Sr-, La-, Nd-, and Y-substituted BaCeO{sub 3} perovskites under oxygen limited conditions. Several of the materials, notably the Ca- and Y-substituted materials, show activity for complete oxidation of the hydrocarbon to CO{sub 2} at temperatures below 650 C. At higher temperatures, the oxidative dehydrogenation (ODH) to ethylene becomes significant. Conversions and ethylene yields are enhanced by the perovskites above the thermal reaction in our system in some cases. The perovskite structure is not retained in the high temperature reaction environment. Rather, a mixture of carbonates and oxides is formed. Loss of the perovskite structure correlates with a loss of activity and selectivity to ethylene.

  6. Locked octahedral tilting in orthorhombic perovskites: At the boundary of the general rule predicting phase transitions

    NASA Astrophysics Data System (ADS)

    Ardit, M.; Dondi, M.; Cruciani, G.

    2017-01-01

    Mainly ruled by oxygen octahedral rotations, perovskite oxides can exhibit zone boundary transitions (ZBTs) either with d Tc/d P >0 or d Tc/d P <0 . Synchrotron structural investigations at high pressure conditions place YA l0.25C r0.75O3 orthorhombic perovskite at the boundary of ZBTs. The absence of changes in the octahedral tilting and a volume reduction with pressure exclusively controlled by an isotropic polyhedral compression set YA l0.25C r0.75O3 as the first finding of a possible asymptote at the Clapeyron relation for predicting ZBTs in perovskites. Furthermore, the discovery of a "locked-tilt perovskite" can pave the way to a new class of functional materials.

  7. Multigap Semiconducting ferroelectric perovskites

    NASA Astrophysics Data System (ADS)

    Jiang, Lai; Grinberg, Ilya; Wang, Fenggong; Davies, Peter; Rappe, Andrew

    2013-03-01

    The energy conversion efficiency of a solar cell is directly related to the band gap of the material. By doping ferroelectric perovskites with Bi5+ on the B-site, we propose low band-gap materials suitable for bulk photovoltaic effect and related solar applications.Our DFT calculations indicate that the low-lying 6 s empty states of the electronegative Bi atom produce empty isolated bands in the gap of the parent materials, effectively lowering the band gap by 1 ~2eV in various perovskites. Ferroelectricity (and therefore inversion symmetry breaking) weakens but survives upon doping, which enables the ``shift current'' mechanism for photocurrent generation, while the decreased band gap helps absorb low energy photons in the visible range. Furthermore, the existence of multiple band gaps allows for solar conversion devices with efficiency beyond the traditional Shockly-Queisser limit, in which successive photon excitations result in carriers with higher energy than a single-step excitation would achieve.

  8. Characterization of surface modification in atomic force microscope-induced nanolithography of oxygen deficient La{sub 0.67}Ba{sub 0.33}MnO{sub 3−δ} thin films

    SciTech Connect

    Tanyi, E. Kevin; Kolagani, Rajeswari M. Srivastava, Parul; Yong, Grace; Stumpf, Christopher; Schaefer, David; Vanderlinde, William

    2014-12-15

    We report our studies of the nanolithographic surface modifications induced by an Atomic Force Microscope (AFM) in epitaxial thin films of oxygen deficient Lanthanum Barium Manganese Oxide (La{sub 0.67}Ba{sub 0.33}MnO{sub 3−δ}). The pattern characteristics depend on the tip voltage, tip polarity, voltage duration, tip force, and humidity. We have used Electron Energy Dispersive X-Ray Spectroscopy (EDS) to analyze the chemical changes associated with the surface modifications produced with a negatively biased AFM tip. A significant increase in the oxygen stoichiometry for the patterned regions relative to the pristine film surface is observed. The results also indicate changes in the cation stoichiometry, specifically a decrease in the Lanthanum and Manganese concentrations and an increase in the Barium concentration in the patterned regions.

  9. A First Principles Investigation of Proton Chemistry in Perovskite-Type Oxides

    NASA Astrophysics Data System (ADS)

    Tauer, Tania Allison

    Certain acceptor-doped perovskite-type oxides show significant promise for deployment into a number of electrochemical device applications, including fuel cells, batteries, and electrolyzers, owing to their rapid proton conductivities at high temperatures. However, limitations in bulk material hydration and slow grain boundary conductivities have reduced the viability of these materials in intermediate temperatures applications. This thesis work uses density functional theory to gain a fundamental understanding of proton and defect chemistry within various perovskite environments in order to identify strategies to increase proton concentration and improve overall proton conductivity. First, material hydration was probed within yttrium-doped barium cerate (BCY) to examine how the thermodynamics of material hydration are influenced by dopant concentration. A model was derived from solely first principle techniques to describe hydration within BCY as a function of dopant concentration, temperature, and partial pressure of water. The resulting model can be used to screen for favorable perovskite-dopant combinations with enhanced hydration capabilities. Next, defect segregation was investigated in the more complex interfacial environment to probe the origin of low proton conductivity across perovskite grain boundaries (GB). The results of this study suggest that screening for perovskite-dopant combinations with strong dopant-oxygen bond strengths may reduce the segregation of dopant ions and oxygen vacancies to the GB interface, mitigating the development of a positive GB core and enhancing proton conduction across the GB. Finally, proton stability was assessed at various interfacial regions within the perovskite material. An examination of proton adsorption at the BaZrO3-vacuum interface reveals a destabilization of protons in the first subsurface layer of the perovskite, yielding a potential barrier for proton diffusion into and out of the perovskite membrane. An

  10. Controlling Octahedral Rotations in a Perovskite via Strain Doping

    NASA Astrophysics Data System (ADS)

    Herklotz, A.; Wong, A. T.; Meyer, T.; Biegalski, M. D.; Lee, H. N.; Ward, T. Z.

    2016-05-01

    The perovskite unit cell is the fundamental building block of many functional materials. The manipulation of this crystal structure is known to be of central importance to controlling many technologically promising phenomena related to superconductivity, multiferroicity, mangetoresistivity, and photovoltaics. The broad range of properties that this structure can exhibit is in part due to the centrally coordinated octahedra bond flexibility, which allows for a multitude of distortions from the ideal highly symmetric structure. However, continuous and fine manipulation of these distortions has never been possible. Here, we show that controlled insertion of He atoms into an epitaxial perovskite film can be used to finely tune the lattice symmetry by modifying the local distortions, i.e., octahedral bonding angle and length. Orthorhombic SrRuO3 films coherently grown on SrTiO3 substrates are used as a model system. Implanted He atoms are confirmed to induce out-of-plane strain, which provides the ability to controllably shift the bulk-like orthorhombically distorted phase to a tetragonal structure by shifting the oxygen octahedra rotation pattern. These results demonstrate that He implantation offers an entirely new pathway to strain engineering of perovskite-based complex oxide thin films, useful for creating new functionalities or properties in perovskite materials.

  11. Controlling octahedral rotations in a perovskite via strain doping

    DOE PAGES

    Herklotz, Andreas; Biegalski, Michael D.; Lee, Ho Nyung; ...

    2016-05-24

    The perovskite unit cell is the fundamental building block of many functional materials. The manipulation of this crystal structure is known to be of central importance to controlling many technologically promising phenomena related to superconductivity, multiferroicity, mangetoresistivity, and photovoltaics. The broad range of properties that this structure can exhibit is in part due to the centrally coordinated octahedra bond flexibility, which allows for a multitude of distortions from the ideal highly symmetric structure. However, continuous and fine manipulation of these distortions has never been possible. Here, we show that controlled insertion of He atoms into an epitaxial perovskite film canmore » be used to finely tune the lattice symmetry by modifying the local distortions, i.e., octahedral bonding angle and length. Orthorhombic SrRuO3 films coherently grown on SrTiO3 substrates are used as a model system. Implanted He atoms are confirmed to induce out-of-plane strain, which provides the ability to controllably shift the bulk-like orthorhombically distorted phase to a tetragonal structure by shifting the oxygen octahedra rotation pattern. Lastly, these results demonstrate that He implantation offers an entirely new pathway to strain engineering of perovskite-based complex oxide thin films, useful for creating new functionalities or properties in perovskite materials.« less

  12. Controlling octahedral rotations in a perovskite via strain doping

    SciTech Connect

    Herklotz, Andreas; Biegalski, Michael D.; Lee, Ho Nyung; Ward, Thomas Zac; Wong, A. T.; Meyer, T.

    2016-05-24

    The perovskite unit cell is the fundamental building block of many functional materials. The manipulation of this crystal structure is known to be of central importance to controlling many technologically promising phenomena related to superconductivity, multiferroicity, mangetoresistivity, and photovoltaics. The broad range of properties that this structure can exhibit is in part due to the centrally coordinated octahedra bond flexibility, which allows for a multitude of distortions from the ideal highly symmetric structure. However, continuous and fine manipulation of these distortions has never been possible. Here, we show that controlled insertion of He atoms into an epitaxial perovskite film can be used to finely tune the lattice symmetry by modifying the local distortions, i.e., octahedral bonding angle and length. Orthorhombic SrRuO3 films coherently grown on SrTiO3 substrates are used as a model system. Implanted He atoms are confirmed to induce out-of-plane strain, which provides the ability to controllably shift the bulk-like orthorhombically distorted phase to a tetragonal structure by shifting the oxygen octahedra rotation pattern. Lastly, these results demonstrate that He implantation offers an entirely new pathway to strain engineering of perovskite-based complex oxide thin films, useful for creating new functionalities or properties in perovskite materials.

  13. Controlling Octahedral Rotations in a Perovskite via Strain Doping

    PubMed Central

    Herklotz, A.; Wong, A. T.; Meyer, T.; Biegalski, M. D.; Lee, H. N.; Ward, T. Z.

    2016-01-01

    The perovskite unit cell is the fundamental building block of many functional materials. The manipulation of this crystal structure is known to be of central importance to controlling many technologically promising phenomena related to superconductivity, multiferroicity, mangetoresistivity, and photovoltaics. The broad range of properties that this structure can exhibit is in part due to the centrally coordinated octahedra bond flexibility, which allows for a multitude of distortions from the ideal highly symmetric structure. However, continuous and fine manipulation of these distortions has never been possible. Here, we show that controlled insertion of He atoms into an epitaxial perovskite film can be used to finely tune the lattice symmetry by modifying the local distortions, i.e., octahedral bonding angle and length. Orthorhombic SrRuO3 films coherently grown on SrTiO3 substrates are used as a model system. Implanted He atoms are confirmed to induce out-of-plane strain, which provides the ability to controllably shift the bulk-like orthorhombically distorted phase to a tetragonal structure by shifting the oxygen octahedra rotation pattern. These results demonstrate that He implantation offers an entirely new pathway to strain engineering of perovskite-based complex oxide thin films, useful for creating new functionalities or properties in perovskite materials. PMID:27215804

  14. Perovskite photovoltaics: Slow recombination unveiled

    NASA Astrophysics Data System (ADS)

    Moser, Jacques-E.

    2017-01-01

    One of the most salient features of hybrid lead halide perovskites is the extended lifetime of their photogenerated charge carriers. This property has now been shown experimentally to originate from a slow, thermally activated recombination process.

  15. Advances in Perovskite Solar Cells

    PubMed Central

    Zuo, Chuantian; Bolink, Henk J.; Han, Hongwei; Huang, Jinsong

    2016-01-01

    Organolead halide perovskite materials possess a combination of remarkable optoelectronic properties, such as steep optical absorption edge and high absorption coefficients, long charge carrier diffusion lengths and lifetimes. Taken together with the ability for low temperature preparation, also from solution, perovskite‐based devices, especially photovoltaic (PV) cells have been studied intensively, with remarkable progress in performance, over the past few years. The combination of high efficiency, low cost and additional (non‐PV) applications provides great potential for commercialization. Performance and applications of perovskite solar cells often correlate with their device structures. Many innovative device structures were developed, aiming at large‐scale fabrication, reducing fabrication cost, enhancing the power conversion efficiency and thus broadening potential future applications. This review summarizes typical structures of perovskite solar cells and comments on novel device structures. The applications of perovskite solar cells are discussed. PMID:27812475

  16. The Bright Side of Perovskites.

    PubMed

    Colella, Silvia; Mazzeo, Marco; Rizzo, Aurora; Gigli, Giuseppe; Listorti, Andrea

    2016-11-03

    Incubating in the rise of perovskite photovoltaic era, the advances in material design encourage further promising optoelectronic exploitations. Here, we evaluate halide perovskite envisioning light-emitting applications, with a particular focus to the role that this material can effectively play in the field, discussing advantages and limitations with respect to state of art competing players. Specific benefits derive from the use of low dimensional and nanostructured perovskites, marginally exploited in photovoltaic devices, allowing for a tuning of the excited states properties and for the obtainment of intrinsic resonating structures. Thanks to these unique properties, halide perovskite ensure a great potential for the development of high-power applications, such as lighting and lasing.

  17. Efficient ambient-air-stable solar cells with 2D-3D heterostructured butylammonium-caesium-formamidinium lead halide perovskites

    NASA Astrophysics Data System (ADS)

    Wang, Zhiping; Lin, Qianqian; Chmiel, Francis P.; Sakai, Nobuya; Herz, Laura M.; Snaith, Henry J.

    2017-09-01

    Perovskite solar cells are remarkably efficient; however, they are prone to degradation in water, oxygen and ultraviolet light. Cation engineering in 3D perovskite absorbers has led to reduced degradation. Alternatively, 2D Ruddlesden-Popper layered perovskites exhibit improved stability, but have not delivered efficient solar cells so far. Here, we introduce n-butylammonium cations into a mixed-cation lead mixed-halide FA0.83Cs0.17Pb(IyBr1‑y)3 3D perovskite. We observe the formation of 2D perovskite platelets, interspersed between highly orientated 3D perovskite grains, which suppress non-radiative charge recombination. We investigate the relationship between thin-film composition, crystal alignment and device performance. Solar cells with an optimal butylammonium content exhibit average stabilized power conversion efficiency of 17.5 ± 1.3% with a 1.61-eV-bandgap perovskite and 15.8 ± 0.8% with a 1.72-eV-bandgap perovskite. The stability under simulated sunlight is also enhanced. Cells sustain 80% of their 'post burn-in' efficiency after 1,000 h in air, and close to 4,000 h when encapsulated.

  18. Exsolution trends and co-segregation aspects of self-grown catalyst nanoparticles in perovskites

    NASA Astrophysics Data System (ADS)

    Kwon, Ohhun; Sengodan, Sivaprakash; Kim, Kyeounghak; Kim, Gihyeon; Jeong, Hu Young; Shin, Jeeyoung; Ju, Young-Wan; Han, Jeong Woo; Kim, Guntae

    2017-06-01

    In perovskites, exsolution of transition metals has been proposed as a smart catalyst design for energy applications. Although there exist transition metals with superior catalytic activity, they are limited by their ability to exsolve under a reducing environment. When a doping element is present in the perovskite, it is often observed that the surface segregation of the doping element is changed by oxygen vacancies. However, the mechanism of co-segregation of doping element with oxygen vacancies is still an open question. Here we report trends in the exsolution of transition metal (Mn, Co, Ni and Fe) on the PrBaMn2O5+δ layered perovskite oxide related to the co-segregation energy. Transmission electron microscopic observations show that easily reducible cations (Mn, Co and Ni) are exsolved from the perovskite depending on the transition metal-perovskite reducibility. In addition, using density functional calculations we reveal that co-segregation of B-site dopant and oxygen vacancies plays a central role in the exsolution.

  19. {sup 89}Y NMR and Cu NQR of hydrogenated oxygen-deficient YBa{sub 2}Cu{sub 3}O{sub 6.7}

    SciTech Connect

    Goren, S.D.; Korn, C.; Perrin, C.; Hoffmann, W.; Vieth, H.M.; Lueders, K.

    1995-08-01

    The room-temperature {sup 89}Y NMR line shift and line shape as well as the low-temperature Cu NQR lines were obtained as a function of hydrogen concentration for oxygen-depleted hydrogen-doped YBCO (H{sub {ital x}}YBa{sub 2}Cu{sub 3}O{sub 6.7}) in order to investigate the interplay of the effect of hydrogen addition and oxygen removal on the electronic structure and superconducting-antiferromagnetic transition properties. The results seem to indicate that as far as filling the conduction band is concerned, hydrogen contributes twice as many electrons as the chain oxygen contributes holes. In contrast to this, the transition from a superconductor to an antiferromagnet is governed by other considerations which favor a 1:1 ratio. It is also seen that hydrogen enters into either an additional site or a new phase when enough hydrogen is added to oxygen-depleted YBCO.

  20. Magnetoresistance Versus Oxygen Deficiency in Epi-stabilized SrRu1 - x Fe x O3 - δ Thin Films.

    PubMed

    Dash, Umasankar; Acharya, Susant Kumar; Lee, Bo Wha; Jung, Chang Uk

    2017-12-01

    Oxygen vacancies have a profound effect on the magnetic, electronic, and transport properties of transition metal oxide materials. Here, we studied the influence of oxygen vacancies on the magnetoresistance (MR) properties of SrRu1 - x Fe x O3 - δ epitaxial thin films (x = 0.10, 0.20, and 0.30). For this purpose, we synthesized highly strained epitaxial SrRu1 - x Fe x O3 - δ thin films with atomically flat surfaces containing different amounts of oxygen vacancies using pulsed laser deposition. Without an applied magnetic field, the films with x = 0.10 and 0.20 showed a metal-insulator transition, while the x = 0.30 thin film showed insulating behavior over the entire temperature range of 2-300 K. Both Fe doping and the concentration of oxygen vacancies had large effects on the negative MR contributions. For the low Fe doping case of x = 0.10, in which both films exhibited metallic behavior, MR was more prominent in the film with fewer oxygen vacancies or equivalently a more metallic film. For semiconducting films, higher MR was observed for more semiconducting films having more oxygen vacancies. A relatively large negative MR (~36.4%) was observed for the x = 0.30 thin film with a high concentration of oxygen vacancies (δ = 0.12). The obtained results were compared with MR studies for a polycrystal of (Sr1 - x La x )(Ru1 - x Fe x )O3. These results highlight the crucial role of oxygen stoichiometry in determining the magneto-transport properties in SrRu1 - x Fe x O3 - δ thin films.

  1. Electrospinning preparation of oxygen-deficient nano TiO2-x/carbon fibre membrane as a self-standing high performance anode for Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Jing, Mao-xiang; Li, Jing-quan; Han, Chong; Yao, Shan-shan; Zhang, Ji; Zhai, Hong-ai; Chen, Li-li; Shen, Xiang-qian; Xiao, Ke-song

    2017-07-01

    Improving the specific capacity and electronic conductivity of TiO2 can boost its practical application as a promising anode material for lithium ion batteries. In this work, a three-dimensional networking oxygen-deficient nano TiO2-x/carbon fibre membrane was achieved by combining the electrospinning process with a hot-press sintering method and directly used as a self-standing anode. With the synergistic effects of three-dimensional conductive networks, surface oxygen deficiency, high specific surface area and high porosity, binder-free and self-standing structure, etc., the nano TiO2-x/carbon fibre membrane electrode displays a high electrochemical reaction kinetics and a high specific capacity. The reversible capacity could be jointly generated from porous carbon, full-lithiation of TiO2 and interfacial lithium storage. At a current density of 100 mA g-1, the reversible discharge capacity can reach 464 mA h g-1. Even at 500 mA g-1, the discharge capacity still remains at 312 mA h g-1. Compared with pure carbon fibre and TiO2 powder, the TiO2-x/C fibre membrane electrode also exhibits an excellent cycle performance with a discharge capacity of 209 mA h g-1 after 700 cycles at the current density of 300 mA g-1, and the coulombic efficiency always remains at approximately 100%.

  2. Oxygen sensing and signaling.

    PubMed

    van Dongen, Joost T; Licausi, Francesco

    2015-01-01

    Oxygen is an indispensable substrate for many biochemical reactions in plants, including energy metabolism (respiration). Despite its importance, plants lack an active transport mechanism to distribute oxygen to all cells. Therefore, steep oxygen gradients occur within most plant tissues, which can be exacerbated by environmental perturbations that further reduce oxygen availability. Plants possess various responses to cope with spatial and temporal variations in oxygen availability, many of which involve metabolic adaptations to deal with energy crises induced by low oxygen. Responses are induced gradually when oxygen concentrations decrease and are rapidly reversed upon reoxygenation. A direct effect of the oxygen level can be observed in the stability, and thus activity, of various transcription factors that control the expression of hypoxia-induced genes. Additional signaling pathways are activated by the impact of oxygen deficiency on mitochondrial and chloroplast functioning. Here, we describe the molecular components of the oxygen-sensing pathway.

  3. Perovskite solar cells: Stability lies at interfaces

    NASA Astrophysics Data System (ADS)

    Lira-Cantú, Mónica

    2017-07-01

    Perovskite solar cells are developing fast but their lifetimes must be extended. Now, large-area printed perovskite solar modules have been shown to be stable for more than 10,000 hours under continuous illumination.

  4. OXYGEN TRANSPORT CERAMIC MEMBRANES

    SciTech Connect

    Dr. Sukumar Bandopadhyay; Dr. Nagendra Nagabhushana

    2003-01-01

    In the present quarter, the possibility of using a more complex interfacial engineering approach to the development of reliable and stable oxygen transport perovskite ceramic membranes/metal seals is discussed. Experiments are presented and ceramic/metal interactions are characterized. Crack growth and fracture toughness of the membrane in the reducing conditions are also discussed. Future work regarding this approach is proposed are evaluated for strength and fracture in oxygen gradient conditions. Oxygen gradients are created in tubular membranes by insulating the inner surface from the reducing environment by platinum foils. Fracture in these test conditions is observed to have a gradient in trans and inter-granular fracture as opposed to pure trans-granular fracture observed in homogeneous conditions. Fracture gradients are reasoned to be due to oxygen gradient set up in the membrane, variation in stoichiometry across the thickness and due to varying decomposition of the parent perovskite. The studies are useful in predicting fracture criterion in actual reactor conditions and in understanding the initial evolution of fracture processes.

  5. Clear microstructure-performance relationships in Mn-containing perovskite and hexaaluminate compounds prepared by activated reactive synthesis.

    PubMed

    Laassiri, Said; Bion, Nicolas; Duprez, Daniel; Royer, Sébastien; Alamdari, Houshang

    2014-03-07

    Microstructural properties of mixed oxides play essential roles in their oxygen mobility and consequently in their catalytic performances. Two families of mixed oxides (perovskite and hexaaluminate) with different microstructural features, such as crystal size and specific surface area, were prepared using the activated reactive synthesis (ARS) method. It was shown that ARS is a flexible route to synthesize both mixed oxides with nano-scale crystal size and high specific surface area. Redox properties and oxygen mobility were found to be strongly affected by the material microstructure. Catalytic activities of hexaaluminate and perovskite materials for methane oxidation were discussed in the light of structural, redox and oxygen mobility properties.

  6. Crystal structure, microstructure and reducibility of LaNi{sub x}Co{sub 1-x}O{sub 3} and LaFe{sub x}Co{sub 1-x}O{sub 3} Perovskites (0

    SciTech Connect

    Ivanova, S.; Senyshyn, A.; Zhecheva, E.; Tenchev, K.; Stoyanova, R.; Fuess, H.

    2010-04-15

    Nickel and iron substituted LaCoO{sub 3} with rhombohedrally distorted perovskite structure were obtained in the temperature range of 600-900 deg. C by thermal decomposition of freeze-dried citrates and by the Pechini method. The crystal structure, morphology and defective structure of LaCo{sub 1-x}Ni{sub x}O{sub 3} and LaCo{sub 1-x}Fe{sub x}O{sub 3} were characterized by X-ray diffraction and neutron powder diffraction, TEM and SEM analyses and electron paramagnetic resonance spectroscopy. The reducibility was tested by temperature programmed reduction with hydrogen. The products of the partial and complete reduction were determined by ex-situ XRD experiments. The replacement of Co by Ni and Fe led to lattice expansion of the perovskite structure. For perovskites annealed at 900 deg. C, there was a random Ni, Fe and Co distribution. The morphology of the perovskites does not depend on the Ni and Fe content, nor does it depend on the type of the precursor used. LaCo{sub 1-x}Ni{sub x}O{sub 3} perovskites (x>0.1) annealed at 900 deg. C are reduced to Co/Ni transition metal and La{sub 2}O{sub 3} via the formation of oxygen deficient Brownmillerite-type compositions. For LaCo{sub 1-x}Ni{sub x}O{sub 3} annealed at 600 deg. C, Co/Ni metal, in addition to oxygen-deficient perovskites, was formed as an intermediate product at the initial stage of the reduction. The interaction of LaCo{sub 1-x}Fe{sub x}O{sub 3} with H{sub 2} occurs by reduction of Co{sup 3+} to Co{sup 2+} prior to the Fe{sup 3+} ions. The reducibility of Fe-substituted perovskites is less sensitive towards the synthesis procedure in comparison with that of Ni substituted perovskites. - Graphical abstract: LaCo{sub 1-x}Ni{sub x}O{sub 3} and LaCo{sub 1-x}Fe{sub x}O{sub 3} with rhombohedrally distorted perovskite structure were obtained in the temperature range of 600-900 deg. C by thermal decomposition of freeze-dried La-Co/Ni(Fe)-citrates and by the Pechini method. The complete reduction of LaCo{sub 1-x

  7. Chalcogenide Perovskites for Solar Energy Harvesting

    NASA Astrophysics Data System (ADS)

    Perera, Samanthe

    Methylammonium Lead halide perovskites have recently emerged as a promising candidate for realizing high efficient low cost photovoltaic modules. Charge transport properties of the solution processed halide perovskites are comparable to some of the existing absorbers used in the current PV industry which require sophisticated processing techniques. Due to this simple processing required to achieve high efficiencies, halide perovskites have become an active field of research. As a result, perovskite solar cells are rapidly reaching towards theoretical efficiency limit of close to 30%. It's believed that ionicity inherent to perovskite materials is one of the contributing factors for the excellent charge transport properties of perovskites. Despite the growing interest for solar energy harvesting purposes, these halide perovskites have serious limitations such as toxicity and instability that need to be addressed in order to commercialize the solar cells incorporating them. This dissertation focuses on a new class of ionic semiconductors, chalcogenide perovskites for solar energy harvesting purposes. Coming from the family perovskites they are expected to have same excellent charge transport properties inherent to perovskites due to the ionicity. Inspired by few theoretical studies on chalcogenide perovskites, BaZrS3 and its Ti alloys were synthesized by sulfurizing the oxide counterpart. Structural characterizations have confirmed the predicted distorted perovskite phase. Optical characterizations have verified the direct band gap suitable for thin film single junction solar cells. Anion alloying was demonstrated by synthesizing oxysulfides with widely tunable band gap suitable for applications such as solid state lighting and sensing.

  8. Direct observation of hopping induced spin polarization current in oxygen deficient Co-doped ZnO by Andreev reflection technique

    NASA Astrophysics Data System (ADS)

    Yang, Kung-Shang; Huang, Tzu-Yu; Dwivedi, G. D.; Lin, Lu-Kuei; Lee, Shang-Fan; Sun, Shih-Jye; Chou, Hsiung

    2017-07-01

    Oxygen vacancy induced ferromagnetic coupling in diluted magnetic oxide (DMO) semiconductors have been reported in several studies, but technologically more crucial spin-polarized current (SPC) is still under-developed in DMOs. Few studies have claimed that VRH mechanism can originate the SPC, but, how VRH mechanism associated with percolation path, is not clearly understood. We used Point-contact Andreev reflection (PCAR) technique to probe the SPC in Co-doped ZnO (CZO) films. Since the high resistance samples cause broadening in conductance(G)-voltage(V) curves, which may result in an unreliable evaluation of spin polarization, we include two extra parameters, (i) effective temperature and (ii) spreading resistance, for the simulation to avoid the uncertainty in extracting spin polarization. The effective G-V curves and higher spin polarization can be obtained above a certain oxygen vacancy concentration. The number of completed and fragmentary percolation paths is proportional to the concentration of oxygen vacancies. For low oxygen vacancy samples, the Pb-tip has a higher probability of covering fragmentary percolation paths than the complete ones, due to its small contact size. The completed paths may remain independent of one another and get polarized in different directions, resulting in lower spin-polarization value. High oxygen vacancy samples provide a high density of completed path, most of them link to one another by crossing over, and gives rise to high spin-polarization value.

  9. Narrowing of band gap and effective charge carrier separation in oxygen deficient TiO2 nanotubes with improved visible light photocatalytic activity.

    PubMed

    Choudhury, Biswajit; Bayan, Sayan; Choudhury, Amarjyoti; Chakraborty, Purushottam

    2016-03-01

    Oxygen vacancies are introduced into hydrothermally processed TiO2 nanotube by vacuum calcination. Formation of oxygen vacancies modifies the local coordination in TiO2 as evident from Raman spectroscopy and secondary ion mass spectrometry (SIMS) results. The surface area is increased from 172.5m(2)/g in pure to 405.1m(2)/g in defective TiO2 nanotube. The mid-band gap electronic states created by oxygen vacancies are mostly responsible for the effective narrowing of band gap. Charge carrier separation is sufficiently prolonged as the charged oxygen defect states inhibit facile carrier recombination. With high surface area, narrowed band gap and separated charge carriers defective TiO2 nanotube is a suitable candidate in the photodegradation of methylene blue (MB) and phenol under visible light illumination. Photosensitized electron transfer from MB to the conduction band of TiO2 and the photodegradation of MB is facilitated in presence of high density of oxygen vacancies. Unlike MB, phenol absorbs in the UV region and does not easily excited under visible light. Phenol shows activity under visible light by forming charge transfer complex with TiO2. Defect trapped carriers become available at the phenol-TiO2 interface and finally interact with phenol molecule and degrade it.

  10. Perovskite-perovskite tandem photovoltaics with optimized band gaps

    NASA Astrophysics Data System (ADS)

    Eperon, Giles E.; Leijtens, Tomas; Bush, Kevin A.; Prasanna, Rohit; Green, Thomas; Wang, Jacob Tse-Wei; McMeekin, David P.; Volonakis, George; Milot, Rebecca L.; May, Richard; Palmstrom, Axel; Slotcavage, Daniel J.; Belisle, Rebecca A.; Patel, Jay B.; Parrott, Elizabeth S.; Sutton, Rebecca J.; Ma, Wen; Moghadam, Farhad; Conings, Bert; Babayigit, Aslihan; Boyen, Hans-Gerd; Bent, Stacey; Giustino, Feliciano; Herz, Laura M.; Johnston, Michael B.; McGehee, Michael D.; Snaith, Henry J.

    2016-11-01

    We demonstrate four- and two-terminal perovskite-perovskite tandem solar cells with ideally matched band gaps. We develop an infrared-absorbing 1.2-electron volt band-gap perovskite, FA0.75Cs0.25Sn0.5Pb0.5I3, that can deliver 14.8% efficiency. By combining this material with a wider-band gap FA0.83Cs0.17Pb(I0.5Br0.5)3 material, we achieve monolithic two-terminal tandem efficiencies of 17.0% with >1.65-volt open-circuit voltage. We also make mechanically stacked four-terminal tandem cells and obtain 20.3% efficiency. Notably, we find that our infrared-absorbing perovskite cells exhibit excellent thermal and atmospheric stability, not previously achieved for Sn-based perovskites. This device architecture and materials set will enable “all-perovskite” thin-film solar cells to reach the highest efficiencies in the long term at the lowest costs.

  11. Observation of Nanoscale Morphological and Structural Degradation in Perovskite Solar Cells by in Situ TEM.

    PubMed

    Yang, Bin; Dyck, Ondrej; Ming, Wenmei; Du, Mao-Hua; Das, Sanjib; Rouleau, Christopher M; Duscher, Gerd; Geohegan, David B; Xiao, Kai

    2016-11-30

    High-resolution in situ transmission electron microscopy (TEM) and electron energy loss spectroscopy were applied to systematically investigate morphological and structural degradation behaviors in perovskite films during different environmental exposure treatments. In situ TEM experiment indicates that vacuum itself is not likely to cause degradation in perovskites. In addition, these materials were found to degrade significantly when they were heated to ∼50-60 °C (i.e., a solar cell's field operating temperature) under illumination. This observation thus conveys a critically important message that the instability of perovskite solar cells at such a low temperature may limit their real field commercial applications. It was further unveiled that oxygen most likely attacks the CH3NH3(+) organic moiety rather than the PbI6 component of perovskites during ambient air exposure at room temperature. This finding grants a deeper understanding of the perovskite degradation mechanism and suggests a way to prevent degradation of perovskites by tailoring the organic moiety component.

  12. Accelerated degradation of methylammonium lead iodide perovskites induced by exposure to iodine vapour

    NASA Astrophysics Data System (ADS)

    Wang, Shenghao; Jiang, Yan; Juarez-Perez, Emilio J.; Ono, Luis K.; Qi, Yabing

    2017-01-01

    Efficiencies of organic-inorganic lead halide perovskite solar cells (PSCs) have significantly increased in recent years, but instability issues impede their further development and application. Previous studies reported that volatile species (for example, iodine, I2) were generated when perovskites were subjected to moisture, oxygen, light illumination, applied electric field, and thermal stress (all of which are relevant to the operation of PSCs in practical applications). Here we show that I2 vapour causes severe degradation of MAPbI3 (MA: CH3NH3+) perovskite, due to chemical chain reactions. Furthermore, I2 vapour could also induce degradation of other iodide-based perovskites, such as FAPbI3 (FA: HC(NH2)2+) and FA0.8Cs0.2PbI3. The results reveal a universal degradation factor for iodide-based perovskite by I2. As the release of I2 is nearly inevitable during practical applications, this work suggests that MAPbI3 may not be suitable for long-term stable solar cells and it is imperative to develop other types of perovskite material to achieve stable PSCs.

  13. Solution processed deposition of electron transport layers on perovskite crystal surface-A modeling based study

    NASA Astrophysics Data System (ADS)

    Mortuza, S. M.; Taufique, M. F. N.; Banerjee, Soumik

    2017-02-01

    The power conversion efficiency (PCE) of planar perovskite solar cells (PSCs) has reached up to ∼20%. However, structural and chemicals defects that lead to hysteresis in the perovskite based thin film pose challenges. Recent work has shown that thin films of [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) deposited on the photo absorption layer, using solution processing techniques, minimize surface pin holes and defects thereby increasing the PCE. We developed and employed a multiscale model based on molecular dynamics (MD) and kinetic Monte Carlo (kMC) to establish a relationship between deposition rate and surface coverage on perovskite surface. The MD simulations of PCBMs dispersed in chlorobenzene, sandwiched between (110) perovskite substrates, indicate that PCBMs are deposited through anchoring of the oxygen atom of carbonyl group to the exposed lead (Pb) atom of (110) perovskite surface. Based on rates of distinct deposition events calculated from MD, kMC simulations were run to determine surface coverage at much larger time and length scales than accessible by MD alone. Based on the model, a generic relationship is established between deposition rate of PCBMs and surface coverage on perovskite crystal. The study also provides detailed insights into the morphology of the deposited film.

  14. Evolution of the superconductivity during the pressure-induced oxygen ordering process in oxygen-deficient REBa{sub 2}Cu{sub 3}O{sub 6+x} (RE = Y,Nd,La)

    SciTech Connect

    Fita, I.M.; Puzniak, R.; Doroshenko, N.A.; Dyakonov, V.P.; Wisniewski, A.; Szymczak, H.

    1999-11-01

    The pressure controlled oxygen reordering processes in REBa{sub 2}Cu{sub 3}O{sub 6+x}(RE = Y,Nd,La) causing the continuous charge transfer between the CuO{sub x} and CuO{sub 2} planes were investigated. The charge transfer results in the time evolution of superconductivity. A strong acceleration of ordering and disordering processes was found when the RE-ion size increases from Y to La. Pressure induced semiconductor-superconductor transition in LaBa{sub 2}Cu{sub 3}O{sub 6+x} resulted from the oxygen ordering is reported for the first time.

  15. Graded bandgap perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Ergen, Onur; Gilbert, S. Matt; Pham, Thang; Turner, Sally J.; Tan, Mark Tian Zhi; Worsley, Marcus A.; Zettl, Alex

    2017-05-01

    Organic-inorganic halide perovskite materials have emerged as attractive alternatives to conventional solar cell building blocks. Their high light absorption coefficients and long diffusion lengths suggest high power conversion efficiencies, and indeed perovskite-based single bandgap and tandem solar cell designs have yielded impressive performances. One approach to further enhance solar spectrum utilization is the graded bandgap, but this has not been previously achieved for perovskites. In this study, we demonstrate graded bandgap perovskite solar cells with steady-state conversion efficiencies averaging 18.4%, with a best of 21.7%, all without reflective coatings. An analysis of the experimental data yields high fill factors of ~75% and high short-circuit current densities up to 42.1 mA cm-2. The cells are based on an architecture of two perovskite layers (CH3NH3SnI3 and CH3NH3PbI3-xBrx), incorporating GaN, monolayer hexagonal boron nitride, and graphene aerogel.

  16. Graded bandgap perovskite solar cells.

    PubMed

    Ergen, Onur; Gilbert, S Matt; Pham, Thang; Turner, Sally J; Tan, Mark Tian Zhi; Worsley, Marcus A; Zettl, Alex

    2017-05-01

    Organic-inorganic halide perovskite materials have emerged as attractive alternatives to conventional solar cell building blocks. Their high light absorption coefficients and long diffusion lengths suggest high power conversion efficiencies, and indeed perovskite-based single bandgap and tandem solar cell designs have yielded impressive performances. One approach to further enhance solar spectrum utilization is the graded bandgap, but this has not been previously achieved for perovskites. In this study, we demonstrate graded bandgap perovskite solar cells with steady-state conversion efficiencies averaging 18.4%, with a best of 21.7%, all without reflective coatings. An analysis of the experimental data yields high fill factors of ∼75% and high short-circuit current densities up to 42.1 mA cm(-2). The cells are based on an architecture of two perovskite layers (CH3NH3SnI3 and CH3NH3PbI3-xBrx), incorporating GaN, monolayer hexagonal boron nitride, and graphene aerogel.

  17. Oxygen storage properties and catalytic activity of layer-ordered perovskites BaY1-xGdxMn2O5+δ

    SciTech Connect

    Klimkowicz, A.; Świerczek, K.; Rząsa, T.; Takasaki, A.; Dabrowski, B.

    2016-05-01

    Crystal structure, oxygen storage-related and preliminary anaerobic methane combustion studies were conducted for BaY1-xGdxMn2O5+δ (0, 0.25, 0.5, 0.75 and 1) series of oxides prepared by a sol–gel method. All samples were found to possess layered-type A-site cation ordering, with the unit cell volume linearly dependent on the average radius of Y1-xGdx for both the reduced and the oxidized materials. The oxygen content in the temperature range of 400 °C–600 °C indicates change on the order of 1 atomic mole, occurring when the sample's surrounding atmosphere was changed from air to 5 vol.% H2 in Ar. The time dependence of the reduction shows activated character on temperature, with an activation energy, which seems to be related to the oxygen diffusion in the bulk of the materials. Initial data concerning methane combustion in oxygen-free conditions show promising catalytic activity of BaYMn2O6 at elevated temperatures.

  18. Oxygen content of superconducting perovskites, La/sub 2-x/Sr/sub x/CuO/sub y/ and YBa/sub 2/Cu/sub 3/O/sub y/

    SciTech Connect

    Appelman, E.H.; Morss, L.R.; Kini, A.M.; Geiser, U.; Umezawa, A.; Crabtree, G.W.; Carlson, K.D.

    1987-10-07

    Studies of the composition of YBa/sub 2/Cu/sub 3/O/sub y/ in which the oxidation states of Y and Ba are +3 and +2, respectively, have shown a direct relationship between the Cu(II)/Cu(III) ratio and the oxygen stoichiometry. Idometry or hydrogen reduction has generally been used for the Cu(III) determination. A modification of the idometric method that is simple to apply and is particularly suited to analyses of La/sub 2-x/Sr/sub x/CuO/sub y/ and YBa/sub 2/Cu/sub 3/O/sub y/ is described. The results of application to determination of the oxygen content of YBa/sub 2/Cu/sub 3/O/sub y/ are presented, and the oxygen content is related to the crystallographic and superconducting properties of the material. Results indicated that at room-temperature large variations of the oxygen content of the orthorhombic phase of YBa/sub 2/Cu/sub 3/O/sub y/ could occur without change in the lattice parameters or appreciable impairment of the resistive superconducting transition or diamagnetic properties. 13 references, 1 figure, 1 table.

  19. The effect of minor elements on H incorporation in MgSiO3 perovskite

    NASA Astrophysics Data System (ADS)

    Watson, H. C.; Fei, Y.; Hauri, E.; Reid, F.; Jacobsen, S. D.

    2006-12-01

    It has been predicted that silicate perovskite in the lower mantle may be a significant reservoir for hydrogen in the Earth's interior, although quantitative analysis of the hydrogen storage capacity has remained elusive. This is primarily due to difficulties in interpreting FTIR spectra of perovskite samples at room pressure [eg. Murakami et al. 2002, Science 295, 1885-1887, Bolfan-Casanova et al. 2003, Geophys. Res. Lett. 30, 1905, Litasov et al. 2003, EPSL 211, 189-203]. The mechanism by which H is thought to be incorporated into perovskite is through substitution of minor trivalent elements such as Al and Fe. This may open oxygen vacancies that are in turn, filled with OH groups for charge balance , although coupled substitution (e.g. 2Al3+ ----> Si^{4+}+Mg2+) is also a possibility [Navrotsky 1999, Science 284 5421, 1788 - 1789]. We have synthesized Al-bearing, and Al-Fe bearing perovskite samples under hydrous conditions in a multi-anvil apparatus at pressures ranging from 23-26 GPa and 1800°C and 1200°C. The starting materials consisted of either oxide powders with brucite as the source of H2O, or pre-synthesized Al, Fe bearing hydrous enstatite. The resulting perovskite crystals range in size from <20 microns to >100 microns in size. Their major element chemistry has been characterized by electron microprobe, and the H content of samples has been measured by secondary ion mass spectrometry using a 6f Cameca ion microprobe and is substantial (>1000ppm in some samples). Preliminary FTIR measurements support the idea that the H measured is structurally bound in the perovskite crystal. We find a linear correlation between Al and H content in the perovskite, and discussion follows on the substitution mechanisms for minor elements and H into perovskite at conditions relevant to the uppermost lower mantle.

  20. Oxygen-dependent copper toxicity: targets in the chlorophyll biosynthesis pathway identified in the copper efflux ATPase CopA deficient mutant.

    PubMed

    Liotenberg, Sylviane; Steunou, Anne-Soisig; Durand, Anne; Bourbon, Marie-Line; Bollivar, David; Hansson, Mats; Astier, Chantal; Ouchane, Soufian

    2015-06-01

    Characterization of a copA(-) mutant in the purple photosynthetic bacterium Rubrivivax gelatinosus under low oxygen or anaerobic conditions, as well as in the human pathogen Neisseria gonorrhoeae identified HemN as a copper toxicity target enzyme in the porphyrin synthesis pathway. Heme synthesis is, however, unaffected by copper under high oxygen tension because of the aerobic coproporphyrinogen III oxidase HemF. Nevertheless, in the copA(-) mutant under aerobiosis, we show that the chlorophyll biosynthesis pathway is affected by excess copper resulting in a substantial decrease of the photosystem. Analyses of pigments and enzyme activity showed that under low copper concentrations, the mutant accumulated protochlorophyllide, suggesting that the protochlorophyllide reductase activity is affected by excess copper. Increase of copper concentration led to a complete lack of chlorophyll synthesis as a result of the loss of Mg-chelatase activity. Both enzymes are widely distributed from bacteria to plants; both are [4Fe-4S] proteins and oxygen sensitive; our data demonstrate their in vivo susceptibility to copper in the presence of oxygen. Additionally, our study provides the understanding of molecular mechanisms that may contribute to chlorosis in plants when exposed to metals. The role of copper efflux systems and the impact of copper on heme and chlorophyll biosynthesis in phototrophs are addressed.

  1. Hybrid Organic-Inorganic Perovskite Photodetectors.

    PubMed

    Tian, Wei; Zhou, Huanping; Li, Liang

    2017-09-12

    Hybrid organic-inorganic perovskite materials garner enormous attention for a wide range of optoelectronic devices. Due to their attractive optical and electrical properties including high optical absorption coefficient, high carrier mobility, and long carrier diffusion length, perovskites have opened up a great opportunity for high performance photodetectors. This review aims to give a comprehensive summary of the significant results on perovskite-based photodetectors, focusing on the relationship among the perovskite structures, device configurations, and photodetecting performances. An introduction of recent progress in various perovskite structure-based photodetectors is provided. The emphasis is placed on the correlation between the perovskite structure and the device performance. Next, recent developments of bandgap-tunable perovskite and hybrid photodetectors built from perovskite heterostructures are highlighted. Then, effective approaches to enhance the stability of perovskite photodetector are presented, followed by the introduction of flexible and self-powered perovskite photodetectors. Finally, a summary of the previous results is given, and the major challenges that need to be addressed in the future are outlined. A comprehensive summary of the research status on perovskite photodetectors is hoped to push forward the development of this field. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Iridium-based double perovskites for efficient water oxidation in acid media

    PubMed Central

    Diaz-Morales, Oscar; Raaijman, Stefan; Kortlever, Ruud; Kooyman, Patricia J.; Wezendonk, Tim; Gascon, Jorge; Fu, W. T.; Koper, Marc T. M.

    2016-01-01

    The development of active, cost-effective and stable oxygen-evolving catalysts is one of the major challenges for solar-to-fuel conversion towards sustainable energy generation. Iridium oxide exhibits the best available compromise between catalytic activity and stability in acid media, but it is prohibitively expensive for large-scale applications. Therefore, preparing oxygen-evolving catalysts with lower amounts of the scarce but active and stable iridium is an attractive avenue to overcome this economical constraint. Here we report on a class of oxygen-evolving catalysts based on iridium double perovskites which contain 32 wt% less iridium than IrO2 and yet exhibit a more than threefold higher activity in acid media. According to recently suggested benchmarking criteria, the iridium double perovskites are the most active catalysts for oxygen evolution in acid media reported until now, to the best of our knowledge, and exhibit similar stability to IrO2. PMID:27498694

  3. Iridium-based double perovskites for efficient water oxidation in acid media

    NASA Astrophysics Data System (ADS)

    Diaz-Morales, Oscar; Raaijman, Stefan; Kortlever, Ruud; Kooyman, Patricia J.; Wezendonk, Tim; Gascon, Jorge; Fu, W. T.; Koper, Marc T. M.

    2016-08-01

    The development of active, cost-effective and stable oxygen-evolving catalysts is one of the major challenges for solar-to-fuel conversion towards sustainable energy generation. Iridium oxide exhibits the best available compromise between catalytic activity and stability in acid media, but it is prohibitively expensive for large-scale applications. Therefore, preparing oxygen-evolving catalysts with lower amounts of the scarce but active and stable iridium is an attractive avenue to overcome this economical constraint. Here we report on a class of oxygen-evolving catalysts based on iridium double perovskites which contain 32 wt% less iridium than IrO2 and yet exhibit a more than threefold higher activity in acid media. According to recently suggested benchmarking criteria, the iridium double perovskites are the most active catalysts for oxygen evolution in acid media reported until now, to the best of our knowledge, and exhibit similar stability to IrO2.

  4. Ferromagnetism in ruthenate perovskites

    NASA Astrophysics Data System (ADS)

    Dang, Hung T.; Mravlje, Jernej; Millis, Andrew J.

    2014-03-01

    In apparent contrast to the usual rule that stronger correlations favor magnetism and other forms of order, while weaker correlations lead to Fermi liquid metals, it has been experimentally established that CaRuO3, a more correlated material, is a paramagnetic metal with a Fermi liquid ground state while SrRuO3, which is less strongly correlated, is ferromagnetic below a Curie temperature of 160K. We present density functional plus dynamical mean field theory calculations which resolve this conundrum. We show that in these materials ferromagnetism occurs naturally for cubic perovskite systems at moderate correlations but is suppressed both by proximity to the Mott insulating phase and by increasing the amplitude of a GdFeO3 distortion. These factors are strongly related to the differences between Ca and Sr ruthenates and are used as the keys to solve the problem. Placement of the ruthenate materials on the metal-insulator phase diagram and comparison to previous works on the Ruddlesden-Popper materials are also discussed. Supported by the Basic Energy Sciences Program of the US Department of Energy under grant DOE ER046169 and the Columbia-Ecole Polytechnique Alliance program.

  5. The preparation of large surface area lanthanum based perovskite supports for AuPt nanoparticles: tuning the glycerol oxidation reaction pathway by switching the perovskite B site

    PubMed Central

    Evans, Christopher D.; Smith, Paul J.; Manning, Troy D.; Miedziak, Peter J.; Brett, Gemma L.; Armstrong, Robert D.; Bartley, Jonathan K.; Taylor, Stuart H.; Rosseinsky, Matthew J.; Hutchings, Graham J.

    2016-01-01

    Gold and gold alloys, in the form of supported nanoparticles, have been shown over the last three decades to be highly effective oxidation catalysts. Mixed metal oxide perovskites, with their high structural tolerance, are ideal for investigating how changes in the chemical composition of supports affect the catalysts' properties, while retaining similar surface areas, morphologies and metal co-ordinations. However, a significant disadvantage of using perovskites as supports is their high crystallinity and small surface area. We report the use of a supercritical carbon dioxide anti-solvent precipitation methodology to prepare large surface area lanthanum based perovskites, making the deposition of 1 wt% AuPt nanoparticles feasible. These catalysts were used for the selective oxidation of glycerol. By changing the elemental composition of the perovskite B site, we dramatically altered the reaction pathway between a sequential oxidation route to glyceric or tartronic acid and a dehydration reaction pathway to lactic acid. Selectivity profiles were correlated to reported oxygen adsorption capacities of the perovskite supports and also to changes in the AuPt nanoparticle morphologies. Extended time on line analysis using the best oxidation catalyst (AuPt/LaMnO3) produced an exceptionally high tartronic acid yield. LaMnO3 produced from alternative preparation methods was found to have lower activities, but gave comparable selectivity profiles to that produced using the supercritical carbon dioxide anti-solvent precipitation methodology. PMID:27074316

  6. The preparation of large surface area lanthanum based perovskite supports for AuPt nanoparticles: tuning the glycerol oxidation reaction pathway by switching the perovskite B site.

    PubMed

    Evans, Christopher D; Kondrat, Simon A; Smith, Paul J; Manning, Troy D; Miedziak, Peter J; Brett, Gemma L; Armstrong, Robert D; Bartley, Jonathan K; Taylor, Stuart H; Rosseinsky, Matthew J; Hutchings, Graham J

    2016-07-04

    Gold and gold alloys, in the form of supported nanoparticles, have been shown over the last three decades to be highly effective oxidation catalysts. Mixed metal oxide perovskites, with their high structural tolerance, are ideal for investigating how changes in the chemical composition of supports affect the catalysts' properties, while retaining similar surface areas, morphologies and metal co-ordinations. However, a significant disadvantage of using perovskites as supports is their high crystallinity and small surface area. We report the use of a supercritical carbon dioxide anti-solvent precipitation methodology to prepare large surface area lanthanum based perovskites, making the deposition of 1 wt% AuPt nanoparticles feasible. These catalysts were used for the selective oxidation of glycerol. By changing the elemental composition of the perovskite B site, we dramatically altered the reaction pathway between a sequential oxidation route to glyceric or tartronic acid and a dehydration reaction pathway to lactic acid. Selectivity profiles were correlated to reported oxygen adsorption capacities of the perovskite supports and also to changes in the AuPt nanoparticle morphologies. Extended time on line analysis using the best oxidation catalyst (AuPt/LaMnO3) produced an exceptionally high tartronic acid yield. LaMnO3 produced from alternative preparation methods was found to have lower activities, but gave comparable selectivity profiles to that produced using the supercritical carbon dioxide anti-solvent precipitation methodology.

  7. Lewis Acid-Base Adduct Approach for High Efficiency Perovskite Solar Cells.

    PubMed

    Lee, Jin-Wook; Kim, Hui-Seon; Park, Nam-Gyu

    2016-02-16

    Since the first report on the long-term durable 9.7% solid-state perovskite solar cell employing methylammonium lead iodide (CH3NH3PbI3), mesoporous TiO2, and 2,2',7,7'-tetrakis[N,N-di(4-methoxyphenyl)amino]-9,9'-spirobifluorene (spiro-MeOTAD) in 2012, following the seed technologies on perovskite-sensitized liquid junction solar cells in 2009 and 2011, a surge of interest has been focused on perovskite solar cells due to superb photovoltaic performance and extremely facile fabrication processes. The power conversion efficiency (PCE) of perovskite solar cells reached 21% in a very short period of time. Such an unprecedentedly high photovoltaic performance is due to the intrinsic optoelectronic property of organolead iodide perovskite material. Moreover, a high dielectric constant, sub-millimeter scale carrier diffusion length, an underlying ferroelectric property, and ion migration behavior can make organolead halide perovskites suitable for multifunctionality. Thus, besides solar cell applications, perovskite material has recently been applied to a variety fields of materials science such as photodetectors, light emitting diodes, lasing, X-ray imaging, resistive memory, and water splitting. Regardless of application areas, the growth of a well-defined perovskite layer with high crystallinity is essential for effective utilization of its excellent physicochemical properties. Therefore, an effective methodology for preparation of high quality perovskite layers is required. In this Account, an effective methodology for production of high quality perovskite layers is described, which is the Lewis acid-base adduct approach. In the solution process to form the perovskite layer, the key chemicals of CH3NH3I (or HC(NH2)2I) and PbI2 are used by dissolving them in polar aprotic solvents. Since polar aprotic solvents bear oxygen, sulfur, or nitrogen, they can act as a Lewis base. In addition, the main group compound PbI2 is known to be a Lewis acid. Thus, PbI2 has a chance

  8. Expression of a mitochondrial gene orfH79 from CMS-Honglian rice inhibits Escherichia coli growth via deficient oxygen consumption.

    PubMed

    Ding, Xia; Chen, Qiusheng; Bao, Canming; Ai, Aihua; Zhou, Ying; Li, Shaobo; Xie, Hongwei; Zhu, Youlin; Cai, Yaohui; Peng, Xiaojue

    2016-01-01

    Cytoplasmic male sterility (CMS) has often been associated with abnormal mitochondrial open frames (ORF), orfH79 is a mitochondrial chimeric gene responsible for the CMS trait in Honglian (HL) rice. In this study, the weakly produced ORFH79 protein significantly inhibited the growth of E. coli in an oxygen culture, however, the growth of the transformants producing ORFH79 was indistinguishable from the control under anaerobic incubation conditions. In addition, a lower respiration rate, wrinkled bacterial surfaces, and decreased pyruvate kinase and α-ketoglutarate dehydrogenase activities were observed in the ORFH79 produced E. coli. These results indicate that ORFH79 impairs the oxygen respiration of E. coli, which may inhibit E. coli growth.

  9. Stabilization of Oxygen-deficient Structure for Conducting Li4Ti5O12-δ by Molybdenum Doping in a Reducing Atmosphere

    PubMed Central

    Song, Hannah; Jeong, Tae-Gyung; Moon, Young Hoon; Chun, Ho-Hwan; Chung, Kyung Yoon; Kim, Hyung Sun; Cho, Byung Won; Kim, Yong-Tae

    2014-01-01

    Li4Ti5O12 (LTO) is recognized as being one of the most promising anode materials for high power Li ion batteries; however, its insulating nature is a major drawback. In recent years, a simple thermal treatment carried out in a reducing atmosphere has been shown to generate oxygen vacancies (VO) for increasing the electronic conductivity of this material. Such structural defects, however, lead to re-oxidization over time, causing serious deterioration in anode performance. Herein, we report a unique approach to increasing the electronic conductivity with simultaneous improvement in structural stability. Doping of LTO with Mo in a reducing atmosphere resulted in extra charges at Ti sites caused by charge compensation by the homogeneously distributed Mo6+ ions, being delocalized over the entire lattice, with fewer oxygen vacancies (VO) generated. Using this simple method, a marked increase in electronic conductivity was achieved, in addition to an extremely high rate capability, with no performance deterioration over time. PMID:24618982

  10. Interfaces in perovskite solar cells.

    PubMed

    Shi, Jiangjian; Xu, Xin; Li, Dongmei; Meng, Qingbo

    2015-06-03

    The interfacial atomic and electronic structures, charge transfer processes, and interface engineering in perovskite solar cells are discussed in this review. An effective heterojunction is found to exist at the window/perovskite absorber interface, contributing to the relatively fast extraction of free electrons. Moreover, the high photovoltage in this cell can be attributed to slow interfacial charge recombination due to the outstanding material and interfacial electronic properties. However, some fundamental questions including the interfacial atomic and electronic structures and the interface stability need to be further clarified. Designing and engineering the interfaces are also important for the next-stage development of this cell.

  11. Internal photopumping of Nd3+ (2H9/2, 4F5/2) states in yttrium aluminum garnet by excitation transfer from oxygen deficiency centers and Fe3+ continuum emission

    NASA Astrophysics Data System (ADS)

    Hewitt, J. D.; Spinka, T. M.; Senin, A. A.; Eden, J. G.

    2011-07-01

    Photoexcitation of Nd3+ (2H9/2, 4F5/2) states by the broad (˜70 nm FWHM), near-infrared continuum provided by Fe3+ has been observed at 300 K in bulk yttrium aluminum garnet (YAG) crystals doped with trace concentrations (<50 ppm) of Fe, Cr, and Eu. Irradiation of YAG at 248 nm with a KrF laser, which excites the oxygen deficiency center (ODC) in YAG having peak absorption at ˜240 nm, culminates in ODC→Fe3+ excitation transfer and subsequent Fe3+ emission. This internal optical pumping mechanism for rare earth ions is unencumbered by the requirement for donor-acceptor proximity that constrains conventional Förster-Dexter excitation transfer in co-doped crystals.

  12. The performance of spinel bulk-like oxygen-deficient CoGa2O4 as an air-cathode catalyst in microbial fuel cell

    NASA Astrophysics Data System (ADS)

    Liu, Di; Mo, Xiaoping; Li, Kexun; Liu, Yi; Wang, Junjie; Yang, Tingting

    2017-08-01

    Nano spinel bulk-like CoGa2O4 prepared via a facile hydrothermal method is used as a high efficient electrochemical catalyst in activated carbon (AC) air-cathode microbial fuel cell (MFC). The maximum power density of the modified MFC is 1911 ± 49 mW m-2, 147% higher than the MFC of untreated AC cathode. Transmission electron microscope (TEM) and X-ray diffraction (XRD) exhibit the morphology and crystal structure of CoGa2O4. Rotating disk electrode (RDE) confirms the four-electron pathway at the cathode during the oxygen reduction reaction (ORR). Thermogravimetric analysis (TGA) and X-ray photoelectron spectroscopy (XPS) illustrate that the high rate oxygen vacancy exist in the CoGa2O4. The oxygen vacancy of CoGa2O4 plays an important role in catalytic activity. In a word, the prepared nano spinel bulk-like CoGa2O4 provides an alternative to the costly Pt in air-cathode for power output.

  13. Bifunctional oxygen/air electrodes

    NASA Astrophysics Data System (ADS)

    Jörissen, Ludwig

    A selective review on the materials and construction principles used for bifunctional oxygen/air electrodes is given. The discussion emphasizes the catalytically active materials used for the construction of these electrodes, which are a key component in electrically rechargeable air breathing electrochemical systems. Whereas, in acid electrolytes normally noble metal catalysts must be used, there is a possibility to use less expensive transition metal oxides in alkaline electrolytes. Typical transition metal oxides have the perovskite, pyrochlore and spinel structure.

  14. Electrospinning preparation of oxygen-deficient nano TiO2-x/carbon fibre membrane as a self-standing high performance anode for Li-ion batteries.

    PubMed

    Jing, Mao-Xiang; Li, Jing-Quan; Han, Chong; Yao, Shan-Shan; Zhang, Ji; Zhai, Hong-Ai; Chen, Li-Li; Shen, Xiang-Qian; Xiao, Ke-Song

    2017-07-01

    Improving the specific capacity and electronic conductivity of TiO2 can boost its practical application as a promising anode material for lithium ion batteries. In this work, a three-dimensional networking oxygen-deficient nano TiO2-x/carbon fibre membrane was achieved by combining the electrospinning process with a hot-press sintering method and directly used as a self-standing anode. With the synergistic effects of three-dimensional conductive networks, surface oxygen deficiency, high specific surface area and high porosity, binder-free and self-standing structure, etc., the nano TiO2-x/carbon fibre membrane electrode displays a high electrochemical reaction kinetics and a high specific capacity. The reversible capacity could be jointly generated from porous carbon, full-lithiation of TiO2 and interfacial lithium storage. At a current density of 100 mA g(-1), the reversible discharge capacity can reach 464 mA h g(-1). Even at 500 mA g(-1), the discharge capacity still remains at 312 mA h g(-1). Compared with pure carbon fibre and TiO2 powder, the TiO2-x/C fibre membrane electrode also exhibits an excellent cycle performance with a discharge capacity of 209 mA h g(-1) after 700 cycles at the current density of 300 mA g(-1), and the coulombic efficiency always remains at approximately 100%.

  15. Doping of the quadruple perovskites of type Nd 2Ba 2Cu 2Ti 2- xO xO 11,  Mn, Fe, Co, Al and NdBa 3Cu 2Ti 1+ xNb 1- xNb 1- xO 11

    NASA Astrophysics Data System (ADS)

    Rentschler, Thomas

    1997-02-01

    The synthesis of new ceramic materials NdBa 3Cu 2Ti 1+ xNb 1- xO 11 and Nd 2Ba 2Cu 2Ti 2- xM xO 11, M  Mn, Fe, Co, Al with a quadruple perovskite structure was successfully performed. Rietveld refinements verified the oxygen deficient layered a p ∗ a p ∗ 4a p superstructure (space group P4/mmm). Heterovalent doping in these groups of materials was carried out in order to provide a hole carrier concentration in the CuO 2 layers structurally related to the high- Tc superconductors. However, superconductivity was not observed. The formation of oxygen defects is discussed.

  16. Photoluminescence characterisations of a dynamic aging process of organic-inorganic CH3NH3PbBr3 perovskite

    NASA Astrophysics Data System (ADS)

    Sheng, R.; Wen, X.; Huang, S.; Hao, X.; Chen, S.; Jiang, Y.; Deng, X.; Green, M. A.; Ho-Baillie, A. W. Y.

    2016-01-01

    After unprecedented development of organic-inorganic lead halide perovskite solar cells over the past few years, one of the biggest barriers towards their commercialization is the stability of the perovskite material. It is thus important to understand the interaction between the perovskite material and oxygen and/or humidity and the associated degradation process in order to improve device and encapsulation design for better durability. Here we characterize the dynamic aging process in vapour-assisted deposited (VASP) CH3NH3PbBr3 perovskite thin films using advanced optical techniques, such as time-resolved photoluminescence and fluorescence lifetime imaging microscopy (FLIM). Our investigation reveals that the perovskite grains grow spontaneously and the larger grains are formed at room temperature in the presence of moisture and oxygen. This crystallization process leads to a higher density of defects and a shorter carrier lifetime, specifically in the larger grains. Excitation-intensity-dependent steady-state photoluminescence shows both N2 stored and aged perovskite exhibit a super-linear increase of photoluminescence intensity with increasing excitation intensity; and the larger slope in aged sample suggests a larger density of defects is generated, consistent with time-resolved PL measurements.

  17. Systems and methods for scalable perovskite device fabrication

    DOEpatents

    Huang, Jinsong; Dong, Qingfeng; Sao, Yuchuan

    2017-02-28

    Continuous processes for fabricating a perovskite device are described that include using a doctor blade for continuously forming a perovskite layer and using a conductive tape lamination process to form an anode or a cathode layer on the perovskite device.

  18. Monolithic Perovskite Silicon Tandem Solar Cells with Advanced Optics

    SciTech Connect

    Goldschmidt, Jan C.; Bett, Alexander J.; Bivour, Martin; Blasi, Benedikt; Eisenlohr, Johannes; Kohlstadt, Markus; Lee, Seunghun; Mastroianni, Simone; Mundt, Laura; Mundus, Markus; Ndione, Paul; Reichel, Christian; Schubert, Martin; Schulze, Patricia S.; Tucher, Nico; Veit, Clemens; Veurman, Welmoed; Wienands, Karl; Winkler, Kristina; Wurfel, Uli; Glunz, Stefan W.; Hermle, Martin

    2016-11-14

    For high efficiency monolithic perovskite silicon tandem solar cells, we develop low-temperature processes for the perovskite top cell, rear-side light trapping, optimized perovskite growth, transparent contacts and adapted characterization methods.

  19. First-principles calculations of the OH- adsorption energy on perovskite oxide

    NASA Astrophysics Data System (ADS)

    Ohzuku, Hideo; Ikeno, Hidekazu; Yamada, Ikuya; Yagi, Shunsuke

    2016-08-01

    The oxygen evolution reaction (OER) that occurs during water oxidation is of considerable importance as an essential energy conversion reaction for rechargeable metal-air batteries and direct solar water splitting. ABO3 perovskite oxides have been extensively studied because of their high catalytic OER activity. In the present study, the OH- adsorption process on the perovskite surface about different B site cations was investigated by the first-principles calculations. We concluded that the adsorption energy of SrFeO3 surface is larger than that of SrTiO3.

  20. Environmental Effects on the Photophysics of Organic–Inorganic Halide Perovskites

    PubMed Central

    2015-01-01

    The photophysical properties of films of organic–inorganic lead halide perovskites under different ambient conditions are herein reported. We demonstrate that their luminescent properties are determined by the interplay between photoinduced activation and darkening processes, which strongly depend on the atmosphere surrounding the samples. We have isolated oxygen and moisture as the key elements in each process, activation and darkening, both of which involve the interaction with photogenerated carriers. These findings show that environmental factors play a key role in the performance of lead halide perovskites as efficient luminescent materials. PMID:26266592