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Sample records for oxygen deficient perovskite

  1. Enhancing Perovskite Electrocatalysis through Strain Tuning of the Oxygen Deficiency.

    PubMed

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

    2016-06-15

    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. 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. PMID:27232374

  2. Enhancing perovskite electrocatalysis through strain tuning of oxygen deficiency

    DOE PAGESBeta

    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 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. Ca₂Mn₂O₅ as oxygen-deficient perovskite electrocatalyst for oxygen evolution reaction.

    PubMed

    Kim, Jaemin; Yin, Xi; Tsao, Kai-Chieh; Fang, Shaohua; Yang, Hong

    2014-10-22

    This paper presents the use of Ca2Mn2O5 as an oxygen-deficient perovskite electrocatalyst for oxygen evolution reaction (OER) in alkaline media. Phase-pure Ca2Mn2O5 was made under mild reaction temperatures through a reductive annealing method. This oxygen deficient perovskite can catalyze the generation of oxygen at ~1.50 V versus (vs) reversible hydrogen electrode (RHE) electrochemically, and reach an OER mass activity of 30.1 A/g at 1.70 V (vs RHE). In comparison to the perovskite CaMnO3, Ca2Mn2O5 shows higher OER activities. The molecular level oxygen vacancies and high spin electron configuration on manganese in the crystal structures are likely the contributing factors for the enhanced performance. This work demonstrates that oxygen-deficient perovskite, A2B2O5, is a new class of high performance electrocatalyst for those reactions that involve active oxygen intermediates, such as reduction of oxygen and OER in water splitting.

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. Oxide-Ion Conduction in Anion-Deficient Perovskites.

    NASA Astrophysics Data System (ADS)

    Feng, Man

    1995-01-01

    Strategies for the design of an improved oxide -ion electrolyte for medium-temperature fuel cells, sensors, and oxygen pumps are outlined. Anion-deficient oxides with the perovskite structure were chosen for study. Stoichiometric oxides contain a high fraction of vacancies, but vacancy ordering suppresses ionic conductivity. Nevertheless, the brownmillerite rm Ba_2In_2O _5 undergoes an order-disorder transition at 930^circC that allows an estimate of the motional enthalpy of the disordered vacancy. Substitution of both aliovalent and isovalent cations were investigated as a means of suppressing the long-range ordering. Substitution of Nb^{5+}, Ti ^{4+}, Sn^{4+ } could be made for In^{3+ } at the B sites of the ABO_ {3-delta} perovskite structure, and this strategy did suppress long-range ordering of the oxygen vacancies for more than 10 mole % dopant. However, it was found that these dopants have a sufficient preference for octahedral anion coordination that water is introduced into the vacancies below 400^circ C; the protons introduced with the water became dominant conductive species below 400^circ C. At high temperature, the oxide-ion conduction is dominant and, below 930^circC, is enhanced by two orders of magnitude for about 20% dopant whether quadravalent or pentavalent dopants are used. Substitution of La^{3+} for Ba ^{2+} suppressed the introduction of water at low temperature, and the best oxide-ion conduction was achieved in rm Ba_{0.6}La _{0.4}InO_{2.7} isovalent doping of Y for In in rm Ba_2In _2O_5<=ad to the discovery of an extremely high ionic conduction in rm Ba _3Y_4O_9 stabilized at room temperature by quenching from above 1200^ circC. On heating in air, it first decomposes into rm Y_2O_3 and a Ba(OH)_2-BaO_2 mix that becomes an immobilized melt and a fast ionic conductor above 370^circC. With time in air, the melt is transformed to BaCO_3 , which is not conductive. Superior oxide-ion conduction was discovered in the Sr and Mg doped perovskite La

  10. 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.

  11. Structure and magnetism in the oxygen-deficient perovskites Ce{sub 1-x}Sr {sub x}CoO{sub 3-{delta}} (x {>=} 0.90)

    SciTech Connect

    James, M. . E-mail: mja@ansto.gov.au; Wallwork, K.S.; Withers, R.L.; Goossens, D.J.; Wilson, K.F.; Horvat, J.; Wang, X.L.; Colella, M.

    2005-08-11

    We have examined the structure and phase behaviour of strontium-doped Ce{sub 1-x}Sr {sub x}CoO{sub 3-{delta}} and found that the perovskite form is stabilised over a relatively narrow solid solution range (x > 0.85). A combination of electron, powder X-ray and neutron diffraction has revealed tetragonal superstructures of the basic perovskite unit; (I4/mmm) 2a {sub p} x 2a {sub p} x 4a {sub p} (x = 0.90) and (P4/mmm) a {sub p} x a {sub p} x 2a {sub p} (x = 0.95). Magnetisation measurements show ferromagnetic behaviour under applied magnetic fields. Low temperature neutron diffraction of Ce{sub 0.10}Sr{sub 0.90}CoO{sub 2.80} in zero field reveals a magnetic cell of dimension 2a {sub p} x 2a {sub p} x 4a {sub p} with an ordered cobalt moment of 1.7 B.M. at 25 K.

  12. Synthesis, Average Structure, and Magnetic Properties of Oxygen Deficient Perovskites (Ba 2-3 xBi 3 x-1 )(Fe 2 xBi 1-2 x)O 2+3/2 x

    NASA Astrophysics Data System (ADS)

    Boullay, Ph.; Hervieu, M.; Nguyen, N.; Raveau, B.

    1999-10-01

    A new family of oxygen deficient perovskite [Ba2-3xBi3x-1] [Fe2xBi1-2x]O2+3x/2 has been synthesized for 1/3≤x≤1/2. The average structure of these phases is determined using a combination of X-ray, neutron powder diffraction, and electron diffraction. The compounds exhibit a cubic subcell (a=ap) for x≤0.43 and a tetragonal subcell (a≈c≈ap) for 0.43

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

    PubMed

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

    2016-01-01

    Oxygen electrocatalysis, namely of the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER), governs the performance of numerous electrochemical energy systems such as reversible fuel cells, metal-air batteries, and water electrolyzers. However, the sluggish kinetics of these two reactions and their dependency on expensive noble metal catalysts (e.g, Pt or Ir) prohibit the sustainable commercialization of these highly innovative and in-demand technologies. Bifunctional perovskite oxides have emerged as a new class of highly efficient non-precious metal catalysts (NPMC) for oxygen electrocatalysis in alkaline media. In this review, we discuss the state-of-the-art understanding of bifunctional properties of perovskites with regards to their OER/ORR activity in alkaline media and review the associated reaction mechanisms on the oxides surface and the related activity descriptors developed in the recent literature. We also summarize the present strategies to modify their electronic structure and to further improve their performance for the ORR/OER through highlighting the new concepts relating to the role of surface redox chemistry and oxygen deficiency of perovskite oxides for the ORR/OER activity. In addition, we provide a brief account of recently developed advanced perovskite-nanocarbon hybrid bifunctional catalysts with much improved performances. PMID:26247625

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

    PubMed

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

    2016-01-01

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

  15. 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.

  16. 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....

  17. 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....

  18. 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....

  19. 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....

  20. 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....

  1. Synthesis and Characterization of Sr3FeMoO6.88: An Oxygen-Deficient 2D Analogue of the Double Perovskite Sr2FeMoO6

    SciTech Connect

    Veith, Gabriel M; Greenblatt, Martha; Croft, Mark; Ramanujachary, K. V.; Hattrick-Simpers, J.; Lofland, Samuel E.; Nowik, Israel

    2005-01-01

    We have prepared Sr{sub 3}FeMoO{sub 6.88(1)}, an oxygen-deficient two-dimensional analogue of the double perovskite Sr{sub 2}FeMoO{sub 6}, and have investigated its structure and physical properties. According to powder X-ray and neutron diffraction data, Sr{sub 3}FeMoO{sub 6.88} adopts the tetragonal n = 2 Ruddlesden-Popper structure (space group I4/mmm) with a completely disordered B-cation distribution and oxygen vacancies occurring preferentially at the axial O1 sites between the perovskite layers. X-ray absorption near-edge spectroscopy and Moessbauer data are consistent with trivalent Fe and mixed (4+/5+) Mo oxidation state. The compound is semiconducting, showing an intrinsic magnetic transition at {approx}85 K and an additional upturn in the magnetic susceptibility at {approx}270 K, the latter is associated with intergrowth defects. An appreciable magnetoresistance, reaching the value of {approx} -15% at 5 K and 5 T is also observed.

  2. Oxygen and cation ordered perovskite, Ba 2Y 2Mn 4O 11

    NASA Astrophysics Data System (ADS)

    Karppinen, M.; Okamoto, H.; Fjellvåg, H.; Motohashi, T.; Yamauchi, H.

    2004-06-01

    A three-step route has been developed for the synthesis of a new oxygen-ordered double perovskite, BaYMn 2O 5.5 or Ba 2Y 2Mn 4O 11. (i) The A-site cation ordered perovskite, BaYMn 2O 5+ δ, is first synthesized at δ≈0 by an oxygen-getter-controlled low-O 2-pressure encapsulation technique utilizing FeO as the getter for excess oxygen. (ii) The as-synthesized, oxygen-deficient BaYMn 2O 5.0 phase is then readily oxygenated to the δ≈1 level by means of 1-atm-O 2 annealing at low temperatures. (iii) By annealing this fully oxygenated BaYMn 2O 6.0 in flowing N 2 gas at moderate temperatures the new intermediate oxygen content oxide, BaYMn 2O 5.5 or Ba 2Y 2Mn 4O 11, is finally obtained. From thermogravimetric observation it is seen that the final oxygen depletion from δ≈1.0 to 0.5 occurs in a single sharp step about 600°C, implying that the oxygen stoichiometry of BaYMn 2O 5+ δ is not continuously tunable within 0.5< δ<1.0. For BaYMn 2O 5.5 synchrotron X-ray diffraction analysis reveals an orthorhombic crystal lattice and a long-range ordering of the excess oxygen atoms in the YO 0.5 layer. The magnetic behavior of BaYMn 2O 5.5 (with a ferromagnetic transition at ˜133 K) is found different from those previously reported for the known phases, BaYMn 2O 5.0 and BaYMn 2O 6.0.

  3. 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

  4. Design Principles of Perovskites for Thermochemical Oxygen Separation.

    PubMed

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

    2015-06-01

    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. PMID:25925955

  5. Design Principles of Perovskites for Thermochemical Oxygen Separation.

    PubMed

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

    2015-06-01

    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.

  6. 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....

  7. 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....

  8. 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....

  9. 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....

  10. 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....

  11. 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.

  12. 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

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

    DOE PAGESBeta

    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

  14. 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.

  15. Anion charge storage through oxygen intercalation in LaMnO3 perovskite pseudocapacitor electrodes

    NASA Astrophysics Data System (ADS)

    Mefford, J. Tyler; Hardin, William G.; Dai, Sheng; Johnston, Keith P.; Stevenson, Keith J.

    2014-07-01

    Perovskite oxides have attracted significant attention as energy conversion materials for metal-air battery and solid-oxide fuel-cell electrodes owing to their unique physical and electronic properties. Amongst these unique properties is the structural stability of the cation array in perovskites that can accommodate mobile oxygen ions under electrical polarization. Despite oxygen ion mobility and vacancies having been shown to play an important role in catalysis, their role in charge storage has yet to be explored. Herein we investigate the mechanism of oxygen-vacancy-mediated redox pseudocapacitance for a nanostructured lanthanum-based perovskite, LaMnO3. This is the first example of anion-based intercalation pseudocapacitance as well as the first time oxygen intercalation has been exploited for fast energy storage. Whereas previous pseudocapacitor and rechargeable battery charge storage studies have focused on cation intercalation, the anion-based mechanism presented here offers a new paradigm for electrochemical energy storage.

  16. 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. PMID:27478888

  17. Selective hydrogen oxidation in the presence of C3 hydrocarbons using perovskite oxygen reservoirs.

    PubMed

    Beckers, Jurriaan; Drost, Ruben; van Zandvoort, Ilona; Collignon, Paul F; Rothenberg, Gadi

    2008-05-16

    Perovskite-type oxides, ABO(3), can be successfully applied as solid "oxygen reservoirs" in redox reactions such as selective hydrogen combustion. This reaction is part of a novel process for propane oxidative dehydrogenation, wherein the lattice oxygen of the perovskite is used to combust hydrogen selectively from the dehydrogenation mixture at 550 degrees C. This gives three key advantages: it shifts the dehydrogenation equilibrium to the side of the desired products, heat is generated, thus aiding the endothermic dehydrogenation, and it simplifies product separation (H(2)O vs H(2)). Furthermore, the process is safer since it uses the catalysts' lattice oxygen instead of gaseous O(2). We screened fourteen perovskites for activity, selectivity and stability in selective hydrogen combustion. The catalytic properties depend strongly on the composition. Changing the B atom in a series of LaBO(3) perovskites shows that Mn and Co give a higher selectivity than Fe and Cr. Replacing some of the La atoms with Sr or Ca also affects the catalytic properties. Doping with Sr increases the selectivity of the LaFeO(3) perovskite, but yields a catalyst with low selectivity in the case of LaCrO(3). Conversely, doping LaCrO(3) with Ca increases the selectivity. The best results are achieved with Sr-doped LaMnO(3), with selectivities of up to 93 % and activities of around 150 mumol O m(-2). This catalyst, La(0.9)Sr(0.1)MnO(3), shows excellent stability, even after 125 redox cycles at 550 degrees C (70 h on stream). Notably, the activity per unit surface area of the perovskite catalysts is higher than that of doped cerias, the current benchmark of solid oxygen reservoirs.

  18. 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}.

  19. 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. PMID:26271910

  20. 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.

  1. 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.

  2. Enhanced Bifunctional Oxygen Catalysis in Strained LaNiO3 Perovskites

    DOE PAGESBeta

    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 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

  3. 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.

  4. Nonstoichiometric perovskite CaMnO(3-δ) for oxygen electrocatalysis with high activity.

    PubMed

    Du, Jing; Zhang, Tianran; Cheng, Fangyi; Chu, Wangsheng; Wu, Ziyu; Chen, Jun

    2014-09-01

    Perovskite oxides offer efficient and cheap electrocatalysts for both oxygen reduction reactions and oxygen evolution reactions (ORR/OER) in diverse oxygen-based electrochemical technologies. In this study, we report a facile strategy to enhance the electrocatalytic activity of CaMnO3 by introducing oxygen defects. The nonstoichiometric CaMnO(3-δ) (0 < δ ≤ 0.5) was prepared through thermal reduction of pristine perovskite microspheres and nanoparticles, which were synthesized from thermal-decomposition of carbonate precursors and the Pechini route, respectively. The as-prepared samples were analyzed by chemical titration, structural refinement, thermogravimetric analysis, and energy spectrometry. In 0.1 M KOH aqueous solution, the nonstoichiometric CaMnO(3-δ) with δ near 0.25 and an average Mn valence close to 3.5 exhibited the highest ORR activity (36.7 A g(-1) at 0.70 V vs RHE, with onset potential of 0.96 V), which is comparable to that of benchmark Pt/C. Density functional theory (DFT) studies and electrical conductivity measurement revealed that the enhanced ORR kinetics is due to facilitated oxygen activation and improved electrical properties. Besides high activity, the nonstoichiometric perovskite oxides showed respectable catalytic stability. Furthermore, the moderate oxygen-defective CaMnO(3-δ) (δ ≈ 0.25) favored the OER because of the improved electrical conductivity. This study makes nonstoichiometric CaMnO(3-δ) a promising active, inexpensive bifunctional catalytic material for reversible ORR and OER.

  5. Incommensurate Nuclear and Magnetic Structure of the Oxygen-Deficient Perovskites (Ba 2-3 xBi 3 x-1 )(Fe 2 xBi 1-2 x)O 2+3/2 x (0.43≤ x≤0.50)

    NASA Astrophysics Data System (ADS)

    Boullay, Ph.; Grebille, D.; Hervieu, M.; Raveau, B.; Suard, E.

    1999-11-01

    The actual nuclear and magnetic structures of the oxygen perovskites [Ba2-3xBi3x-1][Fe2xBi1-2x]O2+3x/2 (0.40oxygen vacancies are evidenced in the superstructure. The antiferromagnetic (AF) ordering is the same for all the members: iron spins are antiferromagnetically coupled along [110] and along [001] forming (001) AF planes.

  6. Impact of microstructure on oxygen semi-permeation performance of perovskite membranes: Understanding of oxygen transport mechanisms

    NASA Astrophysics Data System (ADS)

    Reichmann, M.; Geffroy, P.-M.; Richet, N.; Chartier, T.

    2016-08-01

    The influence of dense membrane microstructures on semi permeation performance is still not well understood, and no consensus or explanation can be established from the literature. The apparent discrepancy is likely due to a poor understanding of the oxygen transport mechanisms through the membrane and, specifically, to the impact of the microstructure on the oxygen surface exchange kinetics. The aim of this paper is to provide a better understanding of the impact of microstructures on oxygen transport mechanisms through the membrane. Two reference materials, Ba0.5Sr0.5Fe0.7Co0.3O3 (BSFCo) and La0.5Sr0.5Fe0.7Ga0.3O3 (LSFG) perovskites, are considered to explain the discrepancies observed in the literature.

  7. 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

    2016-03-01

    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. PMID:26813048

  8. 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

  9. 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...

  10. 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...

  11. 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...

  12. 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...

  13. 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...

  14. 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...

  15. 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...

  16. 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...

  17. 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...

  18. 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...

  19. 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...

  20. 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...

  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 77.102 - 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...

  3. 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...

  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. 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.

  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. PMID:26963760

  8. Hafnium carbide formation in oxygen deficient hafnium oxide thin films

    NASA Astrophysics Data System (ADS)

    Rodenbücher, C.; Hildebrandt, E.; Szot, K.; Sharath, S. U.; Kurian, J.; Komissinskiy, P.; Breuer, U.; Waser, R.; Alff, L.

    2016-06-01

    On highly oxygen deficient thin films of hafnium oxide (hafnia, HfO2-x) contaminated with adsorbates of carbon oxides, the formation of hafnium carbide (HfCx) at the surface during vacuum annealing at temperatures as low as 600 °C is reported. Using X-ray photoelectron spectroscopy the evolution of the HfCx surface layer related to a transformation from insulating into metallic state is monitored in situ. In contrast, for fully stoichiometric HfO2 thin films prepared and measured under identical conditions, the formation of HfCx was not detectable suggesting that the enhanced adsorption of carbon oxides on oxygen deficient films provides a carbon source for the carbide formation. This shows that a high concentration of oxygen vacancies in carbon contaminated hafnia lowers considerably the formation energy of hafnium carbide. Thus, the presence of a sufficient amount of residual carbon in resistive random access memory devices might lead to a similar carbide formation within the conducting filaments due to Joule heating.

  9. 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.

  10. 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.

  11. 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.

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

    DOEpatents

    Rieke, Peter C.; Coffey, Gregory W.; Pederson, Larry R.; Marina, Olga A.; Hardy, John S.; Singh, Prabhaker; Thomsen, Edwin C.

    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.

  13. 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.

  14. 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.

  15. Oxygen vacancy ordering within anion-deficient Ceria

    SciTech Connect

    Hull, S.; Norberg, S.T.; Ahmed, I.; Eriksson, S.G.; Marrocchelli, D.; Madden, P.A.

    2009-10-15

    The structural properties of anion deficient ceria, CeO{sub 2-{delta}}, have been studied as a function of oxygen partial pressure, p(O{sub 2}), over the range 0>=log{sub 10p}(O{sub 2})>=-18.9 at 1273(2) K using the neutron powder diffraction technique. Rietveld refinement of the diffraction data collected on decreasing p(O{sub 2}) showed increases in the cubic lattice parameter, a, the oxygen nonstoichiometry, delta, and the isotropic thermal vibration parameters, u{sub Ce} and u{sub O}, starting at log{sub 10p}(O{sub 2}){approx}-11. The increases are continuous, but show a distinct kink at log{sub 10p}(O{sub 2}){approx}-14.5. Analysis of the total scattering (Bragg plus diffuse components) using reverse Monte Carlo (RMC) modelling indicates that the O{sup 2-} vacancies preferentially align as pairs in the <111> cubic directions as the degree of nonstoichiometry increases. This behaviour is discussed with reference to the chemical crystallography of the CeO{sub 2}-Ce{sub 2}O{sub 3} system at ambient temperature and, in particular, to the nature of the long-range ordering of O{sup 2-} vacancies within the crystal structure of Ce{sub 7}O{sub 12}. - Graphical abstract: Partial radial distribution function for oxygen vacancies within CeO{sub 1.710} at 1273 K (solid line) showing the increased tendency for local ordering in <111> directions compared to a random distribution (dashed line).

  16. 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.

  17. 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...

  18. 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...

  19. 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...

  20. 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...

  1. 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...

  2. Optically-Induced Persistent Magnetization in Oxygen Deficient Strontium Titanate

    NASA Astrophysics Data System (ADS)

    Crooker, Scott

    2015-03-01

    Interest in electronics and spintronics based on complex oxide materials has exploded in recent years, fueled by the ability to grow atomically-precise heterostructures of various oxides 1. A foundational material in this burgeoning field is strontium titanate, a (nominally) non-magnetic wide-bandgap semiconductor. Owing to its ubiquity in oxide materials science, studies of SrTiO3's interesting dielectric, lattice, and optical properties represent mature research areas. However, renewed interest in SrTiO3 was recently sparked by observations of unexpected spin and magnetization phenomena at interfaces between SrTiO3 and other nonmagnetic oxides 1. The formation and distribution of oxygen vacancies (VO) in SrTiO3 are widely thought to play an essential but as-yet-incompletely understood role in these emergent phenomena. Here we demonstrate a surprising new aspect to the phenomenology of magnetism in SrTiO3 by reporting the observation of an optically-induced and persistent magnetization in slightly oxygen-deficient SrTiO3-δ bulk crystals, using magnetic circular dichroism spectroscopy and optically-coupled SQUID studies 2. This magnetization appears below 18K, persists for hours below 10K, and is tunable via the polarization and wavelength of sub-bandgap (400-500 nm) light. As such, magnetic patterns can be ``written'' into SrTiO3-δ, and subsequently read out, using light alone. This magnetism occurs only in crystals containing VO, and is consistent with a metastable spin polarization of VO-related defect complexes. These data reveal a detailed interplay between magnetism, lattice defects, and light in an archetypal complex oxide material, which may yield new insights into the recent exciting spin physics observed at oxide interfaces.

  3. 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.

  4. Oxygen vacancy clustering and electron localization in oxygen-deficient SrTiO(3): LDA + U study.

    PubMed

    Cuong, Do Duc; Lee, Bora; Choi, Kyeong Mi; Ahn, Hyo-Shin; Han, Seungwu; Lee, Jaichan

    2007-03-16

    We find, using a local density approximation +Hubbard U method, that oxygen vacancies tend to cluster in a linear way in SrTiO(3), a prototypical perovskite oxide, accompanied by strong electron localization at the 3d state of the nearby Ti transition metal ion. The vacancy clustering and the associated electron localization lead to a profound impact on materials properties, e.g., the reduction in free-carrier densities, the appearance of characteristic optical spectra, and the decrease in vacancy mobility. The high stability against the vacancy migration also suggests the physical reality of the vacancy cluster.

  5. Universal collaborative couplings between oxygen-octahedral rotations and antiferroelectric distortions in perovskites

    NASA Astrophysics Data System (ADS)

    Bellaiche, L.; Íñiguez, Jorge

    2013-07-01

    We identify two elemental interatomic couplings that control the collaborative (as opposed to competing) interaction between the O6 octahedral rotations (usually called antiferrodistortive or AFD modes) and the antiferroelectric (AFE) displacement patterns of the A-site cations in oxides with the ABO3 perovskite structure. Straightforward analytical derivations allow us to reproduce and explain the origin of various long-range AFE orders that have been previously found in different phases of several perovskite compounds, all possessing simple or even complex long-range AFD patterns. Our analysis also leads to the prediction of original peculiar combinations of AFD and AFE orders that are awaiting to be observed.

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

    DOE PAGESBeta

    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 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

  7. 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.

  8. Oxygen surface exchange and diffusion in the new perovskite oxide ion conductor LaGaO{sub 3}

    SciTech Connect

    Ishihara, Tatsumi; Honda, Miho; Takita, Yusaku; Kilner, J.A.

    1997-03-19

    One of the aims of these experiments was to verify that the oxygen ion is the majority carrier in LaGaO{sub 3}-based materials, as they are thought to exhibit p-type conductivity in the high oxygen partial pressure range. Specifically, we have investigated oxygen surface exchange and diffusion in La{sub 0.9}Sr{sub 0.1}Ga{sub 0.8}Mg{sub 0.2}O{sub 3-x} by {sup 18}O isotopic exchange and SIMS at high partial pressures of oxygen (0.1 MPa). In conclusion, these results show that bulk oxygen diffusion in LSGM is very rapid. By a comparison of the oxygen self-diffusivity obtained from tracer and ionic conductivity, the electrical conductivity observed is ionic in the temperature range we have measured. The surface exchange coefficients are anomalous when compared to other perovskite oxides. The activation enthalpy for surface exchange is higher than that for self diffusion coefficient, a finding observed for two other solid oxide electrolytes with the fluorite structure. This behavior is thought to originate in the low electron concentrations found in these electrolyte materials, particularly at the lowest temperatures. 13 refs., 2 figs.

  9. Engineering the electronic state of a perovskite electrocatalyst for synergistically enhanced oxygen evolution reaction.

    PubMed

    Guo, Yuqiao; Tong, Yun; Chen, Pengzuo; Xu, Kun; Zhao, Jiyin; Lin, Yue; Chu, Wangsheng; Peng, Zhenmeng; Wu, Changzheng; Xie, Yi

    2015-10-21

    A surface hydrogen effect to modulate the pure electronic-state transition in perovskite Ca0.9 Yb0.1 MnO3 synergistically generates a more suitable eg electron filling status and better conductivity. This achieves 100 times higher catalytic activity compared to that of a pristine sample. PMID:26316037

  10. Computational Study of Oxygen Diffusion along a[100] Dislocations in the Perovskite Oxide SrTiO3.

    PubMed

    Waldow, Stephan P; De Souza, Roger A

    2016-05-18

    We used classical molecular-dynamics simulations to study the atomistic structure of, and the diffusion of oxygen ions along, the periodic array of edge dislocations comprising a symmetrical 6.0° [100] tilt grain boundary in SrTiO3. The results indicate that, at elevated temperatures, the two types of dislocation core (TiO2-type and SrO-type) that make up the boundary are stable and that oxygen-deficient cores maintain their dissociated structures. They also confirm that oxygen vacancies prefer to reside at the cores rather than in the bulk. Tracer diffusion coefficients of oxygen were obtained for oxygen-deficient bulk and grain-boundary simulation cells at temperatures in the range of 1000 ≤ T/K ≤ 2300. Calculated values of the oxygen-vacancy diffusion coefficient for the bulk phase agree extremely well with published experimental data. Tracer diffusion coefficients obtained for the grain-boundary cell are, in comparison to those for the bulk, lower in magnitude and have a higher activation enthalpy, indicating that, relative to the bulk, the migration of oxygen ions along a[100] dislocation cores in SrTiO3 is hindered. These results provide further support for the decoupled model of filament formation in resistively switching SrTiO3. PMID:27121113

  11. 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.

  12. Oxygen Deficient YBa 2 Cu 3 O 7-δ : Two Superconducting Phases

    NASA Astrophysics Data System (ADS)

    Stankowski, J.; ¦L+/-Zak, A.; Kempiñski, W.; Andrzejewski, B.; Reichel, B.; Plesch, G.

    2003-03-01

    A set of oxygen deficient powder and granular samples of YBa 2 Cu 3 O 7-δ ceramics was studied by means of thermogravimetric and magnetically modulated microwave absorption methods. Especially the last method has turned out to be a powerful method, which was used to determine the dependence of critical temperature T c on the oxygen parameter δ. Using these methods it has been shown that the removing of oxygen evokes the inhomogeneous oxygen distribution in the samples and a change in carrier concentration till to the loss of superconducting properties. A superconducting phase with T_c=60 K, which occurs in oxygen deficient YBa 2 Cu 3 O 7-δ sample, is an unstable phase.

  13. Correlations between the oxygen deficiency and the laser damage resistance of different oxide films

    NASA Astrophysics Data System (ADS)

    Xu, Cheng; Yi, Peng; Fan, Heliang; Qi, Jianwei; Qiang, Yinghuai; Liu, Jiongtian; Tao, Chunxian; Li, Dawei

    2014-01-01

    Ta2O5, ZrO2 and HfO2 films are deposited on BK7 substrates by electron beam evaporation method. The effects of oxygen deficiency on the optical properties and laser-induced damage threshold (LIDT) are investigated by the combination of experimental methods and first principles calculations. The results show that the oxygen deficiency weakens the transmittance, whereas it enhances the absorption of all the films. Once the oxide vacancy appears, the band gaps decrease greatly, which seriously decrease the LIDT. The calculated negative vacancy energies indicate that, when the oxygen vacancy exists, Ta2O5 is most easily to be damaged, next is ZrO2 and the last is HfO2. It is consistent with the LIDT results that Ta2O5 increases 64.8%, ZrO2 increases 19.4% and HfO2 increases 12.9% when the oxygen vacancy is eliminated.

  14. Metalloporphyrin-modified perovskite-type oxide for the electroreduction of oxygen

    NASA Astrophysics Data System (ADS)

    Nagai, Tsukasa; Yamazaki, Shin-ichi; Asahi, Masafumi; Siroma, Zyun; Fujiwara, Naoko; Ioroi, Tsutomu

    2015-10-01

    Perovskite-type oxide-carbon (Vulcan XC72) mixture (La0.6Sr0.4Mn0.6Fe0.4O3/C) was modified by a metalloporphyrin (cobalt octaethylporphyrin: Co-OEP) having two-electron O2 reduction activity, and its electrochemical reduction activity for O2 (ORR) was investigated in an alkaline solution by rotating ring disk electrode (RRDE) voltammetry. The Co-OEP/La0.6Sr0.4Mn0.6Fe0.4O3/C catalyst showed improved ORR activity, with a positive shift of the onset potential. In addition, a decreased ring current compared to Co-OEP/C suggested that the quasi-four-electron reduction of O2 was also enhanced. Further experiments showed that ORR activity was also enhanced by Co-OEP-modification of other types of carbon (Ketjenblack EC600JD, Denka Black) or perovskite-type oxide (La0.6Ca0.4Mn0.6Fe0.4O3, La0.8Sr0.2Co0.6Fe0.4O3). In the case of the addition of other porphyrin complexes (cobalt tetraphenylporphyrin (Co-TPP), iron octaethylporphyrin (Fe-OEP)) to a La0.6Sr0.4Mn0.6Fe0.4O3/C catalyst, the onset potential did not shift to the positive side due to the lower activity compared to Co-OEP.

  15. Predicting oxygen vacancy non-stoichiometric concentration in perovskites from first principles

    NASA Astrophysics Data System (ADS)

    Luo, Heng; Shin, Yongwoo; Yu, Yang; Cetin, Deniz; Ludwig, Karl; Pal, Uday; Basu, Soumendra N.; Gopalan, Srikanth; Lin, Xi

    2014-12-01

    Formation of oxygen vacancies by introducing various mixed-valent cation dopants is a common practice to improve the cathode performance in solid oxide fuel cells. A computational procedure is developed in this work to predict the equilibrium oxygen vacancy non-stoichiometric concentrations at experimentally relevant temperatures and oxygen partial pressures for both bulk and surface oxide phases. The calculations are based on the first-principles density functional theory and a constrained free-energy functional. Quantitative agreements are found by direct comparisons to the thermogravimetry and solid electrolyte coulometry measurements for the strontium-doped lanthanum cobalt iron oxides at different compositions. Our results indicate that the oxygen vacancies are energetically stabilized at surfaces for all temperatures and all oxygen partial pressures, while such surface stabilization effects become stronger at higher temperatures and lower oxygen partial pressures.

  16. Oxygen reactivity of mammalian sulfite oxidase provides a concept for the treatment of sulfite oxidase deficiency.

    PubMed

    Belaidi, Abdel A; Röper, Juliane; Arjune, Sita; Krizowski, Sabina; Trifunovic, Aleksandra; Schwarz, Guenter

    2015-07-15

    Mammalian sulfite oxidase (SO) is a dimeric enzyme consisting of a molybdenum cofactor- (Moco) and haem-containing domain and catalyses the oxidation of toxic sulfite to sulfate. Following sulfite oxidation, electrons are passed from Moco via the haem cofactor to cytochrome c, the terminal electron acceptor. In contrast, plant SO (PSO) lacks the haem domain and electrons shuttle from Moco to molecular oxygen. Given the high similarity between plant and mammalian SO Moco domains, factors that determine the reactivity of PSO towards oxygen, remained unknown. In the present study, we generated mammalian haem-deficient and truncated SO variants and demonstrated their oxygen reactivity by hydrogen peroxide formation and oxygen-consumption studies. We found that intramolecular electron transfer between Moco and haem showed an inverse correlation to SO oxygen reactivity. Haem-deficient SO variants exhibited oxygen-dependent sulfite oxidation similar to PSO, which was confirmed further using haem-deficient human SO in a cell-based assay. This finding suggests the possibility to use oxygen-reactive SO variants in sulfite detoxification, as the loss of SO activity is causing severe neurodegeneration. Therefore we evaluated the potential use of PEG attachment (PEGylation) as a modification method for future enzyme substitution therapies using oxygen-reactive SO variants, which might use blood-dissolved oxygen as the electron acceptor. PEGylation has been shown to increase the half-life of other therapeutic proteins. PEGylation resulted in the modification of up to eight surface-exposed lysine residues of SO, an increased conformational stability and similar kinetic properties compared with wild-type SO. PMID:26171830

  17. Oxygen reactivity of mammalian sulfite oxidase provides a concept for the treatment of sulfite oxidase deficiency.

    PubMed

    Belaidi, Abdel A; Röper, Juliane; Arjune, Sita; Krizowski, Sabina; Trifunovic, Aleksandra; Schwarz, Guenter

    2015-07-15

    Mammalian sulfite oxidase (SO) is a dimeric enzyme consisting of a molybdenum cofactor- (Moco) and haem-containing domain and catalyses the oxidation of toxic sulfite to sulfate. Following sulfite oxidation, electrons are passed from Moco via the haem cofactor to cytochrome c, the terminal electron acceptor. In contrast, plant SO (PSO) lacks the haem domain and electrons shuttle from Moco to molecular oxygen. Given the high similarity between plant and mammalian SO Moco domains, factors that determine the reactivity of PSO towards oxygen, remained unknown. In the present study, we generated mammalian haem-deficient and truncated SO variants and demonstrated their oxygen reactivity by hydrogen peroxide formation and oxygen-consumption studies. We found that intramolecular electron transfer between Moco and haem showed an inverse correlation to SO oxygen reactivity. Haem-deficient SO variants exhibited oxygen-dependent sulfite oxidation similar to PSO, which was confirmed further using haem-deficient human SO in a cell-based assay. This finding suggests the possibility to use oxygen-reactive SO variants in sulfite detoxification, as the loss of SO activity is causing severe neurodegeneration. Therefore we evaluated the potential use of PEG attachment (PEGylation) as a modification method for future enzyme substitution therapies using oxygen-reactive SO variants, which might use blood-dissolved oxygen as the electron acceptor. PEGylation has been shown to increase the half-life of other therapeutic proteins. PEGylation resulted in the modification of up to eight surface-exposed lysine residues of SO, an increased conformational stability and similar kinetic properties compared with wild-type SO.

  18. 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. PMID:11285889

  19. Kinetic study for the formation of the oxygen-deficient magnetite

    SciTech Connect

    Togawa, T.; Wada, Y.; Yoshida, T.; Tsuji, M.; Tamaura, Y.

    1994-12-31

    An oxygen-deficient magnetite (Fe{sub 3}O{sub 4{minus}{delta}}) has been found to exist in the range of (0 < {delta} < 0.12) in the course of H{sub 2}-reduction of magnetite to {alpha}-Fe at 300 C. The formation of the oxygen-deficient magnetite was studied kinetically. In the temperature range of 250--350 C, the rate constants, k{sub 1} and k{sub 2}, were determined for the forward and reverse reactions, respectively. The rate of formation of the oxygen-deficient magnetite depends on the partial pressure of H{sub 2} gas. The rate constant k{sub 1}, was 10{sup {minus}9.58} at 300 C and the reaction order was 1.11 with respect to the partial pressure of H{sub 2} gas. The rate of reverse reaction depended on the partial pressure H{sub 2}O gas and the oxygen deficiency of magnetite, {delta}. The rate constant of the reverse reaction, k{sub 2}, was 10{sup {minus}2.54} at 300 C, and the reaction orders were 0.45 and 0.99 with respect to the partial pressure of H{sub 2}O gas and the {delta} value respectively. The activation energies for the forward and reverse reactions were determined to be 63.8 kJ/mol and 25.5 kJ/mol from the Arrhenius equation.

  20. 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.

  1. 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

    2014-01-01

    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/cm(2), and fill factor 0.64 had been achieved for our champion device.

  2. Reversible oxygen removal and uptake in the La2ZnMnO6 double perovskite: Performance in symmetrical SOFC cells

    NASA Astrophysics Data System (ADS)

    Martínez-Coronado, R.; Aguadero, A.; Alonso, J. A.; Fernández-Díaz, M. T.

    2013-04-01

    A polycrystalline oxygen-stoichiometric La2ZnMnO6 double-perovskite oxide has been prepared by soft-chemistry procedures, followed by annealing in air at 800 °C. A reduced specimen, with a La2ZnMnO6-δ composition, has been obtained by topotactical oxygen removal in an H2/N2 (5%/95%) flow at 600 °C. The structural characterization has been conducted from neutron powder diffraction (NPD) data, very sensitive to the contrast between Zn and Mn and the oxygen stoichiometry. Both perovskites (oxidized and reduced) crystallize in the monoclinic P21/n space group, exhibiting an antisite Zn/Mn disorder of about 15% and 14%, respectively. The partial reduction of Mn4+ to Mn3+ in the reduced phase is accompanied with the occurrence of oxygen vacancies, located at the axial octahedral sites. Thermogravimetric analysis (TGA) substantiates the oxygen stoichiometry and the stability range. Magnetic susceptibility measurements indicate an antiferromagnetic behaviour, confirming the presence of Mn3+ ions in the structure. The magnetic structure of the reduced phase, determined from NPD data at 3 K, shows an antiferromagnetic G-type coupling between Mn at 2c and 2d sites (promoted by the anti-site disorder); the ordered magnetic moment at Mn site is 0.789 μB at 3 K. Both phases display a semiconductor-like behaviour with a maximum conductivity of 0.052 S cm-1 for the reduced phase at 650 °C, due to the occurrence of Mn3+-Mn4+ mixed valence. Moreover, the measured thermal expansion coefficients perfectly match with the values usually displayed by SOFC electrolytes. The reversibility and versatility of the present compounds as catalysts for oxygen reduction (cathode) or fuel oxidation (anode) were tested in single SOFC cells yielding power density spanning from 120 to 155 W/cm2 using these perovskites as anode, cathode and symmetric electrodes for SOFC.

  3. 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.

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

    DOE PAGESBeta

    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. 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

  5. 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. 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.

  6. Modeling the paraelectric aging effect in the acceptor doped perovskite ferroelectrics: role of oxygen vacancy.

    PubMed

    Zhou, Yumei; Xue, Dezhen; Ding, Xiangdong; Zhang, Lixue; Sun, Jun; Ren, Xiaobing

    2013-10-30

    The time dependence of physical properties in the paraelectric phase was probed recently in a Mn(3+) doped (Ba0.8Sr0.2)TiO3 ceramic, providing a simple situation (without spontaneous polarization or domain walls) to quantify the role of the oxygen vacancy during aging. In the present study, we propose a quantitative model for paraelectric aging to understand how the distribution of the oxygen vacancy evolves with time and consequently influences the dielectric response of the paraelectric phase. First, by comparing dielectric behavior of paraelectric aging in a Mn(3+) doped (Ba0.75Sr0.25)TiO3 ceramic and the dielectric tunable effect, an internal bias field E(in) related to the oxygen vacancy is shown to exist in the paraelectric phase. Second, by introducing such a time dependent E(in) in a Landau-type model, we reproduce the dielectric response of Mn(3+) doped (Ba0.8Sr0.2)TiO3 ceramic during paraelectric aging. It is suggested that the increase of dielectric permittivity can be ascribed to the decrease of E(in) with time. The investigation of paraelectric aging is helpful for understanding the role of the oxygen vacancy in influencing the physical properties of ferroelectric materials.

  7. Oxygen deficiency in Ba2YCu3O7- δ: The need for a microscopic description

    NASA Astrophysics Data System (ADS)

    Batlogg, B.; Cava, R. J.

    1987-12-01

    The physical properties, such as crystal structure, resistivity, Tc and normal state susceptibility have been studied in Ba 2YCu 3O 7-δ as a function of oxygen deficiency δ. Oxygen was removed in a controlled way at relatively low temperatures employing a Zr-gettering technique. Not only do we find a second superconducting phase with Tc∼60 K and with new (short-range) crystallographic periodicity along the b-direction, but we also find that all physical properties depend on the manner in which oxygen is removed. Variations of physical properties among samples with the same over-all oxygen content can be consistently associated with the occupation of the various O-sites in the structure.

  8. Oxygen deficiency hazards associated with liquefied gas systems development of a program of controls

    SciTech Connect

    Miller, T.M.; Mazur, P.O.

    1983-01-01

    The use of liquefied gases in industry and research has become commonplace. Release into the atmosphere of these gases, whether intentional or not, will result in a displacement of air and a reduction in the oxygen concentration. Exposure to reduced levels of oxygen levels may cause reduced abilities, unconsciousness, or death. This paper describes the derivation of a novel program of controls for oxygen deficiency hazards. The key to this approach is a quantitative assessment of risk for each planned operation and the application of control measures to reduce that risk to an acceptable level. Five risk levels evolve which are based on the probability of fatality. Controls such as training, oxygen monitoring equipment, self-rescue respirators, and medical surveillance are required when the probability of fatality exceeds 10/sup -7/ per hour. The quantitative nature of this program ensures an appropriate level of control without undue burden or expense. 11 references, 5 figures, 3 tables.

  9. Ultrathin Spinel-Structured Nanosheets Rich in Oxygen Deficiencies for Enhanced Electrocatalytic Water Oxidation.

    PubMed

    Bao, Jian; Zhang, Xiaodong; Fan, Bo; Zhang, Jiajia; Zhou, Min; Yang, Wenlong; Hu, Xin; Wang, Hui; Pan, Bicai; Xie, Yi

    2015-06-15

    Electrochemical water splitting is a clean technology for H2 fuels, but greatly hindered by the slow kinetics of the oxygen evolution reaction (OER). Herein, a series of spinel-structured nanosheets with oxygen deficiencies and ultrathin thicknesses were designed to increase the reactivity and the number of active sites of the catalysts, which were then taken as an excellent platform for promoting the water oxidation process. Theoretical investigations showed that the oxygen vacancies confined in the ultrathin nanosheet could lower the adsorption energy of H2O, leading to increased OER efficiency. As expected, the NiCo2O4 ultrathin nanosheets rich in oxygen vacancies exhibited a large current density of 285 mA cm(-2) at 0.8 V and a small overpotential of 0.32 V, both of which are superior to the corresponding values of bulk samples or samples with few oxygen deficiencies and even higher than those of most reported non-precious-metal catalysts. This work should provide a new pathway for the design of advanced OER catalysts.

  10. 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.

  11. Exceptionally long-ranged lattice relaxation in oxygen-deficient Ta2O5

    NASA Astrophysics Data System (ADS)

    Yang, Yong; Sugino, Osamu; Kawazoe, Yoshiyuki

    2014-10-01

    The lattice relaxation in oxygen-deficient Ta2O5 is investigated using first-principles calculations. The presence of a charge-neutral oxygen vacancy can result in a long-ranged lattice relaxation which extends beyond 18 Å from the vacancy site. The lattice relaxation has significant effects on the vacancy formation energy as well as the electronic structures. The long-ranged behavior of the lattice relaxation is explained in terms of the Hellmann-Feynman forces and the potential energy surface related to the variation of Ta-O bond lengths.

  12. 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

    2011-12-01

    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.

  13. 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.

  14. 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.

  15. 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. PMID:24778239

  16. 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

  17. 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.

  18. 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.

  19. "Ba6Nb4RuO18" and "LaBa4Nb3RuO15" - The structural consequences of substituting paramagnetic cations into AnBn-1O3n cation-deficient perovskite oxides

    NASA Astrophysics Data System (ADS)

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

    2016-06-01

    The B-cation deficient perovskite phases Ba6Nb4RuO18 and LaBa4Nb3RuO15 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 Ba6Nb4TiO18 and LaBa4Nb3TiO15) they adopt 5-layer and 4-layer B-cation deficient perovskite structures respectively, and are better described as Ba5Nb3.33Ru0.81O15 and Ba3.16La0.84Nb2.36Ru0.72O12. 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 d0 and non-d0 transition metal cations.

  20. 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

  1. 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.

  2. Oxygen deficient ZnO1-x nanosheets with high visible light photocatalytic activity

    NASA Astrophysics Data System (ADS)

    Guo, Hong-Li; Zhu, Qing; Wu, Xi-Lin; Jiang, Yi-Fan; Xie, Xiao; Xu, An-Wu

    2015-04-01

    Zinc oxide is one of the most important wide-band-gap (3.2 eV) materials with versatile properties, however, it can not be excited by visible light. In this work, we have developed an exquisite and simple way to prepare oxygen-deficient ZnO1-x nanosheets with a gray-colored appearance and excellent visible light photocatalytic activity. Detailed analysis based on UV-Vis absorption spectra, X-band electron paramagnetic resonance (EPR) spectra, and photoluminescence (PL) spectra confirms the existence of oxygen vacancies in ZnO1-x. The incorporation of oxygen defects could effectively extend the light absorption of ZnO1-x into the visible-light region due to the fact that the energy of the localized state is located in the forbidden gap. Thus, our obtained ZnO1-x shows a higher photodegradation of methyl orange (MO) compared to defect-free ZnO under visible light illumination. Additionally, the high content of &z.rad;OH radicals with a strong photo-oxidation capability over the ZnO1-x nanosheets significantly contributes to the improvement in the photocatalytic performance. Our oxygen deficient ZnO1-x sample shows a very high photocatalytic activity for the degradation of MO even after 5 cycles without any obvious decline. The results demonstrate that defect engineering is a powerful tool to enhance the optoelectronic and photocatalytic performances of nanomaterials.Zinc oxide is one of the most important wide-band-gap (3.2 eV) materials with versatile properties, however, it can not be excited by visible light. In this work, we have developed an exquisite and simple way to prepare oxygen-deficient ZnO1-x nanosheets with a gray-colored appearance and excellent visible light photocatalytic activity. Detailed analysis based on UV-Vis absorption spectra, X-band electron paramagnetic resonance (EPR) spectra, and photoluminescence (PL) spectra confirms the existence of oxygen vacancies in ZnO1-x. The incorporation of oxygen defects could effectively extend the light

  3. 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.

  4. 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.

  5. Oxygen rocking aqueous batteries utilizing reversible topotactic oxygen insertion/extraction in iron-based perovskite oxides Ca1–xLaxFeO3−δ

    PubMed Central

    Hibino, Mitsuhiro; Kimura, Takeshi; Suga, Yosuke; Kudo, Tetsuichi; Mizuno, Noritaka

    2012-01-01

    Developments of large-scale energy storages with not only low cost and high safety but also abundant metals are significantly demanded. While lithium ion batteries are the most successful method, they cannot satisfy all conditions. Here we show the principle of novel lithium-free secondary oxygen rocking aqueous batteries, in which oxygen shuttles between the cathode and anode composed of iron-based perovskite-related oxides Ca0.5La0.5FeOz (2.5 ≤ z ≤ 2.75 and 2.75 ≤ z ≤ 3.0). Compound Ca0.5La0.5FeOz can undergo two kinds of reduction and reoxidation of Fe4+/Fe3+ and Fe3+/Fe2+, that are accompanied by reversible and repeatable topotactic oxygen extraction and reinsertion during discharge and charge processes. PMID:22924108

  6. Reactive Oxygen Species Deficiency Induces Autoimmunity with Type 1 Interferon Signature

    PubMed Central

    Kelkka, Tiina; Kienhöfer, Deborah; Hoffmann, Markus; Linja, Marjo; Wing, Kajsa; Sareila, Outi; Hultqvist, Malin; Laajala, Essi; Chen, Zhi; Vasconcelos, Júlia; Neves, Esmeralda; Guedes, Margarida; Marques, Laura; Krönke, Gerhard; Helminen, Merja; Kainulainen, Leena; Olofsson, Peter; Jalkanen, Sirpa; Lahesmaa, Riitta; Souto-Carneiro, M. Margarida

    2014-01-01

    Abstract Aims: Chronic granulomatous disease (CGD) is a primary immunodeficiency caused by mutations in the phagocyte reactive oxygen species (ROS)–producing NOX2 enzyme complex and characterized by recurrent infections associated with hyperinflammatory and autoimmune manifestations. A translational, comparative analysis of CGD patients and the corresponding ROS-deficient Ncf1m1J mutated mouse model was performed to reveal the molecular pathways operating in NOX2 complex deficient inflammation. Results: A prominent type I interferon (IFN) response signature that was accompanied by elevated autoantibody levels was identified in both mice and humans lacking functional NOX2 complex. To further underline the systemic lupus erythematosus (SLE)-related autoimmune process, we show that naïve Ncf1m1J mutated mice, similar to SLE patients, suffer from inflammatory kidney disease with IgG and C3 deposits in the glomeruli. Expression analysis of germ-free Ncf1m1J mutated mice reproduced the type I IFN signature, enabling us to conclude that the upregulated signaling pathway is of endogenous origin. Innovation: Our findings link the previously unexplained connection between ROS deficiency and increased susceptibility to autoimmunity by the discovery that activation of IFN signaling is a major pathway downstream of a deficient NOX2 complex in both mice and humans. Conclusion: We conclude that the lack of phagocyte-derived oxidative burst is associated with spontaneous autoimmunity and linked with type I IFN signature in both mice and humans. Antioxid. Redox Signal. 21, 2231–2245. PMID:24787605

  7. Doomed pioneers: Gravity-flow deposition and bioturbation in marine oxygen-deficient environments

    NASA Astrophysics Data System (ADS)

    Föilmi, Karl B.; Grimm, Kurt A.

    1990-11-01

    Isolated horizons of Thalassinoides and Gyrolithes burrows appear in exclusive association with gravity-flow deposits within sequences of nonbioturbated hernipelagic sedimentary rocks of the Miocene Monterey Formation of California and the Oligocene-Miocene San Gregorio Formation of Baja California. These burrowed levels are not associated with other ichnogenera such as Zoophycos and Chondrites. We infer a causal relation between gravity flow deposition and the presence of Thalassinoides and Gyrolithes and suggest that these gravity flows entrained thalassinidean crustacea. Upon deposition in oxygen-deficient environments, the surviving borrowers reworked substantial quantities of aminated, commonly organic-rich sediments in an environment from which they were previously excluded. The persistence of or the ecologically rapid return to oxygen-depleted conditions limited the survival time and ecological complexity of the transported infaunal dwellers and rendered them doomed pioneers. Ecological and physiological data support this hypothesis: thalassinidean crustacea have the capability to endure turbulent transport and survive up to 5-7 days of anoxia without being severely limited in their biological activities. The accurate recognition of doomed pioneer trace-fossil assemblages as ephemeral ecological phenomena in otherwise laminated successions may contribute to a better understanding and interpretation of paleo-oxygen levels and basin history.

  8. Electrochromism and small-polaron hopping in oxygen deficient and lithium intercalated amorphous tungsten oxide films

    NASA Astrophysics Data System (ADS)

    Triana, C. A.; Granqvist, C. G.; Niklasson, G. A.

    2015-07-01

    Thin films of Li x WO 3 - z with 0 ≤ x ≤ 0.27 and 0 ≤ z ≤ 0.27 were prepared by sputter deposition followed by electrochemical lithiation. Kramers-Kronig-consistent complex dielectric functions were obtained for these films by numerical inversion of experimental spectra of optical transmittance and reflectance by using a superposition of Tauc-Lorentz and Lorentz oscillator models. Low-energy optical absorption bands were induced by oxygen vacancies and/or by electrochemical intercalation of Li+ species together with charge compensating electrons. The experimental optical conductivity was fitted to a small-polaron model for disordered systems with strong electron-phonon interaction, taking into account transitions near the Fermi level. The optical absorption is due to small-polaron hopping and associated with the formation of W5+ states due to transfer of electrons from oxygen vacancies and/or insertion of Li+ species. The results also show increases in the Fermi level, caused by oxygen deficiency or Li+ insertion, which occur along with a band gap shift towards higher energies for the Li+ intercalated films.

  9. 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.

  10. 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.

  11. Oxygen deficiency and Sn doping of amorphous Ga2O3

    NASA Astrophysics Data System (ADS)

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

    2016-01-01

    The potential of effectively n-type doping Ga2O3 considering its large band gap has made it an attractive target for integration into transistors and solar cells. As a result amorphous GaOx 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 GaOx 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 GaOx 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 GaOx as an electron transport layer in Cu(In,Ga)Se2 and in Cu2O solar cells. Further it is shown that at low deposition temperatures, extrinsic doping with Sn is effective at low Sn concentrations.

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

    NASA Astrophysics Data System (ADS)

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

    2016-07-01

    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.

  13. 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

  14. 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.

  15. Elastic properties of yttrium-doped BaCeO3 perovskite

    NASA Astrophysics Data System (ADS)

    Zhang, Jianzhong; Zhao, Yusheng; Xu, Hongwu; Li, Baosheng; Weidner, Donald J.; Navrotsky, Alexandra

    2007-04-01

    Based on ambient ultrasonic measurements and x-ray diffraction under hydrostatic compression, the authors report here a comparative study of elasticity on oxygen-deficient perovskite, BaCe1-xYxO3-0.5x, with x =0.00 and 0.15. The results show that the presence of 2.5% oxygen vacancy has no measurable effect on the elastic bulk modulus. The shear modulus, however, decreases by approximately 5% in BaCe0.85Y0.15O2.925 perovskite. The differences between Y3+-doped cerate and Al3+-doped silicate suggest that the effect of oxygen vacancy on the elastic properties could be system dependent and may also be sensitive to distribution of oxygen vacancies within structures of the parent compounds.

  16. A-site deficient perovskites in the SrO-ZrO{sub 2}-Nb{sub 2}O{sub 5} system: Composition dependent structures from neutron powder diffraction data

    SciTech Connect

    Schmid, Siegbert; Withers, Ray L.

    2012-07-15

    A series of A-site deficient perovskite-type phases was synthesised and characterised in the SrO-ZrO{sub 2}-Nb{sub 2}O{sub 5} system. The composition range was established as Sr{sub 0.70+x}Zr{sub 0.40+2x}Nb{sub 0.60-2x}O{sub 3}, {approx}0.02{<=}x{<=}0.30, and the resulting structures refined using high resolution neutron powder diffraction data. While structures in this composition range are closely related to the cubic perovskite parent, the symmetry for all investigated compositions is lowered to tetragonal or orthorhombic. For x<0.15 the resulting space group is tetragonal I4/mcm, for x>0.15 it is orthorhombic Pnma and for x=0.15 two phases co-exist, in space groups I4/mcm and Pnma. - Graphical abstract: Structured diffuse intensity indicating additional short range order in the defect perovskite Sr{sub 0.72}Zr{sub 0.44}Nb{sub 0.56}O{sub 3}. Highlights: Black-Right-Pointing-Pointer A-site deficient perovskites synthesised in Sr{sub 0.70+x}Zr{sub 0.40+2x}Nb{sub 0.60-2x}O{sub 3}, {approx}0.02 {<=}x{<=}0.30. Black-Right-Pointing-Pointer Space groups established from X-ray, electron and neutron powder diffraction. Black-Right-Pointing-Pointer Structures refined and phase transition established from neutron diffraction data.

  17. 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

    2016-01-01

    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

  18. Inhomogeneous width of oxygen-deficient centers induced by electron irradiation of silica

    SciTech Connect

    D'Amico, Michele; Leone, Maurizio; Messina, Fabrizio; Cannas, Marco; Boscaino, Roberto

    2009-02-01

    We report a study of the luminescence activity of oxygen-deficient centers stabilized in as-grown synthetic silica, as compared with the same defects induced by {beta} irradiation at increasing doses, ranging from 1.2x10{sup 3} to 5x10{sup 6} kGy. We experimentally observe a progressive broadening of the luminescence band with increasing total electron dose released on samples. By analyzing our data within a theoretical model capable of separating homogeneous and inhomogeneous contribution to the total luminescence linewidth, we observe that the increasing of the width is entirely ascribable to the inhomogeneous component which increases, in the most irradiated sample, of 60% with respect to the value in the as-grown sample. This effect can be due either to the progressive creation of new defects statistically exploring different sites of the matrix, or to a progressive structural transformation of silica host which affects the optical properties of induced point defects.

  19. Carbon solids in oxygen-deficient explosives (LA-UR-13-21151)

    NASA Astrophysics Data System (ADS)

    Peery, Travis

    2013-06-01

    The phase behavior of excess carbon in oxygen-deficient explosives has a significant effect on detonation properties and product equations of state. Mixtures of fuel oil in ammonium nitrate (ANFO) above a stoichiometric ratio demonstrate that even small amounts of graphite, on the order of 5% by mole fraction, can substantially alter the Chapman-Jouget (CJ) state properties, a central ingredient in modeling the products equation of state. Similar effects can be seen for Composition B, which borders the carbon phase boundary between graphite and diamond. Nano-diamond formation adds complexity to the product modeling because of surface adsorption effects. I will discuss these carbon phase issues in our equation of state modeling of detonation products, including our statistical mechanics description of carbon clustering and surface chemistry to properly treat solid carbon formation. This work is supported by the Advanced Simulation and Computing Program, under the NNSA.

  20. 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.

  1. 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.

  2. 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

  3. 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.

  4. 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.

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

    PubMed

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

    2016-06-06

    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.

  6. 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. PMID:26585386

  7. 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. PMID:27604172

  8. 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.

  9. 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. PMID:26418118

  10. 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.

  11. Initial experience with recombinant antithrombin to treat antithrombin deficiency in patients on extracorporeal membrane oxygenation.

    PubMed

    Niimi, Kevin S; Fanning, Jeffrey J

    2014-03-01

    Acquired antithrombin (AT) deficiency has been associated with patients on extracorporeal membrane oxygenation (ECMO) as a result of hemodilution, blood coagulation activation, and the use of heparin. Replacement of AT has been typically utilized through the use of fresh-frozen plasma or AT concentrate. Antithrombin alfa (ATryn) is a recombinant form of AT (rAT) with an identical amino acid sequence as that of plasma-derived antithrombin. The primary objective of this study is to examine the relationship of rAT dose to measured plasma antithrombin activity in a small series of patients who received rAT while on ECMO. A retrospective chart review was performed of all patients at Medical City Children's Hospital who received ATryn while supported on ECMO between December 2011 and April 2012. Five patients were identified and the patients' weight, bolus dose of ATryn, drip rate of ATryn, and AT blood levels were collected for analysis. The median age of these patients was 1 month (range, 1 day to 3.75 years). Because no dosing guidelines exist for pediatric ECMO, a starting dose of ATryn was chosen based on the manufacturer's labeled indication (prevention of thromboembolic events in patients with AT hereditary deficiency). The median dose of rAT was 368 IU/kg/day (range, 104-520 IU/kg/day) to obtain AT activity level of 80-120%. The average time to reach the targeted AT activity level (80-120%) was 12.7 hours (range, 11-17 hours). Our findings suggest that the published ATryn dose may be inadequate to reach desired AT activity concentrations for pediatric patients on ECMO. Difference in patient population, use of extracorporeal circuits, and the use of heparin are likely explanations for this finding. We would also recommend frequent checking of AT levels while delivering this drug because making timely adjustments is necessary for achieving and maintaining the target AT activity level. PMID:24779124

  12. Energetics of perovskite-type materials applied in solid oxide fuel cells (SOFCs): Electrolytes, cathodes and interconnects

    NASA Astrophysics Data System (ADS)

    Cheng, Jihong

    oxygen vacancies, which strongly depend on the oxygen partial pressure and temperature. Major defects are dopants, oxygen vacancies and electron holes. La1-xSrxFeO3-delta (cathode materials) and La1-x-AxCrO 3-delta (A = Ca or Sr) (interconnect materials) were chosen for study. The overall energetic trends in these complex perovskites are modeled by several competing factors: (1) the chemical nature of dopant ions (acidity/basicity), (2) coupled substitution involving oxygen vacancy formation, (3) redox of the transition metal in each sample series with a given dopant composition, and (4) short-range oxygen vacancy ordering in oxygen-deficient samples.

  13. 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.

  14. 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.

  15. 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.

  16. Subtle local structural variations in oxygen deficient niobium germanate thin film glasses as revealed by x-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Sahiner, M. A.; Nabizadeh, A.; Rivella, D.; Cerqueira, L.; Hachlica, J.; Morea, R.; Gonzalo, J.; Woicik, J. C.

    2016-05-01

    The local electronic and crystal structure of niobium-lead-germanate, Nb2O5-PbO- GeO2 (NPG), glass thin films on silicon substrates were probed by XANES and EXAFS. NPG glasses are promising candidates for applications in nonlinear optical devices because they exhibit interesting optical characteristics such as high nonlinear third order optical susceptibility. In this work NPG glasses were prepared with pulsed laser deposition method with varying oxygen partial pressure to induce thin films with different oxygen stoichiometry. Previously, it was shown that oxygen stoichiometry has a very important effect to produce unusual high optical susceptibility. Detailed EXAFS and XANES analyses in a series of NPG thin films revealed the subtle variations in the local environment around Nb atoms and the Nb oxidation states caused by oxygen deficiencies.

  17. 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.

  18. 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. PMID:25764431

  19. 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

  20. 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

  1. Giant oxygen isotope effect on the metal-insulator transition of RNiO{sub 3} perovskites

    SciTech Connect

    Medarde, M.; Fauth, F.; Furrer, A.; Lacorre, P.; Conder, K.

    1998-08-01

    The metal to insulator transition displayed by all the members of the perovskite family RNiO{sub 3} (R = 4f rare earth different from La) has attracted a lot of interest since it constitutes one of the few examples of this phenomenon in perfectly stoichiometric compounds. In spite of the great deal of work performed during the last six years, the mechanism responsible for the electronic localization is still a matter of controversy. The observation of unusually large O isotope shifts on the metal-insulator temperature T{sub MI} reported in this study represents an important advance since it clearly proves the dominant role of the electron lattice interaction as driving force for the transition. Moreover, the good agreement between this observation and a simple model based on the existence of Jahn-Teller polarons in the metallic state gives further qualitative and quantitative support to the polaronic picture recently suggested to account for O isotope effects in other 3d transition metal oxides containing Jahn-Teller ions.

  2. 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}}.

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. Cation-Deficient Perovskite-Related (Ba,La) nTi n- δO 3 n ( n≥4 δ) Microphases in the La 4Ti 3O 12-BaTiO 3 System: An HRTEM Approach

    NASA Astrophysics Data System (ADS)

    Trolliard, G.; Harre, N.; Mercurio, D.; Frit, B.

    1999-07-01

    The large nonstoichiometric domain, observed in the La4Ti3O12-rich part of the La4Ti3O12-BaTiO3 system, has been shown to correspond to a continuous series of cation-deficient perovskite-related (Ba,La)nTin-δO3n (n≥4δ) microphases. The crystal structures of these microphases have been analyzed by electron diffraction and high-resolution electron microscopy. They can be described as coherent intergrowths of P-perovskite-like blocks La4Ti3O12 and Q-perovskite-like blocks BaLa4Ti4O15, respectively, constitutive of the simple basic terms n=4 and n=5 of the previously identified (Ba,La)nTin-1O3n series. The corresponding BaQLa4(P+Q)Ti3P+4QO12P+15Q microphases can thus be denoted by 4P5Q in a compact form. In fact, only the 4P51 intergrowth sequences have been observed. Eight of these are clearly shown by direct imaging. No intergrowth terms were observed for compositions ranging from BaLa4Ti4O15 (n=5) to Ba2La4Ti5O18 (n=6). The ability of the system to develop coherent intergrowths has been discussed in the light of information provided by an accurate analysis of crystal structures of the basic members of the series: La4Ti3O12 (n=4), BaLa4Ti4O15 (n=5), and Ba2La4Ti5O18 (n=6).

  8. 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

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

    PubMed

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

    2016-06-21

    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. 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.

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

    DOE PAGESBeta

    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 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

  11. Impact of seasonal oxygen deficiency on the phosphorous geochemistry of surface sediments along the Western Continental Shelf of India

    NASA Astrophysics Data System (ADS)

    Jacob, Josia; Ghosh, Prosenjit; Balchandran, K. K.; George, Rejomon

    2010-08-01

    The intensification of the natural coastal hypoxic zone over the western Indian shelf in the recent years and its impact on the biogeochemistry and marine life is a matter of concern. This study examines the influence of the seasonal oxygen deficiency on the phosphorus geochemistry of the surface sediments along the western continental shelf of India (WCSI). Speciation of phosphorus along with the geochemical characteristics (total organic carbon - TOC, total nitrogen - TN, and total phosphorus - TP) of the surface sediments and the hydrography of the western continental shelf of India (WCSI) were studied, during late summer monsoon (LSM) and spring intermonsoon (SIM). The hydrography of the WCSI revealed upwelling and associated seasonal oxygen deficiency with denitrifying suboxic conditions along the inner shelf and hypoxic conditions along the outer shelf. High concentrations of dissolved phosphate (PO4) and dissolved Iron (Fe) were also observed in the subsurface water of the inner shelf during LSM. The shelf water of the WCSI was oligotrophic and oxygen rich during SIM. A latitudinal enrichment of TOC, TN and TP in the surface sediments was observed at 13-17° N, along the WCSI during LSM, where seasonal suboxia was intense. Authigenic apatite bound phosphorus (Paut) was the major phosphorus species along the WCSI during LSM whereas detrital flourapatite bound phosphorus (Pdet) was the major species during SIM. Substantial depletion of reactive iron(III)-bound phosphorus (ΔPFe) was observed in the surface sediments of the WCSI during LSM which showed significant correlation with the enrichment of PO4 (ΔPO4) in the overlying water during LSM compared to SIM. PO4 diffusing into the water column from the sediments by reductive dissolution of PPFe probably leads to high dissolved PO4 along the inner shelf water during LSM which agrees with the existing hypothesis. Hence, phosphorus geochemistry of the surface sediments plays a major role in the biogeochemical

  12. Can oxygen deficient SmFeAsO1 - x be synthesized?: Unintentional incorporation of hydride ion at oxygen vacancy site

    NASA Astrophysics Data System (ADS)

    Muraba, Yoshinori; Iimura, Soshi; Matsuishi, Satoru; Hosono, Hideo

    Hydrogen substitution and introduction of oxygen vacancy are effective electron doping methods for the LnFeAsO. However, their Tc vs e-/Fe diagrams do not entirely overlap each other, while Tc vs lattice dimension relationships are very similar. These contradictions can be understood by assuming that unintentional hydrogen is incorporated into the oxygen vacancy. To examine the preferred electron-dopant species in LnFeAsO and the influence of the atmosphere during synthesis on the formation of LnFeAsO1- x , we try to synthesize the SmFeAsO1- x under three well-controlled atmosphere (H2O, H2 and H2O- and H2-free). Under H2O and H2 atmosphere, hydrogen were incorporated at oxygen sites as the hydride ion and SmFeAsO1- x Hx was formed. On the other hand, when H2O and H2 were removed from synthetic process, nearly stoichiometric SmFeAsO was formed. Furthermore, DFT calculations showed that H-substituted samples are more stable than oxygen deficient samples. These results strongly imply that the reported LnFeAsO1- x was contaminated with unintentional hydrogen and LnFeAsO1- x Hx was misidentified as LnFeAsO1- x .

  13. 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

    2016-09-01

    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. PMID:27556281

  14. Enhancing the hole-conductivity of spiro-OMeTAD without oxygen or lithium salts by using spiro(TFSI)₂ in perovskite and dye-sensitized solar cells.

    PubMed

    Nguyen, William H; Bailie, Colin D; Unger, Eva L; McGehee, Michael D

    2014-08-01

    2,2',7,7'-Tetrakis(N,N-di-p-methoxyphenylamine)-9,9'-spirobifluorene (spiro-OMeTAD), the prevalent organic hole transport material used in solid-state dye-sensitized solar cells and perovskite-absorber solar cells, relies on an uncontrolled oxidative process to reach appreciable conductivity. This work presents the use of a dicationic salt of spiro-OMeTAD, named spiro(TFSI)2, as a facile means of controllably increasing the conductivity of spiro-OMeTAD up to 10(-3) S cm(-1) without relying on oxidation in air. Spiro(TFSI)2 enables the first demonstration of solid-state dye-sensitized solar cells fabricated and operated with the complete exclusion of oxygen after deposition of the sensitizer with higher and more reproducible device performance. Perovskite-absorber solar cells fabricated with spiro(TFSI)2 show improved operating stability in an inert atmosphere. Gaining control of the conductivity of the HTM in both dye-sensitized and perovskite-absorber solar cells in an inert atmosphere using spiro(TFSI)2 is an important step toward the commercialization of these technologies.

  15. 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.

  16. 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

    2016-01-01

    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

  17. 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

  18. 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.

  19. 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).

  20. 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. PMID:27143344

  1. Electron-microscopy study of the microstructures in oxygen-deficient pure zirconia and yttrium-doped zirconia

    SciTech Connect

    Kim, Y.M.

    1988-01-01

    The microstructures of oxygen-deficient pure zirconia and 5 mol% Y{sub 2}O{sub 3}-ZrO{sub 2} made by skull melting and/or vacuum sintering were studied by conventional transmission electron microscopy, high-resolution electron microscopy (HREM) and image simulation with multislice calculation. Oxygen-deficient pure zirconia shows heavy twinning and a high density of stacking faults and dislocations. The atomic nature of the (100) twin interface in monoclinic zirconia was determined using HREM and simulation. The fault vectors of the stacking faults lying on the (010) plane were determined. The stacking faults seem to accommodate part of the nonstoichiometry. Zirconia that was reduced to a greater extent by vacuum annealing and quenching from 2000{degree}C has many twinning dislocations at the (100) twin interfaces. The growth tips of the twins have regularly spaced fringes. The HREM study has shown that both of these features are zonal twinning dislocations of height three times d{sub 100}. The twin growth has been explained in terms of lattice shearing by zonal twinning dislocations and lattice shuffling. The range of microstructural features observed provides a means to interpret the kinetics of decomposition of the cubic phase.

  2. 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

  3. 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.

  4. Synthesis of anion-deficient layered perovskites, ACa[sub 2]Nb[sub 3-x]M[sub x]O[sub 10-x] (A = Rb, Cs; M = Al, Fe), exhibiting ion-exchange and intercalation. Evidence for the formation of layered brownmillerites, ACa[sub 2]Nb[sub 2]AlO[sub 9] (A = Cs, H)

    SciTech Connect

    Uma, S.; Gopalakrishnan, J. )

    1994-07-01

    Anion-deficient layered perovskite oxides of the formula, ACa[sub 2]Nb[sub 3-x]M[sub x]O[sub 10-x] (A = Rb, Cs; M = Al, Fe) for 0 < x [le] 1.0, possessing tetragonal structures similar to the parent ACa[sub 2]Nb[sub 3]O[sub 10], have been synthesized. The interlayer A cations in these materials are readily exchanged with protons in aqueous HNO[sub 3] to give the protonated derivatives, HCa[sub 2]Nb[sub 3-x]M[sub x]O[sub 10-x]; the latter are solid Bronsted acids intercalating a number of organic amines including aniline (pK[sub a] = 4.63). The distribution of acid sites in the interlaying region of HCa[sub 2]Nb[sub 2]MO[sub 9] inferred from n-alkylamine intercalation suggests that oxygen vacancies and Nb/M atoms are disordered in the ACa[sub 2]Nb[sub 2]MO[sub 9] samples prepared at 1100-1200[degrees]C. Annealing a disordered sample of CsCa[sub 2]Nb[sub 2]AlO[sub 9] for a long time at lower temperatures tends to order the Nb/Al atoms and oxygen vacancies to produce octahedral (NbO[sub 6/2])-tetrahedral (AlO[sub 4/2])-octahedral (NbO[sub 6/2]) layer sequence reminiscent of the brownmillerite structure. 22 refs., 7 figs., 5 tabs.

  5. 17O NMR study of the doped electrons in lightly oxygen-deficient cubic SrMnO3 -x

    NASA Astrophysics Data System (ADS)

    Trokiner, A.; Verkhovskii, S.; Volkova, Z.; Gerashenko, A.; Mikhalev, K.; Germov, A.; Yakubovskii, A.; Korolev, A.; Dabrowski, B.; Tyutyunnik, A.

    2016-05-01

    The spin susceptibility of the localized Mn (t2 g) electrons, χs, and the spatially distributed spin density of the doped electrons were investigated by 17O nuclear magnetic resonance (NMR) in the paramagnetic (PM) and antiferromagnetic (AF) phases of electron-doped SrMnO3 -x ceramics with the cubic structure. Three lightly doped samples (2 x <0.015 ) were studied with TN=220 K-240 K. In the PM state χs increases gradually from TN and reaches a broad maximum above ˜1.5 TN . The gapped behavior of χs indicates a low-dimensional short-range spin order persisting above TN. These short-range one-dimensional correlations are consistent with 17O NMR results obtained at room temperature, which show that Mn magnetic moments are aligned along the edges of the cubic unit cell. Above 350 K all doped electrons are fast-moving eg electrons. They provide the uniform polarization of the localized spins which increases χs and the increasing doping shifts the oxygen-deficient SrMnO3 -x oxide towards a ferromagnetic (FM) metallic state. At lower T the doped electrons are heterogeneously distributed in the oxide: The fraction of the fast-moving electrons diminishes and vanishes below 100 K, while the remaining doped electrons slow down their hopping and each of them creates a FM domain. These FM domains which are detected below 10 K by 55Mn NMR can be considered as small-size magnetic polarons. Their T -activated hopping in the G-type AF lattice was probed by 17O spin-echo experiments. The energy barrier of hopping shows a trend to grow with increasing doping, indicating that the de Gennes metallic ground state cannot be achieved in oxygen-deficient SrMnO3 -x oxides, probably due to detrimental oxygen vacancy defects.

  6. 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

  7. 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.

  8. Strain-driven oxygen deficiency in multiferroic SrMnO3 thin films

    NASA Astrophysics Data System (ADS)

    Agrawal, P.; Guo, J.; Yu, P.; Hébert, C.; Passerone, D.; Erni, R.; Rossell, M. D.

    2016-09-01

    The structural and electronic properties of a series of SrMnO3 thin films grown on different substrates leading to different biaxial strains are examined by means of aberration-corrected high-angle annular dark-field scanning transmission electron microscopy and electron energy-loss spectroscopy (EELS). Here, we report a comprehensive theoretical investigation on the impact of oxygen nonstoichiometry and strain on the O-K and Mn-L2 ,3 electron energy-loss near-edge structures of SrMnO3 with the aid of the all-electron density functional theory code wien2k. Our experimental and theoretical EELS data reveal pronounced peak-height changes and energy shifts as a function of strain, which are ascribed to differences in the oxygen vacancy density rather than to a direct effect of lattice distortions. In addition, we find that the formation of oxygen vacancies in SrMnO3 is likely to be enhanced by tensile strain. Compared to the unstrained material, the vacancy formation energy is reduced by 0.25 eV under 3.78% tensile strain.

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

    DOE PAGESBeta

    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-reducedmore » BaTiO3-δ is due to the appearance of nonferroelectric cubic lattice.« less

  11. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2016-06-01

    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.

  13. 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

  14. 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.

  15. 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. PMID:24989042

  16. 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. PMID:27455174

  17. 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.

  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 tantalum pentoxide from first-principles calculations

    SciTech Connect

    Bondi, Robert J. Desjarlais, Michael P.; Thompson, Aidan P.; Brennecka, Geoff L.; Marinella, Matthew J.

    2013-11-28

    We apply first-principles density-functional theory (DFT) calculations, ab-initio molecular dynamics, and the Kubo-Greenwood formula to predict electrical conductivity in Ta{sub 2}O{sub x} (0 ≤ x ≤ 5) as a function of composition, phase, and temperature, where additional focus is given to various oxidation states of the O monovacancy (V{sub O}{sup n}; n = 0,1+,2+). In the crystalline phase, our DFT calculations suggest that V{sub O}{sup 0} prefers equatorial O sites, while V{sub O}{sup 1+} and V{sub O}{sup 2+} are energetically preferred in the O cap sites of TaO{sub 7} polyhedra. Our calculations of DC conductivity at 300 K agree well with experimental measurements taken on Ta{sub 2}O{sub x} thin films (0.18 ≤ x ≤ 4.72) and bulk Ta{sub 2}O{sub 5} 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 Ta{sub 2}O{sub 5} electronic structure provide further theoretical basis to substantiate V{sub O}{sup 0} as a donor dopant in Ta{sub 2}O{sub 5}. Furthermore, this dopant-like behavior is specific to the neutral case and not observed in either the 1+ or 2+ oxidation states, which suggests that reduction and oxidation reactions may effectively act as donor activation and deactivation mechanisms, respectively, for V{sub O}{sup n} in Ta{sub 2}O{sub 5}.

  20. Fluorination of epitaxial oxides: synthesis of perovskite oxyfluoride thin films.

    PubMed

    Moon, Eun Ju; Xie, Yujun; Laird, Eric D; Keavney, David J; Li, Christopher Y; May, Steven J

    2014-02-12

    While the synthesis of ABO3 perovskite films has enabled new strategies to control the functionality of this material class, the chemistries that have been realized in thin film form constitute only a fraction of those accessible to bulk chemists. Here, we report the synthesis of oxyfluoride films, where the incorporation of F may provide a new means to tune physical properties in thin films by modifying electronic structure. Fluorination is achieved by spin coating a poly(vinylidene fluoride) (PVDF) solution onto oxygen-deficient films. The film/polymer bilayer is then annealed, promoting the diffusion of F into the film. We have used this method to synthesize SrFeO(3-α)Fγ films, as confirmed by X-ray photoemission spectroscopy and X-ray absorption spectroscopy. PMID:24443775

  1. 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

  2. Effects of predation and oxygen deficiency on different age classes of the amphipod Monoporeia affinis

    NASA Astrophysics Data System (ADS)

    Sandberg, E.; Bonsdorff, E.

    1996-06-01

    Predation by the big brackish-water isopod Saduria entomon on two age-classes (juveniles and adults) of the small deposit-feeding amphipod Monoporeia (syn. Pontoporeia) affinis was studied at different oxygen conditions (normoxia>11 mg/l O 2, and moderate hypoxia 4 mg/l O 2). Vulnerability of juvenile and adult M. affinis was studied in single and mixed age-class treatments. The proportions of juveniles and adults were varied at one total numerical density. The predatory effects were measured as numbers of individuals consumed and of total biomass intake (mg ash-free dry weight). The highest predation rate (in numbers) was detected in the single-prey treatment with juvenile M. affinis, both in normoxia and moderate hypoxia. No preference for any of the two size classes was found in the treatment with equal numbers of adults and juveniles. In normoxia, the total number of prey consumed decreased with increasing proportions of adults, while intake increased in terms of biomass. In moderate hypoxia, high proportions of adults reduced the predation rate of S. entomon to such an extent that also the intake in terms of biomass was significantly negatively affected.

  3. A New Family of Perovskite Catalysts for Oxygen-Evolution Reaction in Alkaline Media: BaNiO3 and BaNi(0.83)O(2.5).

    PubMed

    Lee, Jin Goo; Hwang, Jeemin; Hwang, Ho Jung; Jeon, Ok Sung; Jang, Jeongseok; Kwon, Ohchan; Lee, Yeayeon; Han, Byungchan; Shul, Yong-Gun

    2016-03-16

    Establishment of a sustainable energy society has been strong driving force to develop cost-effective and highly active catalysts for energy conversion and storage devices such as metal-air batteries and electrochemical water splitting systems. This is because the oxygen evolution reaction (OER), a vital reaction for the operation, is substantially sluggish even with precious metals-based catalysts. Here, we show for the first time that a hexagonal perovskite, BaNiO3, can be a highly functional catalyst for OER in alkaline media. We demonstrate that the BaNiO3 performs OER activity at least an order of magnitude higher than an IrO2 catalyst. Using integrated density functional theory calculations and experimental validations, we unveil that the underlying mechanism originates from structural transformation from BaNiO3 to BaNi(0.83)O(2.5) (Ba6Ni5O15) over the OER cycling process.

  4. A New Family of Perovskite Catalysts for Oxygen-Evolution Reaction in Alkaline Media: BaNiO3 and BaNi(0.83)O(2.5).

    PubMed

    Lee, Jin Goo; Hwang, Jeemin; Hwang, Ho Jung; Jeon, Ok Sung; Jang, Jeongseok; Kwon, Ohchan; Lee, Yeayeon; Han, Byungchan; Shul, Yong-Gun

    2016-03-16

    Establishment of a sustainable energy society has been strong driving force to develop cost-effective and highly active catalysts for energy conversion and storage devices such as metal-air batteries and electrochemical water splitting systems. This is because the oxygen evolution reaction (OER), a vital reaction for the operation, is substantially sluggish even with precious metals-based catalysts. Here, we show for the first time that a hexagonal perovskite, BaNiO3, can be a highly functional catalyst for OER in alkaline media. We demonstrate that the BaNiO3 performs OER activity at least an order of magnitude higher than an IrO2 catalyst. Using integrated density functional theory calculations and experimental validations, we unveil that the underlying mechanism originates from structural transformation from BaNiO3 to BaNi(0.83)O(2.5) (Ba6Ni5O15) over the OER cycling process. PMID:26910187

  5. Electric transport coefficients in highly epitaxial LaBaCo2O5 + δ films with "p-to-n" transition induced by oxygen deficiency

    NASA Astrophysics Data System (ADS)

    Shaibo, J.; Zhang, Q. Y.; Wang, Y. Q.; Hu, H. C.; Li, X. N.; Pan, L. J.

    2016-08-01

    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 LaBaCo2O5 + 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 cm2/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.

  6. Oxygen deficiency induced deterioration in microstructure and magnetic properties at Y3Fe5O12/Pt interface

    NASA Astrophysics Data System (ADS)

    Song, Dongsheng; Ma, Li; Zhou, Shiming; Zhu, Jing

    2015-07-01

    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 Y3Fe5O12 (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.

  7. 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.

  8. 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

  9. Polarization twist in perovskite ferrielectrics.

    PubMed

    Kitanaka, Yuuki; Hirano, Kiyotaka; Ogino, Motohiro; Noguchi, Yuji; Miyayama, Masaru; Moriyoshi, Chikako; Kuroiwa, Yoshihiro

    2016-09-02

    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.

  10. Polarization twist in perovskite ferrielectrics.

    PubMed

    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

  11. Exchange of Silicon by Trivalent Cations of Iron or Aluminium in Calcium Silicate Perovskite

    NASA Astrophysics Data System (ADS)

    Bläß, U. W.; Boffa-Ballaran, T.; Frost, D. J.; Langenhorst, F.; McCammon, C. A.; Seifert, F.; van Aken, P. A.

    2003-04-01

    Based on experiments it is widely accepted that calcium silicate perovskite is an important constituent of the Earth's transition zone and the lower mantle as a host mineral for calcium as well as for trace elements. In addition the incorporation of Fe3+ or Al3+ and the associated creation of oxygen vacancies could lead to drastic changes in physical and structural properties. In other perovskites such effects are well known: In MgSiO3 perovskite the incorporation of even a few percent of these elements strongly affects the elastic and transport properties. At higher concentrations of vacancies ordering may occur, as in the model system Ca(FexTi1-x)O3-x/2, in which a complete ordering of oxygen vacancies in pseudocubic \\{100\\} planes causes the formation of several intermediate phases. Multianvil experiments in the system Ca(FexSi1-x)O3-x/2 were run at several P-T conditions and a buffered oxygen fugacity of Re-ReO2, and have shown that the maximum exchange of silicon by trivalent iron in CaSiO3 - perovskite is limited to 4% at 16 GPa. This probably disordered phase is clearly separated by a solvus from an ordered perovskite phase with the composition Ca(Fe0.4Si0.6)O2.8. No further oxygen deficient perovskites exist at more iron rich compositions, except the endmember CaFeO2.5, which we observed to be stable at less than 5 GPa only. The unique Ca(Fe0.4Si0.6)O2.8 phase could be examined in detail by optical microscopy, X-ray diffraction, M&{uml;o}ssbauer spectroscopy, electron microprobe, transmission electron microscopy and electron energy loss spectroscopy. All observations indicate that the structure can be characterised by oxygen deficient tetrahedral double layers perpendicular to pseudocubic <111> directions, alternating with eight octahedral perovskite layers, which are one half each occupied by silicon and iron. With aluminium an analogous phase exists with the composition Ca(Al0.4Si0.6)O2.8, where a similar diffraction pattern suggests the same type of

  12. 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.

  13. Acceptor-oxygen vacancy defect dipoles and fully coordinated defect centers in a ferroelectric perovskite lattice: Electron paramagnetic resonance analysis of Mn2+ in single crystal BaTiO3

    NASA Astrophysics Data System (ADS)

    Maier, R. A.; Pomorski, T. A.; Lenahan, P. M.; Randall, C. A.

    2015-10-01

    Defect dipoles are significant point defects in perovskite oxides as a result of their impact on oxygen vacancy dynamics. Electron paramagnetic resonance (EPR) was used to investigate the local defect structure of single crystal BaTiO3 doped with manganese. These results, along with a re-analysis of literature data, do not support the conclusion that transition metal-oxygen vacancy nearest neighbor defect dipoles ( M nT i ″ - VO • • ) × in ferroelectric BaTiO3 are majority defect centers as previously reported. Local symmetry analysis of the zero-field splitting term of the spin Hamiltonian supports the assignment of fully coordinated defect centers as opposed to defect dipoles for resonance signals at geff ˜ 2. A newly discovered defect center with g⊥ ˜ 6 is observed in the manganese doped system, and it is argued that this defect center belongs to an associated defect complex or defect dipole. This newly reported strong axial defect center, however, is present in small, minor concentrations compared to the well-known Mn2+ center with zero-field splitting of D ˜ 645 MHz. In regard to relative concentration, it is concluded that the dominant point defect related to the Mn2+ ion doped in BaTiO3 corresponds to B-site substitution with six nearest neighbor anions in octahedral coordination.

  14. Gene expression profiling reveals decreased expression of two hemoglobin genes associated with increased consumption of oxygen in Chironomus tentans exposed to atrazine: a possible mechanism for adapting to oxygen deficiency.

    PubMed

    Anderson, Troy D; Jin-Clark, Ying; Begum, Khurshida; Starkey, Sharon R; Zhu, Kun Yan

    2008-01-31

    Atrazine is an extensively used triazine herbicide in agricultural and residential areas and has been routinely detected in many surface and ground waters. This study reveals various up- and down-regulated genes associated with hypoxic stress in atrazine-treated fourth-instar Chironomus tentans larvae (midges) by using restriction fragment differential display-PCR. Two down-regulated hemoglobin cDNAs were isolated from the midges. Northern blot analysis indicated CteHb-IIbeta and CteHb-III mRNA expressions decreased by 36 and 21%, respectively, in midges exposed to atrazine at 1 microg/L for 96h. Decreased hemoglobin gene expression was associated with elevated oxygen consumption in atrazine-treated midges. Midges exposed to atrazine at 1 microg/L increased their oxygen consumption by 47%, whereas midges exposed to atrazine at 1000 microg/L for 48h increased their oxygen consumption by 66%. Our study demonstrates for the first time that atrazine, at environmentally relevant concentrations, can elevate respiration, possibly eliciting counteractive measures at the transcriptional level to adapt to oxygen deficiency in an ecologically important aquatic insect. Our results further suggest that the ability to modulate both the quantity and quality of Hb serves as an adaptive response to counteract the initial onset of oxygen deficiency induced by atrazine in midges.

  15. Energetics of magnesium, strontium, and barium doped lanthanum gallate perovskites

    NASA Astrophysics Data System (ADS)

    Cheng, Jihong; Navrotsky, Alexandra

    2004-01-01

    LaGaO 3 perovskites doped with Sr or Ba at the La site and Mg at the Ga site were prepared by solid-state reaction or sol-gel method and characterized. Enthalpies of formation from constituent oxides at 298 K were determined by high-temperature oxide melt solution calorimetry. Energetic trends are discussed in terms of defect chemistry. As oxygen deficiency increases, formation enthalpies define three trends, LaGa 1- yMg yO 3- δ (LGM), La 1- xSr xGa 1- yMg yO 3- δ (LSGM), and La 1- xBa xGa 1- yMg yO 3- δ (LBGM). They become less exothermic with increasing doping, suggesting a dominant destabilization effect from oxygen vacancies. The endothermic enthalpy of vacancy formation is 275±37, 166±18 and 138±12 kJ/mol of VO·· for LGM, LBGM and LSGM, respectively. Tolerance factor and ion size mismatch also affect enthalpies. In terms of energetics, Sr is the best dopant for the La site and Mg for the Ga site, supporting earlier studies, including oxygen ion conductivity and computer modeling.

  16. Hydrogen-Substituted Superconductors SmFeAsO(1-x)Hx Misidentified As Oxygen-Deficient SmFeAsO(1-x).

    PubMed

    Muraba, Yoshinori; Iimura, Soshi; Matsuishi, Satoru; Hosono, Hideo

    2015-12-01

    We investigated the preferred electron dopants at the oxygen sites of 1111-type SmFeAsO by changing the atmospheres around the precursor with the composition of Sm:Fe:As:O = 1:1:1:1 - x in high-pressure synthesis. Under H2O and H2 atmospheres, hydrogens derived from H2O or H2 molecules were introduced into the oxygen sites as a hydride ion, and SmFeAsO(1-x)Hx was obtained. However, when the H2O and H2 sources were removed from the synthetic process, nearly stoichiometric SmFeAsO was obtained and the maximum amount of oxygen vacancies introduced remained x = 0.05(4). Density functional theory calculations indicated that substitution of hydrogen in the form of H(-) is more stable than the formation of an oxygen vacancy at the oxygen site of SmFeAsO. These results strongly imply that oxygen-deficient SmFeAsO(1-x) reported previously is SmFeAsO(1-x)Hx with hydride ion incorporated unintentionally during high-pressure synthesis. PMID:26587763

  17. In situ formation of oxygen vacancy in perovskite Sr(0.95)Ti(0.8)Nb(0.1)M(0.1)O3 (M = Mn, Cr) toward efficient carbon dioxide electrolysis.

    PubMed

    Zhang, Jun; Xie, Kui; Wei, Haoshan; Qin, Qingqing; Qi, Wentao; Yang, Liming; Ruan, Cong; Wu, Yucheng

    2014-11-18

    In this work, redox-active Mn or Cr is introduced to the B site of redox stable perovskite Sr(0.95)Ti(0.9)Nb(0.1)O3.00 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 Sr(0.95)Ti(0.9)Nb(0.1)O3.00 to reduced Sr(0.95)Ti(0.9)Nb(0.1)O2.90 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 Sr(0.95)Ti(0.8)Nb(0.1)M(0.1)O3.00 (M = Mn, Cr) to Sr(0.95)Ti(0.8)Nb(0.1)M0.1O2.85. 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.

  18. 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.

  19. Mass-specific respiration of mesozooplankton and its role in the maintenance of an oxygen-deficient ecological barrier (BEDOX) in the upwelling zone off Chile upon presence of a shallow oxygen minimum zone

    NASA Astrophysics Data System (ADS)

    Donoso, Katty; Escribano, Ruben

    2014-01-01

    A shallow oxygen minimum zone (OMZ) in the coastal upwelling zone off Chile may vertically confine most zooplankton to a narrow (< 50 m) upper layer. From laboratory experiments, we estimated oxygen consumption of the mesozooplankton community obtained in Bay of Mejillones, northern Chile (23°S) in May 2010, December 2010 and August 2011. Mass-specific respiration rates were in the range of 8.2-24.5 μmol O2 mg dry mass- 1 day- 1, at an average temperature of 12 °C. Estimates of the mesozooplankton biomass in the water column indicated that its aerobic respiration may remove daily a maximum of about 20% of oxygen available at the base of the oxycline. Since previous work indicates that zooplankton aggregate near the base of the oxycline, the impact of aerobic respiration on oxygen content might be even stronger at this depth. Mesozooplankton respiration, along with community respiration by microorganisms near the base of the oxycline and a strongly stratified condition (limiting vertical flux of O2), are suggested as being critical factors causing and maintaining a persistent subsurface oxygen-deficient ecological barrier (BEDOX) in the upwelling zone. This BEDOX layer can have a major role in affecting and regulating zooplankton distribution and their dynamics in the highly productive coastal upwelling zone of the Humboldt Current System.

  20. 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.

  1. 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

  2. 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.

  3. 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

    2016-01-01

    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.

  4. Ferroelectric-to-Relaxor Crossover and Oxygen Vacancy Hopping in Compositionally-Disordered Perovskites - KtA(1-x)Nb(x)O(3):Ca

    SciTech Connect

    Samara, G.A.; Boatner, L.A.

    1999-07-26

    It is shown that lattice disorder induced by Nb and Ca substitution has a strong influence on the dielectric and relaxational properties of KTaO{sub 3}. Both substituents are believed to occupy off-center positions at the Ta site, and the difference in valence between the Ca{sup 2+} and Ta{sup 5+} ions leads to the formation of oxygen vacancies (V{sub 0}). Specifically, for a KTa{sub 1{minus}x}Nb{sub x}O{sub 3}:Ca crystal with x = 0.023 and with a 0.055 at.% Ca doping they observe: (1) a ferroelectric transition at atmospheric pressure (1 bar); (2) a large enhancement of the transition temperature by Ca doping; (3) a pressure-induced crossover from ferroelectric-to-relaxor behavior; (4) the impending vanishing of the relaxor phase at high pressure; (5) the reorientation of the Ca-oxygen vacancy (Ca:V{sub 0}) pair defect; and (6) the variation of the energetics and dynamics of this reorientation with pressure. Most of these effects are associated with Nb- and Ca-induced dipolar entities and appear to be general features of soft mode ferroelectrics with random-site polar nanodomains. The ferroelectric-to-relaxor crossover can be understood in terms of a large decrease with pressure in the correlation length among polar nanodomains--a unique property of soft ferroelectric mode systems.

  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. Molecular Diversity of Denitrifying Genes in Continental Margin Sediments within the Oxygen-Deficient Zone off the Pacific Coast of Mexico

    PubMed Central

    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

    2003-01-01

    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. PMID:12788762

  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. 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.

  9. Recent advances of lanthanum-based perovskite oxides for catalysis

    DOE PAGESBeta

    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

  10. Perovskite ferroelectric nanomaterials

    NASA Astrophysics Data System (ADS)

    Nuraje, Nurxat; Su, Kai

    2013-09-01

    In this review, the main concept of ferroelectricity of perovskite oxides and related materials at nanometer scale and existing difficulties in the synthesis of those nanocrystals are discussed. Important effects, such as depolarization field and size effect, on the existence of ferroelectricity in perovskite nanocrystals are deliberated. In the discussion of modeling works, different theoretical calculations are pinpointed focusing on their studies of lattice dynamics, phase transitions, new origin of ferroelectricity in nanostructures, etc. As the major part of this review, recent research progress in the facile synthesis, characterization and various applications of perovskite ferroelectric nanomaterials, such as BaTiO3, PbTiO3, PbZrO3, and BiFeO3, are also scrutinized. Perspectives concerning the future direction of ferroelectric nanomaterials research and its potential applications in renewable energy, etc., are presented. This review provides an overview in this area and guidance for further studies in perovskite ferroelectric nanomaterials and their applications.In this review, the main concept of ferroelectricity of perovskite oxides and related materials at nanometer scale and existing difficulties in the synthesis of those nanocrystals are discussed. Important effects, such as depolarization field and size effect, on the existence of ferroelectricity in perovskite nanocrystals are deliberated. In the discussion of modeling works, different theoretical calculations are pinpointed focusing on their studies of lattice dynamics, phase transitions, new origin of ferroelectricity in nanostructures, etc. As the major part of this review, recent research progress in the facile synthesis, characterization and various applications of perovskite ferroelectric nanomaterials, such as BaTiO3, PbTiO3, PbZrO3, and BiFeO3, are also scrutinized. Perspectives concerning the future direction of ferroelectric nanomaterials research and its potential applications in renewable

  11. Intact polar lipids of Thaumarchaeota and anammox bacteria as indicators of N-cycling in the Eastern Tropical North Pacific oxygen deficient zone

    NASA Astrophysics Data System (ADS)

    Sollai, M.; Hopmans, E. C.; Schouten, S.; Keil, R. G.; Sinninghe Damsté, J. S.

    2015-03-01

    In the last decade our understanding of the marine nitrogen cycle has improved considerably thanks to the discovery of two novel groups of microorganisms: ammonia-oxidizing archaea (AOA) and anaerobic ammonia-oxidizing (anammox) bacteria. Both groups are important in oxygen deficient zones (ODZs), where they substantially affect the marine N-budget. These two groups of microbes are also well known for producing specific membrane lipids, which can be used as biomarkers to trace their presence in the environment. We investigated the occurrence and distribution of AOA and anammox bacteria in the water column of the Eastern Tropical North Pacific (ETNP) ODZ, one of the most prominent ODZs worldwide. Suspended particulate matter (SPM) was collected at different depths of the water column in high resolution, at both a coastal and an open ocean setting. The SPM was analyzed for AOA- and anammox bacteria-specific intact polar lipids (IPLs), i.e. hexose-phosphohexose (HPH)-crenarchaeol and phosphatidylcholine (PC)-monoether ladderane. Comparison with oxygen profiles reveals that both the microbial groups are able to thrive at low (<1 μM) concentrations of oxygen. Our results indicate a clear niche segregation of AOA and anammox bacteria in the coastal waters of the ETNP, but a partial overlap of the two niches of these microbial species in the open water setting. The latter distribution suggests the potential for an interaction between the two microbial groups at the open ocean site, either as competition or cooperation.

  12. 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.

  13. 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. PMID:27127984

  14. Iron deficiency.

    PubMed

    Scrimshaw, N S

    1991-10-01

    The world's leading nutritional problem is iron deficiency. 66% of children and women aged 15-44 years in developing countries have it. Further, 10-20% of women of childbearing age in developed countries are anemic. Iron deficiency is identified with often irreversible impairment of a child's learning ability. It is also associated with low capacity for adults to work which reduces productivity. In addition, it impairs the immune system which reduces the body's ability to fight infection. Iron deficiency also lowers the metabolic rate and the body temperature when exposed to cold. Hemoglobin contains nearly 73% of the body's iron. This iron is always being recycled as more red blood cells are made. The rest of the needed iron does important tasks for the body, such as binds to molecules that are reservoirs of oxygen for muscle cells. This iron comes from our diet, especially meat. Even though some plants, such as spinach, are high in iron, the body can only absorb 1.4-7% of the iron in plants whereas it can absorb 20% of the iron in red meat. In many developing countries, the common vegetarian diets contribute to high rates of iron deficiency. Parasitic diseases and abnormal uterine bleeding also promote iron deficiency. Iron therapy in anemic children can often, but not always, improve behavior and cognitive performance. Iron deficiency during pregnancy often contributes to maternal and perinatal mortality. Yet treatment, if given to a child in time, can lead to normal growth and hinder infections. However, excess iron can be damaging. Too much supplemental iron in a malnourished child promotes fatal infections since the excess iron is available for the pathogens use. Many countries do not have an effective system for diagnosing, treating, and preventing iron deficiency. Therefore a concerted international effort is needed to eliminate iron deficiency in the world.

  15. In situ observation of oxygen deficiency occurring during electron irradiation in high Tc superconductor YBa2Cu3Oy.

    PubMed

    Akase, Z; Tomokiyo, Y; Watanabe, M

    2001-07-01

    The decreasing process of oxygen in YBa2Cu3Oy is investigated through high resolution electron microscopy (HREM) and convergent beam electron diffraction (CBED). Measurements of the axial length in HREM images show that oxygen content y decreases faster near a twin boundary than at the inner part of a twin lamella. The transformation from an orthorhombic to a tetragonal phase starts at a twin boundary and the transformed region propagates to an inner region of lamella. Lattice strains are observed near boundaries between transformed and non-transformed regions. The transformation is almost complete within 30 s during observation of HREM images at 400 kV and at room temperature. A value of y was quantitatively measured by analysing observed intensities of energy-filtered CBED patterns with the dynamical theory. The value of y decreases from 6.9 to 6.5 when 200 kV electrons are irradiated for 160 s in a microscope at 108 K. More precise analysis of the intensities provides information on charge distribution along the c-axis as well as local oxygen content at a spatial resolution of several nanometres. PMID:11454148

  16. Perovskite solid electrolytes for SOFC

    SciTech Connect

    Sammells, A.F.

    1992-09-01

    Selected perovskite solid electrolytes incorporated into research size fuel cells have shown stability for > 4000 hours at 600{degrees}C. Perovskite lattice requirements which favor low E{sub a} for ionic conduction include (i) that the perovskite lattice possess a moderate enthalpy of formation, (ii) perovskite lattice possess large free volumes, (iii) that the lattice minimally polarizes the mobile ion and (iv) that the crystallographic saddle point r{sub c} for ionic conduction is {approx_equal} 1.

  17. Perovskite solid electrolytes for SOFC

    SciTech Connect

    Sammells, A.F.

    1992-01-01

    Selected perovskite solid electrolytes incorporated into research size fuel cells have shown stability for > 4000 hours at 600{degrees}C. Perovskite lattice requirements which favor low E{sub a} for ionic conduction include (i) that the perovskite lattice possess a moderate enthalpy of formation, (ii) perovskite lattice possess large free volumes, (iii) that the lattice minimally polarizes the mobile ion and (iv) that the crystallographic saddle point r{sub c} for ionic conduction is {approx equal} 1.

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. 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

  3. H2S Reactivity on Oxygen-Deficient Heterotrimetallic Cores: Cluster Fluxionality Simulates Dynamic Aspects of Surface Chemical Reactions.

    PubMed

    Adhikari, Debashis; Raghavachari, Krishnan

    2016-01-28

    Understanding the mechanistic aspects of heterogeneous reactions on supported metal catalysts is challenging due to several disparate factors, among which the dynamic nature of the surface is a major contributor. In this study, the dynamic aspect of a surface has been probed by choosing small metal clusters as illustrative models. Two anionic hetero-trimetallic clusters, namely, W2TcO6(-) and W2OsO6(-), were reacted with H2S gas to exhibit splitting of the gas molecule and complete oxygen-sulfur exchange in the metal core. During this atom-exchange process, the core exhibits remarkable fluxionality to augment a thiol proton migration from one metal center to another, as well as a rapid interchange of the terminal and bridging oxygens. The fluxional nature of the core is further evidenced by two oppositely oriented oxo groups working in concert to accomplish the proton transfer, upon introduction of sulfur inside the core. These fluxional processes in the small hetero-trimetallic cores closely resemble the dynamic nature of the surface in a heterogeneous reaction. Throughout the fluxional processes investigated in this study, two-state reactivity and multiple instances of spin crossover are observed in our computational studies. Interestingly, the neutral hetero-trimetallic cores can also undergo complete oxygen-sulfur exchange reaction with H2S. The investigated metal clusters are promising materials, since they not only can liberate dihydrogen from water (reported in J. Phys. Chem. A, 2014, 118, 11047) but also can completely strip the sulfur from environmentally hazardous H2S gas.

  4. 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

  5. Vortex Phase Diagram as a Function of Oxygen Deficiency in Untwinned YBa_2Cu_3O_y

    NASA Astrophysics Data System (ADS)

    Nishizaki, Terukazu

    2000-03-01

    This talk will present recent results of the vortex phase diagram of untwinned YBa2Cu3Oy (YBCO) single crystals with a different oxygen content under high magnetic fields up to 30T. We show that the first-order vortex lattice melting line T_m(H) and the second-order vortex glass transition line T_g(H) terminate at the critical point H_cp and the field-driven disordering transition line separates the vortex solid phase into the Bragg glass and the vortex glass phases(T. Nishizaki et al., Phys. Rev. B 58, 11169 (1998).). The value of H_cp strongly depends on the oxygen content and the vortex lattice melting transition is observed up to 30 T for fully oxidized YBCO (y~=7, T_c~=87.5 K). For optimally doped YBCO (T_c~= 93 K), on the other hand, T_g(H) decreases with increasing temperature and approaches to the vortex lattice melting line well below the critical point of T_m(H), indicating the existence of the new vortex state such as a vortex slush regime between T_g(H) and T_m(H). Thermodynamic properties are also examined above and below the terminal point of T_g(H). We find that the entropy change at the first-order melting transition becomes considerably small above the terminal field of T_g(H). The novel vortex phase diagram is discussed.

  6. 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

  7. Intact polar lipids of Thaumarchaeota and anammox bacteria as indicators of N cycling in the eastern tropical North Pacific oxygen-deficient zone

    NASA Astrophysics Data System (ADS)

    Sollai, M.; Hopmans, E. C.; Schouten, S.; Keil, R. G.; Sinninghe Damsté, J. S.

    2015-08-01

    In the last decade our understanding of the marine nitrogen cycle has improved considerably thanks to the discovery of two novel groups of microorganisms: ammonia-oxidizing archaea (AOA) and anaerobic ammonia-oxidizing (anammox) bacteria. Both groups are important in oxygen-deficient zones (ODZs), where they substantially affect the marine N budget. These two groups of microbes are also well known for producing specific membrane lipids, which can be used as biomarkers to trace their presence in the environment. We investigated the occurrence and distribution of AOA and anammox bacteria in the water column of the eastern tropical North Pacific (ETNP) ODZ, one of the most prominent ODZs worldwide. Suspended particulate matter (SPM) was collected at different depths of the water column in high resolution, at both a coastal and an open-ocean setting. The SPM was analyzed for AOA- and anammox bacteria-specific intact polar lipids (IPLs), i.e., hexose-phosphohexose (HPH)-crenarchaeol and phosphatidylcholine (PC)-monoether ladderane. Comparison with oxygen profiles reveals that both the microbial groups are able to thrive at low (< 1 μM) concentrations of oxygen. Our results indicate a clear niche segregation of AOA and anammox bacteria in the coastal waters of the ETNP but a partial overlap of the two niches of these microbial species in the open-water setting. The latter distribution suggests the potential for an interaction between the two microbial groups at the open-ocean site, although the nature of this hypothetical interaction (i.e., either competition or cooperation) remains unclear.

  8. 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.

  9. 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

  10. 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.

  11. Electronic structure and magnetic properties of oxygen deficient low-index surfaces of SnO2

    NASA Astrophysics Data System (ADS)

    Han, Ruilin; Yan, Yu

    2016-07-01

    In order to elucidate the origin of the observed ferromagnetism in SnO2 nano-particles and films, we systematically investigate the electronic structure and magnetic properties of the reduced (110), (100) and (101) surfaces of SnO2 and study the role of singly charged oxygen vacancy (VO1 +) at (110), (100), (101) and (001) surfaces on the electronic structure and magnetic properties of SnO2 by using first-principles calculation. The results show that the stable reduced (110), (100) and (101) surfaces of SnO2 are nonmagnetic, which is similar to early published results, where one neutral O vacancy at the low-index surfaces of SnO2 produce spin non-splitting defect states. By contrast, although VO1 + at the (110), (100) and (101) surfaces of SnO2 do not induce the magnetism, VO1 + at the (001) surface of SnO2 induce magnetic moment, which mainly originate from partially filled 5p orbitals of the reduced Sn atom and partially filled 2p orbitals of the O atoms around the reduced Sn atom. More importantly, the magnetic coupling between moments induced by two VO1 + at the (001) surface of SnO2 is ferromagnetic, and this coupling can be attributed to the p-p hybridization interaction involving polarized electrons. The last result supports the experimental evidence that the observed ferromagnetism in undoped SnO2 originate from VO1 + at the surfaces.

  12. 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.

  13. 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

  14. Rapid Synthesis of Thin and Long Mo17O47 Nanowire-Arrays in an Oxygen Deficient Flame.

    PubMed

    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

  15. TLR2/4 deficiency prevents oxygen-induced vascular degeneration and promotes revascularization by downregulating IL-17 in the retina

    PubMed Central

    He, Chang; Lai, Peilong; Wang, Jing; Zhou, Tian; Huang, Zijing; Zhou, Lingli; Liu, Xialin

    2016-01-01

    Vascular degeneration is a critical pathological process in many human degenerative diseases, which need efficient ways to revascularization. However, little is known about cellular and molecular mechanisms that are used during vascular degeneration and revascularization. Here, we show that Toll-like receptor 2 and 4 (TLR2/4) double deficiency suppressed hyperoxia induced retinal vessel regression in an oxygen-induced retinopathy (OIR) model. Notably, the TLR2/4−/− mice experienced more revascularization after reduced vessel regression compared with wild-type mice, accompanied with less activation of glial cells. Mechanistically, TLR2/4 activation can tip the balance between Th17 cells and regulatory T cells towards Th17 cells, a critical source of the IL-17A. Less migration and infiltration of IL-17A-expressing proinflammatory cells but elevated regulatory T cells were observed in OIR-retinae from TLR2/4−/− mice. Coincidentally, TLR2/4 deficiency suppressed IL-17A production and increased expressions of anti-inflammatory genes. Furthermore, IL-17A promoted activation of glial cells. IL-17A blockade using a neutralizing antibody alleviated retinal cell apoptosis and glial activation in C57/B6-OIR mice, demonstrating the important role of IL-17A pathway in glial function during revascularization. Thus TLR2/4-mediated IL-17A inflammatory signaling is involved in vessel degeneration and revascularization, indicating that modulation of the TLR2/4-IL-17A pathway may be a novel therapeutic strategy for degenerative diseases. PMID:27297042

  16. 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

  17. 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.

  18. 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.

  19. 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

  20. 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

    2015-01-01

    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

  1. 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.

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. 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. PMID:24943986

  7. 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.

  8. 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.

  9. Atomic and electronic structures of single-layer FeSe on SrTiO3(001): The role of oxygen deficiency

    DOE PAGESBeta

    Bang, Junhyeok; Li, Zhi; Sun, Y. Y.; Samanta, Amit; Zhang, Y. Y.; Zhang, Wenhao; Wang, Lili; Chen, X.; Ma, Xucun; Xue, Q.-K.; et al

    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

  10. Alloy B-10, a new nickel-based alloy for strong chloride-containing, highly acidic and oxygen-deficient environments

    SciTech Connect

    Kohler, M.; Kirchheiner, R.; Stenner, F.

    1998-12-31

    Alloy B-10 is a Ni-Mo-Cr alloy, recently developed for highly acidic but oxygen-deficient environments in the chemical process and environmental protection industries. The new nickel-based alloy with nominally (wt. %) 62 Ni, 24 MO, 8 Cr and 6 Fe, exhibits excellent corrosion resistance in intermediate concentrations of sulfuric acid, as well as in hydrochloric acid, even with additions of small amounts of oxidizing agents. In a simulated Flue Gas Desulfurization (FGD) environment of sulfuric acid of pH 1 with additions of 7% chloride and 0.01% fluoride, and also containing 15% gypsum the new alloy demonstrated high crevice corrosion resistance at 100 C, whereas a common Ni-Cr-Mo alloy of the C-type suffers crevice corrosion under the same conditions. This new alloy can easily be welded without filler or using matching filler. Good practical experience has been gained with Alloy B-10 in a district heating power station as a tube sheet and bottom wall liner for a glass tube heat exchanger working at 130 C with condensing 70% sulfuric acid.

  11. Understanding the Oxygen Vacancy in Tungsten Trioxide

    NASA Astrophysics Data System (ADS)

    Wang, Wennie; Janotti, Anderson; van de Walle, Chris G.

    2015-03-01

    Tungsten trioxide (WO3) has a variety of applications in gas sensors, photocatalysis, and smart windows. As an electrochromic BO3 perovskite, WO3 turns from transparent to blue upon doping. This color change is correlated with a drop in transmittance of near-IR radiation, and is used in smart windows for energy efficiency. In addition to monovalent species doping that modulates optical properties, oxygen deficiencies have been found to have a similar electrochromic effect. The influence of oxygen vacancies on electronic structure and how it corresponds to electrochromic behavior remains a topic of debate. In this work, we examine the oxygen vacancy in monoclinic WO3 and its influence on electronic structure using density functional theory with a hybrid functional. We investigate the relative stability of different charge states and its implications for electrical properties, such as conductivity and electrochromism. We find oxygen vacancies to be shallow donors, and explore similarities and differences with monovalent species doping. Finally, we compare our theoretical findings with experiment to elucidate how vacancies may contribute to electrochromic behavior. This work is supported by DOE and NSF.

  12. 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

  13. Atomistic mechanism leading to complex antiferroelectric and incommensurate perovskites

    NASA Astrophysics Data System (ADS)

    Patel, Kinnary; Prosandeev, Sergey; Yang, Yurong; Xu, Bin; Íñiguez, Jorge; Bellaiche, L.

    2016-08-01

    An atomic interaction is identified in all perovskite compounds, such as A B O3 oxides, that can potentially result in unconventional structures. The term is harmonic in nature and couples the motions of the A cations with the rotations of the oxygen octahedra in the perovskite lattice. When strong enough, this coupling leads to hybrid normal modes that present both (anti)polar and rotational characters, which are keys to understand a variety of exotic phases. For example, we show that not only does this new coupling explain the long-period soft phonons characterizing prototype antiferroelectric PbZrO3, but it also provides us with an unified description of the complex antipolar structures of a variety of perovskites, including the possible occurrence of incommensurate phases. This coupling is further demonstrated to result, in the continuum limit, in an energy invariant adopting an analytical form that has been previously overlooked, to the best of our knowledge.

  14. 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.

  15. 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.

  16. Crystal Structure of a Layered Perovskite Niobate KCa 2Nb 3O 10

    NASA Astrophysics Data System (ADS)

    Fukuoka, Hiroshi; Isami, Toshiyuki; Yamanaka, Shoji

    2000-04-01

    The crystal structure of a layered perovskite niobate KCa2Nb3O10 was investigated through single-crystal X-ray analysis. The niobate crystallized in the orthorhombic system Cmcm with lattice constants of a=3.8802(9) Å, b=29.508(6) Å, c=7.714(1) Å, V=883.2(2) Å3. The final refinement using the 908 independent reflections converged into R=4.1%, and Rw=4.7%. The structure of KCa2Nb3O10 was composed of triple-layered perovskite slabs, potassium ions being situated between the slabs. The adjacent perovskite slabs, stacking along the c axis, were mutually displaced with a displacement vector of a→/2. The potassium ions were coordinated by six oxygen atoms to form two short and four long bonds. Apparent disordering was observed in the equatorial oxygen sites of the central niobium atoms in the triple perovskite slabs.

  17. 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.

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. Perovskite electrodes and method of making the same

    SciTech Connect

    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.

  5. 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.

  6. The contrasting effect of the Ta/Nb ratio in (111)-layered B-site deficient hexagonal perovskite Ba5Nb4-xTaxO15 crystals on visible-light-induced photocatalytic water oxidation activity of their oxynitride derivatives.

    PubMed

    Hojamberdiev, Mirabbos; Bekheet, Maged F; Zahedi, Ehsan; Wagata, Hajime; Vequizo, Junie Jhon M; Yamakata, Akira; Yubuta, Kunio; Gurlo, Aleksander; Domen, Kazunari; Teshima, Katsuya

    2016-08-01

    The effect of the Ta/Nb ratio in the (111)-layered B-site deficient hexagonal perovskite Ba5Nb4-xTaxO15 (0 ≤ x ≤ 4) crystals grown by a KCl flux method on visible-light-induced photocatalytic water oxidation activity of their oxynitride derivatives BaNb1-xTaxO2N (0 ≤ x ≤ 1) was investigated. The Rietveld refinement of X-ray data revealed that all Ba5Nb4-xTaxO15 samples were well crystallized in the space group P3[combining macron]m1 (no. 164). Phase-pure BaNb1-xTaxO2N (0 ≤ x ≤ 1) porous structures were obtained by nitridation of the flux-grown oxide crystals at 950 °C for 20, 25, 30, 35, and 40 h, respectively. The absorption edge of BaNb1-xTaxO2N (0 ≤ x ≤ 1) was slightly shifted from 720 to 690 nm with the increasing Ta/Nb ratio. The O2 evolution rate gradually progressed and reached the highest value (127.24 μmol in the first 2 h) with the Ta content up to 50 mol% but decreased at 75 and 100 mol% presumably due to the reduced specific surface area and high density of structural defects, such as grain boundaries acting as recombination centers, originated from high-temperature nitridation for prolonged periods. Transient absorption spectroscopy provided evidence for the effect of the Ta/Nb ratio on the behavior and energy states of photogenerated charge carriers, indicating a direct correlation with photocatalytic water oxidation activity of BaNb1-xTaxO2N. PMID:27437784

  7. 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.

  8. 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.

  9. 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.

  10. 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

  11. 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

  12. Controlling octahedral rotations in a perovskite via strain doping

    DOE PAGESBeta

    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 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

  13. 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.

  14. 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.

  15. 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.

  16. 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

    2014-03-01

    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. PMID:24448203

  17. Organometal Trihalide Perovskite Spintronics

    NASA Astrophysics Data System (ADS)

    Sun, Dali

    The family of organometal trihalide perovskite (OTP), CH3NH3PbX3 (where X is halogen) has recently revolutionized the photovoltaics field, and shows promise in applications such as solar energy harnessing, light emitting diodes, field effect transistors and laser action. The OTP spin characteristic properties are influenced by the large spin-orbit-coupling of the Pb atoms, and thus may offer a new class of semiconductors for spin-based applications. In this talk we will summarize the `magnetic field effect' on photocurrent and electroluminescence in OTP optoelectronic devices, and photoluminescence from OTP films; and report more recent studies of pure spin-current and spin-aligned carrier injection in OTP spintronics devices using `spin-pumping' and `spin-injection', respectively. We measured relatively large inverse-spin-Hall effect using pulsed microwave excitation in OTP devices at resonance with a ferromagnetic (FM) layer, and giant magnetoresistance in OTP-based spin-valves. Our studies launch the field of OTP spintronics. Research sponsored by the DOE, Office of Science, Grant DE-SC0014579. Work done in collaboration with Chuang Zhang, Marzieh Kavand, Kipp J. van Schooten, Hans Malissa, Matthew Groesbeck, Ryan Mclaughlin, Christoph Boehme, and Z. Valy Vardeny.

  18. 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

  19. 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

    2016-07-01

    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

  20. Magnetic susceptibility anisotropy of grain-aligned oxygen-deficient Y 1Ba 2Cu 3O x (6.46⪕ x⪕6.98)

    NASA Astrophysics Data System (ADS)

    Lee, Moohee; Tea, N.; Song, Y.-Q.; Halperin, W. P.; Thiel, J.; Kennard, M. A.; Poeppelmeier, K. R.; Fang, M. M.; Welp, U.

    1992-10-01

    The anisotropic susceptibility of YBa 2Cu 3O x (6.46⪕ x⪕6.98) has been measured as a function of oxygen composition. Samples were prepared by a high temperature zirconium-getter annealing technique followed by magnetic orientation in epoxy. The normal state magnetic susceptibility was found to be weakly dependent on temperature. The room temperature values of the susceptibility decrease linearly as the oxygen composition decreases, whereas the difference in susceptibilities for magnetic fields parallel and perpendicular to the c-axis is nearly constant. This suggests that in this range of oxygen composition the susceptibility anisotropy comes mostly from the anisotropic part of the Van Vleck susceptibility and the spin susceptibility remains nearly isotropic. Neutron diffraction results show a significant oxygen occupancy at the O(5) site. Nuclear quadrupolar and magnetic resonance spectra of the plane copper indicate a marked degree of electronic disorder, confirming that there are microscopic structural effects from the high temperature zirconium-getter annealing procedure.

  1. 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.

  2. 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

  3. 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

  4. 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.

  5. 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

  6. Iridium-based double perovskites for efficient water oxidation in acid media.

    PubMed

    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

  7. Perovskite catalysts for oxidative coupling

    DOEpatents

    Campbell, K.D.

    1991-06-25

    Perovskites of the structure A[sub 2]B[sub 2]C[sub 3]O[sub 10] are useful as catalysts for the oxidative coupling of lower alkane to heavier hydrocarbons. A is alkali metal; B is lanthanide or lanthanum, cerium, neodymium, samarium, praseodymium, gadolinium or dysprosium; and C is titanium.

  8. Perovskite catalysts for oxidative coupling

    DOEpatents

    Campbell, Kenneth D.

    1991-01-01

    Perovskites of the structure A.sub.2 B.sub.2 C.sub.3 O.sub.10 are useful as catalysts for the oxidative coupling of lower alkane to heavier hydrocarbons. A is alkali metal; B is lanthanide or lanthanum, cerium, neodymium, samarium, praseodymium, gadolinium or dysprosium; and C is titanium.

  9. Oxygen safety

    MedlinePlus

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

  10. Stabilization of oxygen-deficient structure for conducting Li4Ti5O12-δ by molybdenum doping in a reducing atmosphere.

    PubMed

    Song, Hannah; Jeong, Tae-Gyung; Moon, Young Hoon; Chun, Ho-Hwan; Chung, Kyung Yoon; Kim, Hyung Sun; Cho, Byung Won; Kim, Yong-Tae

    2014-03-12

    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 Mo(6+) 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.

  11. 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. PMID:27478742

  12. 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.

  13. Photoluminescence characterisations of a dynamic aging process of organic-inorganic CH3NH3PbBr3 perovskite.

    PubMed

    Sheng, R; Wen, X; Huang, S; Hao, X; Chen, S; Jiang, Y; Deng, X; Green, M A; Ho-Baillie, A W Y

    2016-01-28

    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. PMID:26753563

  14. 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.

  15. 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

  16. Stability limits of the perovskite structure in the Y-Ba-Cu-O system

    NASA Astrophysics Data System (ADS)

    Bormann, R.; Nölting, J.

    1989-05-01

    The equilibrium (molecular) oxygen partial pressure of the Y1Ba2Cu3O7-x phase has been measured by an electrochemical method. The investigations are focused on the low-temperature range between 560 and 750 °C and on oxygen stoichiometries close to the oxygen-poor phase boundary. In particular, the oxygen partial pressure has been determined below which the perovskite structure becomes thermodynamically unstable. This critical value should be considered during the preparation of high Tc Y1Ba2Cu3O7-x superconductors, especially in the case of an in situ preparation of thin films.

  17. Electrochemical properties of mixed conducting (La,M)(CoFe) oxide perovskites (M=3DSr, Ca, and Ba)

    SciTech Connect

    Stevenson, J.W.; Armstrong, T.R.; Bates, J.L.

    1996-04-01

    Electrical properties and oxygen permeation properties of solid mixed-conducting electrolytes (La,M)(CoFe) oxide perovskites (M=3DSr, Ca, and Ba) have been characterized. These materials are potentially useful as passive membranes to separate high purity oxygen from air and as the cathode in a fuel cell. Dilatometric linear expansion measurements were performed as a function of temperature and oxygen partial pressure to evaluate the stability.

  18. High-efficiency perovskite solar cells with long operation lifetime (Presentation Recording)

    NASA Astrophysics Data System (ADS)

    Yang, Chenchen; Cao, Weiran; Shewmon, Nathan T.; Xue, Jiangeng

    2015-10-01

    Perovskite solar cells have attracted tremendous attention for their outstanding energy conversion efficiency in the past few years. Due to the development of active materials, device architectures and processing methods, power conversion efficiency (PCE) of perovskite solar cells is now growing up to 20%. Beyond the efficiency, to get rid of Lead, the widely-used toxic element in the perovskite layers, as well as to improve the device/module operation lifetime are the other two major challenges that need to be solved before their commercialization. Here, we apply a layer of ZnO nanoparticles onto to a planar perovskite solar cell, which can not only improve the electron transport/extraction in the devices but highly improve the device operation lifetime. The devices were fabricated by spin-coating a poly(3,4-ethylenedioxythuiphene):polystyrene sulfonate (PEDOT:PSS) layer onto a glass/ITO substrate, followed by the deposition of a perovskite layer from a lead chloride (PbCl2) and methyl ammonium iodine (MAI) blend precursor solution. After that, a layer of [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) and a layer of ZnO nanoparticles were successively deposited as the electron transport layers, and the device was finished by thermally evaporation Al as the cathode. Such planar perovskite solar cell with ZnO NPs exhibits a maximum PCE of up to 14.1%, which is about 35% higher than that without the ZnO layer. Moreover, the device remains 80% of its initial PCE after 2500 hours under 1 sum illumination, majorly due to the protection of ZnO layer that prevent the diffusion of oxygen and moisture molecules into the perovskite layers as revealed by x-ray photoelectron spectroscopy studies.

  19. Influence of tungsten substitution and oxygen deficiency on the thermoelectric properties of CaMnO{sub 3−δ}

    SciTech Connect

    Thiel, Philipp; Eilertsen, James; Populoh, Sascha Saucke, Gesine; Shkabko, Andrey; Sagarna, Leyre; Karvonen, Lassi; Döbeli, Max; Weidenkaff, Anke

    2013-12-28

    Polycrystalline tungsten-substituted CaMn{sub 1−x}W{sub x}O{sub 3−δ} (0.00 ≤ x ≤ 0.05) powders were synthesized from a polymeric precursor, pressed and sintered to high density. The impact of tungsten substitution on the crystal structure, thermal stability, phase transition, electronic and thermal transport properties is assessed. Tungsten acts as an electron donator and strongly affects high-temperature oxygen stoichiometry. Oxygen vacancies form in the high figure-of-merit (ZT)-region starting from about T = 1000 K and dominate the carrier concentration and electronic transport far more than the tungsten substitution. The analysis of the transport properties yields that in the investigated regime the band filling is sufficiently high to overcome barriers of polaron transport. Therefore, the Cutler-Mott approach describes the electrical transport more accurately than the Mott approach for small polaron transport. The lattice thermal conductivity near room temperature is strongly suppressed with increasing tungsten concentration due to mass-difference impurity scattering. A ZT of 0.25 was found for x = 0.04 at 1225 K.

  20. Surface-disordered and oxygen-deficient LiTi2-xMnx(PO4-y)3 nanoparticles for enhanced lithium-ion storage

    NASA Astrophysics Data System (ADS)

    Jiang, Xiaolei; Xu, Huayun; Mao, Hongzhi; Yang, Jian; Qian, Yitai

    2016-07-01

    Disordered surface of anode materials accompanied by oxygen vacancies, has been developed as an efficient strategy to promote their charge-transfer kinetics and then improve their electrochemical properties. It is rarely explored for cathode materials before. Here, LiTi2-xMnx(PO4-y)3 nanoparticles with a disordered surface and oxygen vacancies, are synthesized by a hydrothermal method following with an annealing in Ar/H2. Their disordered surface and heteroatom doping by reduced Mn/Ti species, have been supported by HRTEM images, XPS and EDS spectra. After 120 cycles at 0.2 C, these nanoparticles still deliver a capacity of 127 mAh g-1, much higher than the product without any doping, and that without a disordered surface. Even after 500 cycles, the capacity is still at 101 mAh g-1 for 5 C or at 71 mAh g-1 for 20 C. These results could be attributed to the reduced charge-transfer resistance caused by disordered surface, and the enhanced lithium-diffusion induced by doping.

  1. Multiferroic crossover in perovskite oxides

    NASA Astrophysics Data System (ADS)

    Weston, L.; Cui, X. Y.; Ringer, S. P.; Stampfl, C.

    2016-04-01

    The coexistence of ferroelectricity and magnetism in A B O3 perovskite oxides is rare, a phenomenon that has become known as the ferroelectric "d0 rule." Recently, the perovskite BiCoO3 has been shown experimentally to be isostructural with PbTiO3, while simultaneously the d6Co3 + ion has a high-spin ground state with C -type antiferromagnetic ordering. It has been suggested that the hybridization of Bi 6 s states with the O 2 p valence band stabilizes the polar phase, however, we have recently demonstrated that Co3 + ions in the perovskite structure can facilitate a ferroelectric distortion via the Co 3 d -O 2 p covalent interaction [L. Weston, et al., Phys. Rev. Lett. 114, 247601 (2015), 10.1103/PhysRevLett.114.247601]. In this paper, using accurate hybrid density functional calculations, we investigate the atomic, electronic, and magnetic structure of BiCoO3 to elucidate the origin of the multiferroic state. To begin with, we perform a more general first-principles investigation of the role of d electrons in affecting the tendency for perovskite materials to exhibit a ferroelectric distortion; this is achieved via a qualitative trend study in artificial cubic and tetragonal La B O3 perovskites. We choose La as the A cation so as to remove the effects of Bi 6 s hybridization. The lattice instability is identified by the softening of phonon modes in the cubic phase, as well as by the energy lowering associated with a ferroelectric distortion. For the La B O3 series, where B is a d0-d8 cation from the 3 d block, the trend study reveals that increasing the d orbital occupation initially removes the tendency for a polar distortion, as expected. However, for high-spin d5-d7 and d8 cations a strong ferroelectric instability is recovered. This effect is explained in terms of increased pseudo-Jahn-Teller (PJT) p -d vibronic coupling. The PJT effect is described by the competition between a stabilizing force (K0) that favors the cubic phase, and a vibronic term that

  2. Dynamics in oxygen-induced changes in S-layer protein synthesis from Bacillus stearothermophilus PV72 and the S-layer-deficient variant T5 in continuous culture and studies of the cell wall composition.

    PubMed Central

    Sára, M; Kuen, B; Mayer, H F; Mandl, F; Schuster, K C; Sleytr, U B

    1996-01-01

    Stable synthesis of the hexagonally ordered (p6) S-layer protein from the wild-type strain of Bacillus stearothermophilus PV72 could be achieved in continuous culture on complex medium only under oxygen-limited conditions when glucose was used as the sole carbon source. Depending on the adaptation of the wild-type strain to low oxygen supply, the dynamics in oxygen-induced changes in S-layer protein synthesis was different when the rate of aeration was increased to a level that allowed dissimilation of amino acids. If oxygen supply was increased at the beginning of continuous culture, synthesis of the p6 S-layer protein from the wild-type strain (encoded by the sbsA gene) was immediately stopped and replaced by that of a new type of S-layer protein (encoded by the sbsB gene) which assembled into an oblique (p2) lattice. In cells adapted to a prolonged low oxygen supply, first, low-level p2 S-layer protein synthesis and second, synchronous synthesis of comparable amounts of both types of S-layer proteins could be induced by stepwise increasing the rate of aeration. The time course of changes in S-layer protein synthesis was followed up by immunogold labelling of whole cells. Synthesis of the p2 S-layer protein could also be induced in the p6-deficient variant T5. Hybridization data obtained by applying the radiolabelled N-terminal and C-terminal sbsA fragments and the N-terminal sbsB fragment to the genomic DNA of all the three organisms indicated that changes in S-layer protein synthesis were accompanied by chromosomal rearrangement. Chemical analysis of peptidoglycan-containing sacculi and extraction and recrystallization experiments revealed that at least for the wild-type strain, a cell wall polymer consisting of N-acetylglucosamine and glucose is responsible for binding of the p6 S-layer protein to the rigid cell wall layer. PMID:8606191

  3. Research Update: Strategies for improving the stability of perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Habisreutinger, Severin N.; McMeekin, David P.; Snaith, Henry J.; Nicholas, Robin J.

    2016-09-01

    The power-conversion efficiency of perovskite solar cells has soared up to 22.1% earlier this year. Within merely five years, the perovskite solar cell can now compete on efficiency with inorganic thin-film technologies, making it the most promising of the new, emerging photovoltaic solar cell technologies. The next grand challenge is now the aspect of stability. The hydrophilicity and volatility of the organic methylammonium makes the work-horse material methylammonium lead iodide vulnerable to degradation through humidity and heat. Additionally, ultraviolet radiation and oxygen constitute stressors which can deteriorate the device performance. There are two fundamental strategies to increasing the device stability: developing protective layers around the vulnerable perovskite absorber and developing a more resilient perovskite absorber. The most important reports in literature are summarized and analyzed here, letting us conclude that any long-term stability, on par with that of inorganic thin-film technologies, is only possible with a more resilient perovskite incorporated in a highly protective device design.

  4. Improved air stability of perovskite solar cells via solution-processed metal oxide transport layers.

    PubMed

    You, Jingbi; Meng, Lei; Song, Tze-Bin; Guo, Tzung-Fang; Yang, Yang Michael; Chang, Wei-Hsuan; Hong, Ziruo; Chen, Huajun; Zhou, Huanping; Chen, Qi; Liu, Yongsheng; De Marco, Nicholas; Yang, Yang

    2016-01-01

    Lead halide perovskite solar cells have recently attracted tremendous attention because of their excellent photovoltaic efficiencies. However, the poor stability of both the perovskite material and the charge transport layers has so far prevented the fabrication of devices that can withstand sustained operation under normal conditions. Here, we report a solution-processed lead halide perovskite solar cell that has p-type NiO(x) and n-type ZnO nanoparticles as hole and electron transport layers, respectively, and shows improved stability against water and oxygen degradation when compared with devices with organic charge transport layers. Our cells have a p-i-n structure (glass/indium tin oxide/NiO(x)/perovskite/ZnO/Al), in which the ZnO layer isolates the perovskite and Al layers, thus preventing degradation. After 60 days storage in air at room temperature, our all-metal-oxide devices retain about 90% of their original efficiency, unlike control devices made with organic transport layers, which undergo a complete degradation after just 5 days. The initial power conversion efficiency of our devices is 14.6 ± 1.5%, with an uncertified maximum value of 16.1%.

  5. Improved air stability of perovskite solar cells via solution-processed metal oxide transport layers

    NASA Astrophysics Data System (ADS)

    You, Jingbi; Meng, Lei; Song, Tze-Bin; Guo, Tzung-Fang; Yang, Yang (Michael); Chang, Wei-Hsuan; Hong, Ziruo; Chen, Huajun; Zhou, Huanping; Chen, Qi; Liu, Yongsheng; De Marco, Nicholas; Yang, Yang

    2016-01-01

    Lead halide perovskite solar cells have recently attracted tremendous attention because of their excellent photovoltaic efficiencies. However, the poor stability of both the perovskite material and the charge transport layers has so far prevented the fabrication of devices that can withstand sustained operation under normal conditions. Here, we report a solution-processed lead halide perovskite solar cell that has p-type NiOx and n-type ZnO nanoparticles as hole and electron transport layers, respectively, and shows improved stability against water and oxygen degradation when compared with devices with organic charge transport layers. Our cells have a p-i-n structure (glass/indium tin oxide/NiOx/perovskite/ZnO/Al), in which the ZnO layer isolates the perovskite and Al layers, thus preventing degradation. After 60 days storage in air at room temperature, our all-metal-oxide devices retain about 90% of their original efficiency, unlike control devices made with organic transport layers, which undergo a complete degradation after just 5 days. The initial power conversion efficiency of our devices is 14.6 ± 1.5%, with an uncertified maximum value of 16.1%.

  6. An aqueous preoxidation method for monolithic perovskite electrocatalysts with enhanced water oxidation performance

    PubMed Central

    Li, Bo-Quan; Tang, Cheng; Wang, Hao-Fan; Zhu, Xiao-Lin; Zhang, Qiang

    2016-01-01

    Perovskite oxides with poor conductivity call for three-dimensional (3D) conductive scaffolds to demonstrate their superb reactivities for oxygen evolution reaction (OER). However, perovskite formation usually requires high-temperature annealing at 600° to 900°C in air, under which most of the used conductive frameworks (for example, carbon and metal current collectors) are reductive and cannot survive. We propose a preoxidization coupled electrodeposition strategy in which Co2+ is preoxidized to Co3+ through cobalt Fenton reaction in aqueous solution, whereas the reductive nickel framework is well maintained during the sequential annealing under nonoxidative atmosphere. The in situ–generated Co3+ is inherited into oxidized perovskites deposited on 3D nickel foam, rendering the monolithic perovskite electrocatalysts with extraordinary OER performance with an ultralow overpotential of 350 mV required for 10 mA cm−2, a very small Tafel slope of 59 mV dec−1, and superb stability in 0.10 M KOH. Therefore, we inaugurate a unique strategy for in situ hybridization of oxidative active phase with reductive framework, affording superb reactivity of perovskite electrocatalyst for efficient water oxidation.

  7. High-performance perovskite light-emitting diodes via morphological control of perovskite films.

    PubMed

    Yu, Jae Choul; Kim, Da Bin; Jung, Eui Dae; Lee, Bo Ram; Song, Myoung Hoon

    2016-04-01

    Solution-processable perovskite materials have garnered tremendous attention because of their excellent charge carrier mobility, possibility of a tunable optical bandgap, and high photoluminescence quantum efficiency (PLQE). In particular, the uniform morphology of a perovskite film is the most important factor in realizing perovskite light-emitting diodes (PeLEDs) with high efficiency and full-coverage electroluminescence (EL). In this study, we demonstrate highly efficient PeLEDs that contain a perovskite film with a uniform morphology by introducing HBr into the perovskite precursor. The introduction of HBr into the perovskite precursor results in a perovskite film with a uniform, continuous morphology because the HBr increases the solubility of the inorganic component in the perovskite precursor and reduces the crystallization rate of the perovskite film upon spin-coating. Moreover, PeLEDs fabricated using perovskite films with a uniform, continuous morphology, which were deposited using 6 vol% HBr in a dimethylformamide (DMF)/hydrobromic acid (HBr) cosolvent, exhibited full coverage of the green EL emission. Finally, the optimized PeLEDs fabricated with perovskite films deposited using the DMF/HBr cosolvent exhibited a maximum luminance of 3490 cd m(-2) (at 4.3 V) and a luminous efficiency of 0.43 cd A(-1) (at 4.3 V). PMID:26607474

  8. Hidden biosphere in an oxygen-deficient Atlantic open ocean eddy: future implications of ocean deoxygenation on primary production in the eastern tropical North Atlantic

    NASA Astrophysics Data System (ADS)

    Löscher, C. R.; Fischer, M. A.; Neulinger, S. C.; Fiedler, B.; Philippi, M.; Schütte, F.; Singh, A.; Hauss, H.; Karstensen, J.; Körtzinger, A.; Künzel, S.; Schmitz, R. A.

    2015-08-01

    The eastern tropical North Atlantic (ETNA) is characterized by a highly productive coastal upwelling system and a moderate oxygen minimum zone with lowest open ocean oxygen (O2) concentrations of around 40 μmol kg-1. Only recently, the discovery of re-occurring mesoscale eddies with sometimes close to anoxic O2 concentrations (<1 μmol kg-1) and located just below the mixed layer challenged our understanding of O2 distribution and biogeochemical processes in this area. Here, we present the first metagenomic dataset from a deoxygenated anticyclonic modewater eddy in the open waters of the ETNA. In the eddy, we observed a significantly lower bacterial diversity compared to surrounding waters, along with a significant community shift. We detected enhanced primary productivity in the surface layer of the eddy indicated by elevated chlorophyll concentrations and increased carbon uptake rates up to three times as high as in surrounding waters. Carbon uptake below the euphotic zone correlated to the presence of a specific high-light ecotype of Prochlorococcus, which is usually underrepresented in the ETNA. Our combined data indicate that high primary production in the eddy fuels export production and the presence of a specific microbial community responsible for enhanced respiration at shallow depths, below the mixed layer base. Progressively decreasing O2 concentrations in the eddy were found to promote transcription of the key gene for denitrification, nirS, in the O2-depleted core waters. This process is usually absent from the open ETNA waters. In the light of future ocean deoxygenation our results show exemplarily that even distinct events of anoxia have the potential to alter microbial community structures and with that critically impact primary productivity and biogeochemical processes of oceanic water bodies.

  9. Hidden biosphere in an oxygen-deficient Atlantic open-ocean eddy: future implications of ocean deoxygenation on primary production in the eastern tropical North Atlantic

    NASA Astrophysics Data System (ADS)

    Löscher, C. R.; Fischer, M. A.; Neulinger, S. C.; Fiedler, B.; Philippi, M.; Schütte, F.; Singh, A.; Hauss, H.; Karstensen, J.; Körtzinger, A.; Künzel, S.; Schmitz, R. A.

    2015-12-01

    The eastern tropical North Atlantic (ETNA) is characterized by a highly productive coastal upwelling system and a moderate oxygen minimum zone with lowest open-ocean oxygen (O2) concentrations of approximately 40 μmol kg-1. The recent discovery of re-occurring mesoscale eddies with close to anoxic O2 concentrations (< 1 μmol kg-1) located just below the mixed layer has challenged our understanding of O2 distribution and biogeochemical processes in this area. Here, we present the first microbial community study from a deoxygenated anticyclonic modewater eddy in the open waters of the ETNA. In the eddy, we observed significantly lower bacterial diversity compared to surrounding waters, along with a significant community shift. We detected enhanced primary productivity in the surface layer of the eddy indicated by elevated chlorophyll concentrations and carbon uptake rates of up to three times as high as in surrounding waters. Carbon uptake rates below the euphotic zone correlated to the presence of a specific high-light ecotype of Prochlorococcus, which is usually underrepresented in the ETNA. Our data indicate that high primary production in the eddy fuels export production and supports enhanced respiration in a specific microbial community at shallow depths, below the mixed-layer base. The transcription of the key functional marker gene for dentrification, nirS, further indicated a potential for nitrogen loss processes in O2-depleted core waters of the eddy. Dentrification is usually absent from the open ETNA waters. In light of future projected ocean deoxygenation, our results show that even distinct events of anoxia have the potential to alter microbial community structure with critical impacts on primary productivity and biogeochemical processes of oceanic water bodies.

  10. Hidden biosphere in an oxygen-deficient Atlantic open ocean eddy: future implications of ocean deoxygenation on primary production in the eastern tropical North Atlantic

    NASA Astrophysics Data System (ADS)

    Loescher, Carolin; Fischer, Martin; Neulinger, Sven; Fiedler, Björn; Philippi, Miriam; Schütte, Florian; Singh, Arvind; Hauss, Helena; Karstensen, Johannes; Körtzinger, Arne; Schmitz, Ruth

    2016-04-01

    The eastern tropical North Atlantic (ETNA) is characterized by a highly productive coastal upwelling system and a moderate oxygen minimum zone with lowest open ocean oxygen (O2) concentrations of approximately 40 μmol kg-1. The recent discovery of re-occurring mesoscale eddies with close to anoxic O2 concentrations (<1 μmol kg-1) located just below the mixed layer has challenged our understanding of O2 distribution and biogeochemical processes in this area. Here, we present the first microbial community study from a deoxygenated anticyclonic modewater eddy in the open waters of the ETNA. In the eddy, we observed significantly lower bacterial diversity compared to surrounding waters, along with a significant community shift. We detected enhanced primary productivity in the surface layer of the eddy indicated by elevated chlorophyll concentrations and carbon uptake rates of up to three times as high as in surrounding waters. Carbon uptake rates below the euphotic zone correlated to the presence of a specific high-light ecotype of Prochlorococcus, which is usually underrepresented in the ETNA. Our data indicate that high primary production in the eddy fuels export production and supports enhanced respiration in a specific microbial community at shallow depths, below the mixed layer base. The O2-depleted core waters eddy promoted transcription of the key gene for denitrification, nirS. This process is usually absent from the open ETNA waters. In light of future projected ocean deoxygenation, our results show that even distinct events of anoxia have the potential to alter microbial community structure with critical impacts on primary productivity and biogeochemical processes of oceanic water bodies.

  11. Oxides of LANTHANUM(1-X) Strontium(x) COBALT(1 - Iron(y) OXYGEN(3) for Oxygen and Electrical Delivery Systems

    NASA Astrophysics Data System (ADS)

    Tai, Lone-Wen Frank

    Perovskite-type compounds in the system La_{1-x}Sr_{x}Co _{1-y}Fe_{y}O_ {3-delta have been considered as potential cathode materials for solid oxide fuel cells. The purpose of this study was to evaluate the structural, electrical, thermochemical properties of these compositions. The first and second papers of this dissertation dealt with the material synthesis, crystal structure, thermal expansion, thermogravimetry, electrical conductivity, and thermoelectricity of La_{0.8 }Sr_{0.2}Co_{1-y}Fe _{y}O_3 (y = 0-1) and La_{1-x}Sr_{x}Co _{0.2}Fe_{0.8}O_3 (x = 0-1) in air, respectively. Electrical conductivities and thermal expansion coefficients for these compositions were found to increase with Sr and Co contents. The unique temperature and composition dependence of the electrical conductivity observed in both systems were semi-empirically modeled by incorporating several mechanisms which include the hopping conduction of small polarons, a thermally activated charge disproportionation of Co^{3+ }, the ionic compensation by oxygen vacancy, and a preferential electronic compensation of acceptor by forming Fe^{4+} over Co^{4+}.. Phase stability, oxygen content, electrical conductivity, and Seebeck coefficient of La_ {1-x}Sr_{x}Co_{0.2 }Fe_{0.8}O_{3-delta } (x = 0, 0.2, 0.4) as function of temperature and oxygen activity were reported in the third paper. Both the oxygen deficiency and phase stability of compositions with y = 0.8 were found considerably high. It has been demonstrated that the degree of oxygen deficiency in these compositions significantly influences their structural and electrical properties, especially in the high temperature region.

  12. First Principles Studies of ABO3 Perovskite Surfaces and Nanostructures

    NASA Astrophysics Data System (ADS)

    Pilania, Ghanshyam

    Perovskite-type complex oxides, with general formula ABO 3, constitute one of the most prominent classes of metal oxides which finds key applications in diverse technological fields. In recent years, properties of perovskites at reduced dimensions have aroused considerable interest. However, a complete atomic-level understanding of various phenomena is yet to emerge. To fully exploit the materials opportunities provided by nano-structured perovskites, it is important to characterize and understand their bulk and near-surface electronic structure along with the electric, magnetic, elastic and chemical properties of these materials in the nano-regime, where surface and interface effects naturally play a dominant role. In this thesis, state-of-the-art first principles computations are employed to systematically study properties of one- and two-dimensional perovskite systems which are of direct technological significance. Specifically, our bifocal study targets (1) polarization behavior and dielectric response of ABO3 ferroelectric nanowires, and (2) oxygen chemistry relevant for catalytic properties of ABO3 surfaces. In the first strand, we identify presence of novel closure or vortex-like polarization domains in PbTIO3 and BaTiO3 ferroelectric nanowires and explore ways to control the polarization configurations by means of strain and surface chemistry in these prototypical model systems. The intrinsic tendency towards vortex polarization at reduced dimensions and the underlying driving forces are discussed and previously unknown strain induced phase transitions are identified. Furthermore, to compute the dielectric permittivity of nanostructures, a new multiscale model is developed and applied to the PbTiO3 nanowires with conventional and vortex-like polarization configurations. The second part of the work undertaken in this thesis is comprised of a number of ab initio surface studies, targeted to investigate the effects of surface terminations, prevailing chemical

  13. A new generation of high temperature oxygen sensors

    NASA Astrophysics Data System (ADS)

    Spirig, John V.

    -doped manganate perovskite and stabilized zirconia, served as a model system for joining electron carriers to an electrolyte without the creation of undesirable interlayers. Electron microscopy confirmed that intergranular penetration occurred at the joining plane leading to effective bonding between the two dissimilar ceramics. Raman spectral maps of the joining planes obtained with 2-D Raman microscopy demonstrated the absence of any new phases at the interface. A conducting perovskite with a lower Al:Mn ratio, but compensating A-site deficiency, La0.69Sr0.18Al0.45Mn0.55 O3, was joined to YTZP at 1250°C. X-ray diffraction was used to gain structural information on this A-site deficient perovskite. Room temperature resistivity measurements of the electroceramics were performed on joined and unjoined samples to determine the extent to which joining altered electron conduction within the LSAM. Electron microscopy confirmed that intergranular penetration occurred at the joining plane leading to effective bonding between the two dissimilar ceramics. Raman spectral maps of the joined samples demonstrated that joining temperature determines the extent to which interlayers begin to form in the joining plane. X-ray microdiffraction of the joining planes confirmed a threshold temperature for operation of a device created from these materials at 1350°C. A new material with diminished reactivity and high conductivity is presented to serve as a replacement for metal electrodes. In this manner, the model for a new generation of high-temperature oxygen sensors with internal references and ceramic wires is elucidated.

  14. Flexible Hybrid Organic-Inorganic Perovskite Memory.

    PubMed

    Gu, Chungwan; Lee, Jang-Sik

    2016-05-24

    Active research has been done on hybrid organic-inorganic perovskite materials for application to solar cells with high power conversion efficiency. However, this material often shows hysteresis, which is undesirable, shift in the current-voltage curve. The hysteresis may come from formation of defects and their movement in perovskite materials. Here, we utilize the defects in perovskite materials to be used in memory operations. We demonstrate flexible nonvolatile memory devices based on hybrid organic-inorganic perovskite as the resistive switching layer on a plastic substrate. A uniform perovskite layer is formed on a transparent electrode-coated plastic substrate by solvent engineering. Flexible nonvolatile memory based on the perovskite layer shows reproducible and reliable memory characteristics in terms of program/erase operations, data retention, and endurance properties. The memory devices also show good mechanical flexibility. It is suggested that resistive switching is done by migration of vacancy defects and formation of conducting filaments under the electric field in the perovskite layer. It is believed that organic-inorganic perovskite materials have great potential to be used in high-performance, flexible memory devices. PMID:27093096

  15. Achieving High Performance Perovskite Solar Cells

    NASA Astrophysics Data System (ADS)

    Yang, Yang

    2015-03-01

    Recently, metal halide perovskite based solar cell with the characteristics of rather low raw materials cost, great potential for simple process and scalable production, and extreme high power conversion efficiency (PCE), have been highlighted as one of the most competitive technologies for next generation thin film photovoltaic (PV). In UCLA, we have realized an efficient pathway to achieve high performance pervoskite solar cells, where the findings are beneficial to this unique materials/devices system. Our recent progress lies in perovskite film formation, defect passivation, transport materials design, interface engineering with respect to high performance solar cell, as well as the exploration of its applications beyond photovoltaics. These achievements include: 1) development of vapor assisted solution process (VASP) and moisture assisted solution process, which produces perovskite film with improved conformity, high crystallinity, reduced recombination rate, and the resulting high performance; 2) examination of the defects property of perovskite materials, and demonstration of a self-induced passivation approach to reduce carrier recombination; 3) interface engineering based on design of the carrier transport materials and the electrodes, in combination with high quality perovskite film, which delivers 15 ~ 20% PCEs; 4) a novel integration of bulk heterojunction to perovskite solar cell to achieve better light harvest; 5) fabrication of inverted solar cell device with high efficiency and flexibility and 6) exploration the application of perovskite materials to photodetector. Further development in film, device architecture, and interfaces will lead to continuous improved perovskite solar cells and other organic-inorganic hybrid optoelectronics.

  16. Photoinduced enhancement of the c-axis conductivity in oxygen-deficient YBa{sub 2}Cu{sub 3}O{sub x} thin films

    SciTech Connect

    Markowitsch, W.; Stockinger, C.; Lang, W. |; Bierleutgeb, K.; Pedarnig, J.D.; Baeuerle, D.

    1997-09-01

    High quality thin films of oxygen-depleted YBa{sub 2}Cu{sub 3}O{sub x} (x{approx}6.6) were prepared by pulsed-laser deposition on SrTiO{sub 3}, substrates that were cut with tilt angles of 10{degree} and 20{degree} with respect to the [001] direction, resulting in a steplike growth of the layers. The resistance showed a semiconducting behavior along the projection of the c axis to the film surface, but a metallic behavior in the perpendicular direction, indicating that the former is dominated by the c-axis resistivity and the latter by the ab-plane resistivity of YBa{sub 2}Cu{sub 3}O{sub x}. Long-term illumination of the samples with a 100 W halogen lamp resulted in a significant conductivity enhancement in both directions. The photoinduced change of the out-of-plane resistance vs temperature characteristics is comparable to the effect of large hydrostatic pressure, introducing structural changes similar to that of photoexcitation. {copyright} {ital 1997 American Institute of Physics.}

  17. Defective TiO2 with high photoconductive gain for efficient and stable planar heterojunction perovskite solar cells.

    PubMed

    Li, Yanbo; Cooper, Jason K; Liu, Wenjun; Sutter-Fella, Carolin M; Amani, Matin; Beeman, Jeffrey W; Javey, Ali; Ager, Joel W; Liu, Yi; Toma, Francesca M; Sharp, Ian D

    2016-01-01

    Formation of planar heterojunction perovskite solar cells exhibiting both high efficiency and stability under continuous operation remains a challenge. Here, we show this can be achieved by using a defective TiO2 thin film as the electron transport layer. TiO2 layers with native defects are deposited by electron beam evaporation in an oxygen-deficient environment. Deep-level hole traps are introduced in the TiO2 layers and contribute to a high photoconductive gain and reduced photocatalytic activity. The high photoconductivity of the TiO2 electron transport layer leads to improved efficiency for the fabricated planar devices. A maximum power conversion efficiency of 19.0% and an average PCE of 17.5% are achieved. In addition, the reduced photocatalytic activity of the TiO2 layer leads to enhanced long-term stability for the planar devices. Under continuous operation near the maximum power point, an efficiency of over 15.4% is demonstrated for 100 h.

  18. Defective TiO2 with high photoconductive gain for efficient and stable planar heterojunction perovskite solar cells

    PubMed Central

    Li, Yanbo; Cooper, Jason K.; Liu, Wenjun; Sutter-Fella, Carolin M.; Amani, Matin; Beeman, Jeffrey W.; Javey, Ali; Ager, Joel W.; Liu, Yi; Toma, Francesca M.; Sharp, Ian D.

    2016-01-01

    Formation of planar heterojunction perovskite solar cells exhibiting both high efficiency and stability under continuous operation remains a challenge. Here, we show this can be achieved by using a defective TiO2 thin film as the electron transport layer. TiO2 layers with native defects are deposited by electron beam evaporation in an oxygen-deficient environment. Deep-level hole traps are introduced in the TiO2 layers and contribute to a high photoconductive gain and reduced photocatalytic activity. The high photoconductivity of the TiO2 electron transport layer leads to improved efficiency for the fabricated planar devices. A maximum power conversion efficiency of 19.0% and an average PCE of 17.5% are achieved. In addition, the reduced photocatalytic activity of the TiO2 layer leads to enhanced long-term stability for the planar devices. Under continuous operation near the maximum power point, an efficiency of over 15.4% is demonstrated for 100 h. PMID:27534585

  19. Defective TiO2 with high photoconductive gain for efficient and stable planar heterojunction perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Li, Yanbo; Cooper, Jason K.; Liu, Wenjun; Sutter-Fella, Carolin M.; Amani, Matin; Beeman, Jeffrey W.; Javey, Ali; Ager, Joel W.; Liu, Yi; Toma, Francesca M.; Sharp, Ian D.

    2016-08-01

    Formation of planar heterojunction perovskite solar cells exhibiting both high efficiency and stability under continuous operation remains a challenge. Here, we show this can be achieved by using a defective TiO2 thin film as the electron transport layer. TiO2 layers with native defects are deposited by electron beam evaporation in an oxygen-deficient environment. Deep-level hole traps are introduced in the TiO2 layers and contribute to a high photoconductive gain and reduced photocatalytic activity. The high photoconductivity of the TiO2 electron transport layer leads to improved efficiency for the fabricated planar devices. A maximum power conversion efficiency of 19.0% and an average PCE of 17.5% are achieved. In addition, the reduced photocatalytic activity of the TiO2 layer leads to enhanced long-term stability for the planar devices. Under continuous operation near the maximum power point, an efficiency of over 15.4% is demonstrated for 100 h.

  20. Defective TiO2 with high photoconductive gain for efficient and stable planar heterojunction perovskite solar cells.

    PubMed

    Li, Yanbo; Cooper, Jason K; Liu, Wenjun; Sutter-Fella, Carolin M; Amani, Matin; Beeman, Jeffrey W; Javey, Ali; Ager, Joel W; Liu, Yi; Toma, Francesca M; Sharp, Ian D

    2016-01-01

    Formation of planar heterojunction perovskite solar cells exhibiting both high efficiency and stability under continuous operation remains a challenge. Here, we show this can be achieved by using a defective TiO2 thin film as the electron transport layer. TiO2 layers with native defects are deposited by electron beam evaporation in an oxygen-deficient environment. Deep-level hole traps are introduced in the TiO2 layers and contribute to a high photoconductive gain and reduced photocatalytic activity. The high photoconductivity of the TiO2 electron transport layer leads to improved efficiency for the fabricated planar devices. A maximum power conversion efficiency of 19.0% and an average PCE of 17.5% are achieved. In addition, the reduced photocatalytic activity of the TiO2 layer leads to enhanced long-term stability for the planar devices. Under continuous operation near the maximum power point, an efficiency of over 15.4% is demonstrated for 100 h. PMID:27534585

  1. Stability of organometal perovskites with organic overlayers

    SciTech Connect

    Tran, Catherine D. T.; Liu, Yi; Thibau, Emmanuel S.; Llanos, Adrian; Lu, Zheng-Hong

    2015-08-15

    The air-stability of vapour-phase-deposited methylammonium lead triiodide (CH{sub 3}NH{sub 3}PbI{sub 3}) perovskite thin films has been studied using X-ray diffraction. It is found that the perovskite structure without organic coating decomposes completely within a short period of time (∼two days) upon exposure to ambient environment. The degradation of the perovskite structure is drastically reduced when the perovskite films are capped with thin N,N′-Di(1-naphthyl)-N,N′-diphenyl-(1,1′-biphenyl)-4,4′-diamine (NPB) films. We discovered that the amount of lead iodide (PbI{sub 2}), a product of the degradation, grows as a function of time in a sigmoidal manner. Further mathematical modeling analysis shows that the perovskite degradation follows the Avrami equation, a kinetics theory developed for quantifying phase transformations in solid-state materials.

  2. Non-collinear magnetism in multiferroic perovskites.

    PubMed

    Bousquet, Eric; Cano, Andrés

    2016-03-31

    We present an overview of the current interest in non-collinear magnetism in multiferroic perovskite crystals. We first describe the different microscopic mechanisms giving rise to the non-collinearity of spins in this class of materials. We discuss, in particular, the interplay between non-collinear magnetism and ferroelectric and antiferrodistortive distortions of the perovskite structure, and how this can promote magnetoelectric responses. We then provide a literature survey on non-collinear multiferroic perovskites. We discuss numerous examples of spin cantings driving weak ferromagnetism in transition metal perovskites, and of spin-induced ferroelectricity as observed in the rare-earth based perovskites. These examples are chosen to best illustrate the fundamental role of non-collinear magnetism in the design of multiferroicity.

  3. Organohalide Lead Perovskites for Photovoltaic Applications.

    PubMed

    Yusoff, Abd Rashid Bin Mohd; Nazeeruddin, Mohammad Khaja

    2016-03-01

    Perovskite solar cells have recently exhibited a significant leap in efficiency due to their broad absorption, high optical absorption coefficient, very low exciton binding energy, long carrier diffusion lengths, efficient charge collection, and very high open-circuit potential, similar to that of III-IV semiconductors. Unlike silicon solar cells, perovskite solar cells can be developed from a variety of low-temperature solutions processed from inexpensive raw materials. When the perovskite absorber film formation is optimized using solvent engineering, a power conversion efficiency of over 21% has been demonstrated, highlighting the unique photovoltaic properties of perovskite materials. Here, we review the current progress in perovskite solar cells and charge transport materials. We highlight crucial challenges and provide a summary and prospects. PMID:26885884

  4. Copper oxide as a synergistic catalyst for the oxygen reduction reaction on La0.6Sr0.4Co0.2Fe0.8O3-δ perovskite structured electrocatalyst

    NASA Astrophysics Data System (ADS)

    Hong, Tao; Brinkman, Kyle; Xia, Changrong

    2016-10-01

    This work presents the effect of dispersed copper oxide (CuO) nanoparticles on the oxygen reduction reaction (ORR) on a typical solid oxide fuel cell (SOFC) electrocatalyst, La0.6Sr0.4Co0.2Fe0.8O3-δ (LSCF). The ORR kinetics were enhanced by a factor up to 4 at 750 °C as demonstrated by electrical conductivity relaxation measurements used to determine the chemical surface exchange coefficient, kchem. The value of kchem increased from 2.6 × 10-5 cm s-1 to 9.3 × 10-5 cm s-1 at 750 °C when the LSCF surface was coated with submicron CuO particles. The enhanced kchem was attributed to additional reactions that occur on the CuO surface and at the LSCF-CuO-gas three-phase boundaries (3PBs) as suggested by the kchem dependence on CuO coverage and 3PB length. This enhancement was further demonstrated by the introduction of CuO nanoparticles into LSCF electrodes. CuO infiltrated electrodes reduced the interfacial polarization resistance from 2.27 Ω cm2 to 1.5 Ω cm2 at 600 °C and increased the peak power density from 0.54 W cm-2 to 0.72 W cm-2 at 650 °C. Electrochemical impedance spectroscopy indicated that the reduced resistance was due to the shrinkage of the low frequency arc, which is associated with the electrochemical surface exchange reaction.

  5. Folate Deficiency Triggered Apoptosis of Synoviocytes: Role of Overproduction of Reactive Oxygen Species Generated via NADPH Oxidase/Mitochondrial Complex II and Calcium Perturbation

    PubMed Central

    Wu, Jin-Yi; Huang, Chin-Chin; Lu, Fung-Jou; Chuang, Yi-Wen; Chang, Pey-Jium; Chen, Kai-Hua; Hong, Chang-Zern; Yeh, Rang-Hui; Liu, Tsan-Zon; Chen, Ching-Hsein

    2016-01-01

    Despite a plethora of literature has documented that osteoarthritis (OA) is veritably associated with oxidative stress-mediated chondrocyte death and matrix degradation, yet the possible involvement of synoviocyte abnormality as causative factor of OA has not been thoroughly investigated. For this reason, we conduct the current studies to insight into how synoviocytes could respond to an episode of folate-deprived (FD) condition. First, when HIG-82 synoviocytes were cultivated under FD condition, a time-dependent growth impediment was observed and the demise of these cells was demonstrated to be apoptotic in nature mediated through FD-evoked overproduction of reactive oxygen species (ROS) and drastically released of cytosolic calcium (Ca2+) concentrations. Next, we uncovered that FD-evoked ROS overproduction could only be strongly suppressed by either mitochondrial complex II inhibitors (TTFA and carboxin) or NADPH oxidase (NOX) inhibitors (AEBSF and apocynin), but not by mitochondrial complex I inhibitor (rotenone) and mitochondrial complex III inhibitor (antimycin A). Interestingly, this selective inhibition of FD-evoked ROS by mitochondrial complex II and NOX inhibitors was found to correlate excellently with the suppression of cytosolic Ca2+ release and reduced the magnitude of the apoptotic TUNEL-positive cells. Taken together, we present the first evidence here that FD-triggered ROS overproduction in synoviocytes is originated from mitochondrial complex II and NOX. Both elevated ROS in tandem with cytosolic Ca2+ overload serve as final arbitrators for apoptotic lethality of synoviocytes cultivated under FD condition. Thus, folate supplementation may be beneficial to patients with OA. PMID:26771387

  6. Deficient Production of Reactive Oxygen Species Leads to Severe Chronic DSS-Induced Colitis in Ncf1/p47phox-Mutant Mice

    PubMed Central

    Rodrigues-Sousa, Tiago; Ladeirinha, Ana Filipa; Santiago, Ana Raquel; Carvalheiro, Helena; Raposo, Bruno; Alarcão, Ana; Cabrita, António; Holmdahl, Rikard; Carvalho, Lina; Souto-Carneiro, M. Margarida

    2014-01-01

    Background Colitis is a common clinical complication in chronic granulomatous disease (CGD), a primary immunodeficiency caused by impaired oxidative burst. Existing experimental data from NADPH-oxidase knockout mice propose contradictory roles for the involvement of reactive oxygen species in colitis chronicity and severity. Since genetically controlled mice with a point-mutation in the Ncf1 gene are susceptible to chronic inflammation and autoimmunity, we tested whether they presented increased predisposition to develop chronic colitis. Methods Colitis was induced in Ncf1-mutant and wild-type mice by a 1st 7-days cycle of dextran sulfate sodium (DSS), intercalated by a 7-days resting period followed by a 2nd 7-days DSS-cycle. Cytokines were quantified locally in the colon inflammatory infiltrates and in the serum. Leukocyte infiltration and morphological alterations of the colon mucosa were assessed by immunohistochemistry. Results Clinical scores demonstrated a more severe colitis in Ncf1-mutant mice than controls, with no recovery during the resting period and a severe chronic colitis after the 2nd cycle, confirmed by histopathology and presence of infiltrating neutrophils, macrophages, plasmocytes and lymphocytes in the colon. Severe colitis was mediated by increased local expression of cytokines (IL-6, IL-10, TNF-α, IFN-γ and IL-17A) and phosphorylation of Leucine-rich repeat kinase 2 (LRRK2). Serological cytokine titers of those inflammatory cytokines were more elevated in Ncf1-mutant than control mice, and were accompanied by systemic changes in functional subsets of monocytes, CD4+T and B cells. Conclusion This suggests that an ineffective oxidative burst leads to severe chronic colitis through local accumulation of peroxynitrites, pro-inflammatory cytokines and lymphocytes and systemic immune deregulation similar to CGD. PMID:24873968

  7. Reactive oxygen species- and nitric oxide-mediated lung inflammation and mitochondrial dysfunction in wild-type and iNOS-deficient mice exposed to diesel exhaust particles.

    PubMed

    Zhao, Hongwen; Ma, Joseph K; Barger, Mark W; Mercer, Robert R; Millecchia, Lyndell; Schwegler-Berry, Diane; Castranova, Vince; Ma, Jane Y

    2009-01-01

    Pulmonary responses to diesel exhaust particles (DEP) exposure are mediated through enhanced production of reactive oxygen species (ROS) and nitric oxide (NO) by alveolar macrophages (AM). The current study examined the differential roles of ROS and NO in DEP-induced lung injury using C57B/6J wild-type (WT) and inducible NO synthase knockout (iNOS KO) mice. Mice exposed by pharyngeal aspiration to DEP or carbon black particles (CB) (35 mg/kg) showed an inflammatory profile that included neutrophil infiltration, increased lactate dehydrogenase (LDH) activity, and elevated albumin content in bronchoalveolar lavage fluid (BALF) at 1, 3, and 7 d postexposure. The organic extract of DEP (DEPE) did not induce an inflammatory response. Comparing WT to iNOS KO mice, the results show that NO enhanced DEP-induced neutrophils infiltration and plasma albumin content in BALF and upregulated the production of the pro-inflammatory cytokine interleukin 12 (IL-12) by AM. DEP-exposed AM from iNOS KO mice displayed diminished production of IL-12 and, in response to ex vivo lipopolysaccharide (LPS) challenge, decreased production of IL-12 but increased production of IL-10 when compared to cells from WT mice. DEP, CB, but not DEPE, induced DNA damage and mitochondria dysfunction in AM, however, that is independent of cellular production of NO. These results demonstrate that DEP-induced immune/inflammatory responses in mice are regulated by both ROS- and NO-mediated pathways. NO did not affect ROS-mediated mitochondrial dysfunction and DNA damage but upregulated IL-12 and provided a counterbalance to the ROS-mediated adaptive stress response that downregulates IL-12 and upregulates IL-10. PMID:19267316

  8. Unreacted PbI2 as a Double-Edged Sword for Enhancing the Performance of Perovskite Solar Cells.

    PubMed

    Jacobsson, T Jesper; Correa-Baena, Juan-Pablo; Halvani Anaraki, Elham; Philippe, Bertrand; Stranks, Samuel D; Bouduban, Marine E F; Tress, Wolfgang; Schenk, Kurt; Teuscher, Joël; Moser, Jacques-E; Rensmo, Håkan; Hagfeldt, Anders

    2016-08-17

    Lead halide perovskites have over the past few years attracted considerable interest as photo absorbers in PV applications with record efficiencies now reaching 22%. It has recently been found that not only the composition but also the precise stoichiometry is important for the device performance. Recent reports have, for example, demonstrated small amount of PbI2 in the perovskite films to be beneficial for the overall performance of both the standard perovskite, CH3NH3PbI3, as well as for the mixed perovskites (CH3NH3)x(CH(NH2)2)(1-x)PbBryI(3-y). In this work a broad range of characterization techniques including X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), photo electron spectroscopy (PES), transient absorption spectroscopy (TAS), UV-vis, electroluminescence (EL), photoluminescence (PL), and confocal PL mapping have been used to further understand the importance of remnant PbI2 in perovskite solar cells. Our best devices were over 18% efficient, and had in line with previous results a small amount of excess PbI2. For the PbI2-deficient samples, the photocurrent dropped, which could be attributed to accumulation of organic species at the grain boundaries, low charge carrier mobility, and decreased electron injection into the TiO2. The PbI2-deficient compositions did, however, also have advantages. The record Voc was as high as 1.20 V and was found in PbI2-deficient samples. This was correlated with high crystal quality, longer charge carrier lifetimes, and high PL yields and was rationalized as a consequence of the dynamics of the perovskite formation. We further found the ion migration to be obstructed in the PbI2-deficient samples, which decreased the JV hysteresis and increased the photostability. PbI2-deficient synthesis conditions can thus be used to deposit perovskites with excellent crystal quality but with the downside of grain boundaries enriched in organic species, which act as a barrier toward

  9. Unreacted PbI2 as a Double-Edged Sword for Enhancing the Performance of Perovskite Solar Cells.

    PubMed

    Jacobsson, T Jesper; Correa-Baena, Juan-Pablo; Halvani Anaraki, Elham; Philippe, Bertrand; Stranks, Samuel D; Bouduban, Marine E F; Tress, Wolfgang; Schenk, Kurt; Teuscher, Joël; Moser, Jacques-E; Rensmo, Håkan; Hagfeldt, Anders

    2016-08-17

    Lead halide perovskites have over the past few years attracted considerable interest as photo absorbers in PV applications with record efficiencies now reaching 22%. It has recently been found that not only the composition but also the precise stoichiometry is important for the device performance. Recent reports have, for example, demonstrated small amount of PbI2 in the perovskite films to be beneficial for the overall performance of both the standard perovskite, CH3NH3PbI3, as well as for the mixed perovskites (CH3NH3)x(CH(NH2)2)(1-x)PbBryI(3-y). In this work a broad range of characterization techniques including X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), photo electron spectroscopy (PES), transient absorption spectroscopy (TAS), UV-vis, electroluminescence (EL), photoluminescence (PL), and confocal PL mapping have been used to further understand the importance of remnant PbI2 in perovskite solar cells. Our best devices were over 18% efficient, and had in line with previous results a small amount of excess PbI2. For the PbI2-deficient samples, the photocurrent dropped, which could be attributed to accumulation of organic species at the grain boundaries, low charge carrier mobility, and decreased electron injection into the TiO2. The PbI2-deficient compositions did, however, also have advantages. The record Voc was as high as 1.20 V and was found in PbI2-deficient samples. This was correlated with high crystal quality, longer charge carrier lifetimes, and high PL yields and was rationalized as a consequence of the dynamics of the perovskite formation. We further found the ion migration to be obstructed in the PbI2-deficient samples, which decreased the JV hysteresis and increased the photostability. PbI2-deficient synthesis conditions can thus be used to deposit perovskites with excellent crystal quality but with the downside of grain boundaries enriched in organic species, which act as a barrier toward

  10. Preparation and Mixed Conductivity of Mn-DOPED Bi-Sr-Fe-BASED Perovskite Type Oxides

    NASA Astrophysics Data System (ADS)

    Baek, Doohyun; Takamura, Hitoshi

    2013-07-01

    Bi0.7Sr0.3FeO3-δ (BSF) with perovskite structure and Mn-doped BSFs were prepared by solid-state reaction and their mixed conductivities were discussed based on results of electrical conductivity and oxygen permeation measurement through membranes of those compounds. BSF showed only 2 S/cm at 800 °C suggesting that its charge unbalance is likely to be compensated by generation of oxygen vacancies. However, Mn-doping caused the increase of electrical conductivity and the decrease of oxygen permeation rate, that is, the extent of charge compensation by electron holes increased through Mn-doping.

  11. Mixed oxygen ion/electron-conducting ceramics for oxygen separation

    SciTech Connect

    Stevenson, J.W.; Armstrong, T.R.; Armstrong, B.L.

    1996-08-01

    Mixed oxygen ion and electron-conducting ceramics are unique materials that can passively separate high purity oxygen from air. Oxygen ions move through a fully dense ceramic in response to an oxygen concentration gradient, charge-compensated by an electron flux in the opposite direction. Compositions in the system La{sub 1{minus}x}M{sub x}Co{sub 1{minus}y{minus}z}Fe{sub y}N{sub z}O{sub 3{minus}{delta}}, perovskites where M=Sr, Ca, and Ba, and N=Mn, Ni, Cu, Ti, and Al, have been prepared and their electrical, oxygen permeation, oxygen vacancy equilibria, and catalytic properties evaluated. Tubular forms, disks, and asymmetric membrane structures, a thin dense layer on a porous support of the same composition, have been fabricated for testing purposes. In an oxygen partial gradient, the passive oxygen flux through fully dense structures was highly dependent on composition. An increase in oxygen permeation with increased temperature is attributed to both enhanced oxygen vacancy mobility and higher vacancy populations. Highly acceptor-doped compositions resulted in oxygen ion mobilities more than an order of magnitude higher than yttria-stabilized zirconia. The mixed conducting ceramics have been utilized in a membrane reactor configuration to upgrade methane to ethane and ethylene. Conditions were established to balance selectivity and throughput in a catalytic membrane reactor constructed from mixed conducting ceramics.

  12. Water electrolysis on La1-xSrxCoO3-δ perovskite electrocatalysts

    DOE PAGESBeta

    Mefford, J. Tyler; Rong, Xi; Abakumov, Artem M.; Hardin, William G.; Dai, Sheng; Kolpak, Alexie; Johnston, Keith P.; Stevenson, Keith J.

    2016-03-23

    Here, perovskite oxides are attractive candidates as catalysts for the electrolysis of water in alkaline energy storage and conversion systems. However, the rational design of active catalysts has been hampered by the lack of understanding of the mechanism of water electrolysis on perovskite surfaces. Key parameters that have been overlooked include the role of oxygen vacancies, B–O bond covalency, and redox activity of lattice oxygen species. Here we present a series of cobaltite perovskites where the covalency of the Co–O bond and the concentration of oxygen vacancies are controlled through Sr2+ substitution into La1–xSrxCoO3–δ. We attempt to rationalize the highmore » activities of La1–xSrxCoO3–δ through the electronic structure and participation of lattice oxygen in the mechanism of water electrolysis as revealed through ab initio modelling. Using this approach, we report a material, SrCoO2.7, with a high, room temperature-specific activity and mass activity towards alkaline water electrolysis.« less

  13. Water electrolysis on La1-xSrxCoO3-δ perovskite electrocatalysts

    NASA Astrophysics Data System (ADS)

    Mefford, J. Tyler; Rong, Xi; Abakumov, Artem M.; Hardin, William G.; Dai, Sheng; Kolpak, Alexie M.; Johnston, Keith P.; Stevenson, Keith J.

    2016-03-01

    Perovskite oxides are attractive candidates as catalysts for the electrolysis of water in alkaline energy storage and conversion systems. However, the rational design of active catalysts has been hampered by the lack of understanding of the mechanism of water electrolysis on perovskite surfaces. Key parameters that have been overlooked include the role of oxygen vacancies, B-O bond covalency, and redox activity of lattice oxygen species. Here we present a series of cobaltite perovskites where the covalency of the Co-O bond and the concentration of oxygen vacancies are controlled through Sr2+ substitution into La1-xSrxCoO3-δ. We attempt to rationalize the high activities of La1-xSrxCoO3-δ through the electronic structure and participation of lattice oxygen in the mechanism of water electrolysis as revealed through ab initio modelling. Using this approach, we report a material, SrCoO2.7, with a high, room temperature-specific activity and mass activity towards alkaline water electrolysis.

  14. Water electrolysis on La(1-x)Sr(x)CoO(3-δ) perovskite electrocatalysts.

    PubMed

    Mefford, J Tyler; Rong, Xi; Abakumov, Artem M; Hardin, William G; Dai, Sheng; Kolpak, Alexie M; Johnston, Keith P; Stevenson, Keith J

    2016-01-01

    Perovskite oxides are attractive candidates as catalysts for the electrolysis of water in alkaline energy storage and conversion systems. However, the rational design of active catalysts has been hampered by the lack of understanding of the mechanism of water electrolysis on perovskite surfaces. Key parameters that have been overlooked include the role of oxygen vacancies, B-O bond covalency, and redox activity of lattice oxygen species. Here we present a series of cobaltite perovskites where the covalency of the Co-O bond and the concentration of oxygen vacancies are controlled through Sr(2+) substitution into La(1-x)Sr(x)CoO(3-δ) . We attempt to rationalize the high activities of La(1-x)Sr(x)CoO(3-δ) through the electronic structure and participation of lattice oxygen in the mechanism of water electrolysis as revealed through ab initio modelling. Using this approach, we report a material, SrCoO2.7, with a high, room temperature-specific activity and mass activity towards alkaline water electrolysis.

  15. Solid State Structure-Reactivity Studies on Bixbyites, Fluorites and Perovskites Belonging to the Vanadate, Titanate and Cerate Families

    NASA Astrophysics Data System (ADS)

    Shafi, Shahid P.

    This thesis primarily focuses on the systematic understanding of structure-reactivity relationships in two representative systems: bixbyite and related structures as well as indium doped CeO2. Topotactic reaction routes have gained significant attention over the past two decades due to their potential to access kinetically controlled metastable materials. This has contributed substantially to the understanding of solid state reaction pathways and provided first insights into mechanisms. Contrary to the widely used ex-situ methods, in-situ techniques including powder x-ray diffraction and thermogravimetric-differential thermal analysis have been employed extensively throughout this work in order to follow the reaction pathways in real time. Detailed analysis of the AVO3 (A = In, Sc) bixbyite reactivity under oxidative conditions has been carried out and a variety of novel metastable oxygen defect phases have been identified and characterized. The novel metastable materials have oxygen deficient fluorite structures and consequently are potential ion conductors. Structural aspects of the topotactic vs. reconstructive transformations are illustrated with this model system. The structure-reactivity study of AVO3 phases was extended to AVO3 perovskite family. Based on the research methodologies and results from AVO3 bixbyite reactivity studies a generalized mechanistic oxidation pathway has been established with a non-vanadium phase, ScTiO3 bixbyite. However, there is stark contrast in terms of structural stability and features beyond this stability limit during AVO3 and ScTiO3 bixbyite reaction pathways. A series of complex reaction sequences including phase separation and phase transitions were identified during the investigation of ScTiO3 reactivity. The two-step formation pathway for the fluorite-type oxide ion conductor Ce1-xInxO2-delta (0 ≤ x ≤ 0.3) is being reported. The formation of the BaCe1-xInxO 3-delta perovskites and the subsequent CO2-capture reaction

  16. Detection and imaging of the oxygen deficiency in single crystalline YBa{sub 2}Cu{sub 3}O{sub 7−δ} thin films using a scanning positron beam

    SciTech Connect

    Reiner, M.; Gigl, T.; Hugenschmidt, C.; Jany, R.; Hammerl, G.

    2015-03-16

    Single crystalline YBa{sub 2}Cu{sub 3}O{sub 7−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 T{sub c} 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.

  17. Improved chemical and electrochemical stability of perovskite oxides with less reducible cations at the surface.

    PubMed

    Tsvetkov, Nikolai; Lu, Qiyang; Sun, Lixin; Crumlin, Ethan J; Yildiz, Bilge

    2016-09-01

    Segregation and phase separation of aliovalent dopants on perovskite oxide (ABO3) surfaces are detrimental to the performance of energy conversion systems such as solid oxide fuel/electrolysis cells and catalysts for thermochemical H2O and CO2 splitting. One key reason behind the instability of perovskite oxide surfaces is the electrostatic attraction of the negatively charged A-site dopants (for example, ) by the positively charged oxygen vacancies () enriched at the surface. Here we show that reducing the surface concentration improves the oxygen surface exchange kinetics and stability significantly, albeit contrary to the well-established understanding that surface oxygen vacancies facilitate reactions with O2 molecules. We take La0.8Sr0.2CoO3 (LSC) as a model perovskite oxide, and modify its surface with additive cations that are more and less reducible than Co on the B-site of LSC. By using ambient-pressure X-ray absorption and photoelectron spectroscopy, we proved that the dominant role of the less reducible cations is to suppress the enrichment and phase separation of Sr while reducing the concentration of and making the LSC more oxidized at its surface. Consequently, we found that these less reducible cations significantly improve stability, with up to 30 times faster oxygen exchange kinetics after 54 h in air at 530 °C achieved by Hf addition onto LSC. Finally, the results revealed a 'volcano' relation between the oxygen exchange kinetics and the oxygen vacancy formation enthalpy of the binary oxides of the additive cations. This volcano relation highlights the existence of an optimum surface oxygen vacancy concentration that balances the gain in oxygen exchange kinetics and the chemical stability loss. PMID:27295099

  18. Improved chemical and electrochemical stability of perovskite oxides with less reducible cations at the surface

    NASA Astrophysics Data System (ADS)

    Tsvetkov, Nikolai; Lu, Qiyang; Sun, Lixin; Crumlin, Ethan J.; Yildiz, Bilge

    2016-09-01

    Segregation and phase separation of aliovalent dopants on perovskite oxide (ABO3) surfaces are detrimental to the performance of energy conversion systems such as solid oxide fuel/electrolysis cells and catalysts for thermochemical H2O and CO2 splitting. One key reason behind the instability of perovskite oxide surfaces is the electrostatic attraction of the negatively charged A-site dopants (for example, ) by the positively charged oxygen vacancies () enriched at the surface. Here we show that reducing the surface concentration improves the oxygen surface exchange kinetics and stability significantly, albeit contrary to the well-established understanding that surface oxygen vacancies facilitate reactions with O2 molecules. We take La0.8Sr0.2CoO3 (LSC) as a model perovskite oxide, and modify its surface with additive cations that are more and less reducible than Co on the B-site of LSC. By using ambient-pressure X-ray absorption and photoelectron spectroscopy, we proved that the dominant role of the less reducible cations is to suppress the enrichment and phase separation of Sr while reducing the concentration of and making the LSC more oxidized at its surface. Consequently, we found that these less reducible cations significantly improve stability, with up to 30 times faster oxygen exchange kinetics after 54 h in air at 530 °C achieved by Hf addition onto LSC. Finally, the results revealed a `volcano' relation between the oxygen exchange kinetics and the oxygen vacancy formation enthalpy of the binary oxides of the additive cations. This volcano relation highlights the existence of an optimum surface oxygen vacancy concentration that balances the gain in oxygen exchange kinetics and the chemical stability loss.

  19. Large Grained Perovskite Solar Cells Derived from Single-Crystal Perovskite Powders with Enhanced Ambient Stability.

    PubMed

    Yen, Hung-Ju; Liang, Po-Wei; Chueh, Chu-Chen; Yang, Zhibin; Jen, Alex K-Y; Wang, Hsing-Lin

    2016-06-15

    In this study, we demonstrate the large grained perovskite solar cells prepared from precursor solution comprising single-crystal perovskite powders for the first time. The resultant large grained perovskite thin film possesses a negligible physical (structural) gap between each large grain and is highly crystalline as evidenced by its fan-shaped birefringence observed under polarized light, which is very different from the thin film prepared from the typical precursor route (MAI + PbI2).

  20. Perovskites: transforming photovoltaics, a mini-review

    DOE PAGESBeta

    Chilvery, Ashwith Kumar; Batra, Ashok K.; Yang, Bin; Xiao, Kai; Guggilla, Padmaja; Aggarwal, Mohan D.; Surabhi, Raja; Lal, Ravi B.; Currie, James R.; Penn, Benjamin G.

    2015-01-06

    The recent power-packed advent of perovskite solar cells is transforming photovoltaics (PV) with their superior efficiencies, ease of fabrication, and cost. This perovskite solar cell further boasts of many unexplored features that can further enhance its PV properties and lead to it being branded as a successful commercial product. This paper provides a detailed insight of the organometal halide based perovskite structure, its unique stoichiometric design, and its underlying principles for PV applications. Finally, the compatibility of various PV layers and its fabrication methods is also discussed.

  1. Templated Synthesis of Uniform Perovskite Nanowire Arrays.

    PubMed

    Ashley, Michael J; O'Brien, Matthew N; Hedderick, Konrad R; Mason, Jarad A; Ross, Michael B; Mirkin, Chad A

    2016-08-17

    While the chemical composition of semiconducting metal halide perovskites can be precisely controlled in thin films for photovoltaic devices, the synthesis of perovskite nanostructures with tunable dimensions and composition has not been realized. Here, we describe the templated synthesis of uniform perovskite nanowires with controlled diameter (50-200 nm). Importantly, by providing three examples (CH3NH3PbI3, CH3NH3PbBr3, and Cs2SnI6), we show that this process is composition general and results in oriented nanowire arrays on transparent conductive substrates. PMID:27501464

  2. Synthesis and oxygen content dependent properties of hexagonal DyMnO[subscript 3+delta

    SciTech Connect

    Remsen, S.; Dabrowski, B.; Chmaissem, O.; Mais, J.; Szewczyk, A.

    2011-10-28

    Oxygen deficient polycrystalline samples of hexagonal P6{sub 3}cm (space group No.185) DyMnO{sub 3+{delta}} ({delta} < 0) were synthesized in Ar by intentional decomposition of its perovskite phase obtained in air. The relative stability of these phases is in accord with our previous studies of the temperature and oxygen vacancy dependent tolerance factor. Thermogravimetric measurements have shown that hexagonal samples of DyMnO{sub 3+{delta}} (0 {le} {delta} {le} 0.4) exhibit unusually large excess oxygen content, which readily incorporates on heating near 300 C in various partial-pressures of oxygen atmospheres. Neutron and synchrotron diffraction data show the presence of two new structural phases at {delta} {approx} 0.25 (Hex{sub 2}) and {delta} {approx} 0.40 (Hex{sub 3}). Rietveld refinements of the Hex{sub 2} phase strongly suggest it is well modeled by the R3 space group (No.146). These phases were observed to transform back to P6{sub 3}cm above {approx} 350 C when material becomes stoichiometric in oxygen content ({delta} = 0). Chemical expansion of the crystal lattice corresponding to these large changes of oxygen was found to be 3.48 x 10{sup -2} mol{sup -1}. Thermal expansion of stoichiometric phases were determined to be 11.6 x 10{sup -6} and 2.1 x 10{sup -6} K{sup -1} for the P6{sub 3}cm and Hex{sub 2} phases, respectively. Our measurements also indicate that the oxygen non-stoichiometry of hexagonal RMnO{sub 3+{delta}} materials may have important influence on their multiferroic properties.

  3. Synthesis and oxygen content dependent properties of hexagonal DyMnO{sub 3 + sub delta}.

    SciTech Connect

    Remsen, S.; Dabrowski, B.; Chmaissem, O.; Mais, J.; Szewczyk, A.

    2011-07-01

    Oxygen deficient polycrystalline samples of hexagonal P6{sub 3}cm (space group No.185) DyMnO{sub 3+{delta}} ({delta} < 0) were synthesized in Ar by intentional decomposition of its perovskite phase obtained in air. The relative stability of these phases is in accord with our previous studies of the temperature and oxygen vacancy dependent tolerance factor. Thermogravimetric measurements have shown that hexagonal samples of DyMnO{sub 3+{delta}} (0 {<=} {delta} {<=} 0.4) exhibit unusually large excess oxygen content, which readily incorporates on heating near 300 C in various partial-pressures of oxygen atmospheres. Neutron and synchrotron diffraction data show the presence of two new structural phases at {delta} {approx} 0.25 (Hex{sub 2}) and {delta} {approx} 0.40 (Hex{sub 3}). Rietveld refinements of the Hex{sub 2} phase strongly suggest it is well modeled by the R3 space group (No.146). These phases were observed to transform back to P6{sub 3}cm above {approx}350 C when material becomes stoichiometric in oxygen content ({delta} = 0). Chemical expansion of the crystal lattice corresponding to these large changes of oxygen was found to be 3.48 x 10{sup -2} mol{sup -1}. Thermal expansion of stoichiometric phases were determined to be 11.6 x 10{sup -6} and 2.1 x 10{sup -6} K{sup -1} for the P6{sub 3}cm and Hex{sub 2} phases, respectively. Our measurements also indicate that the oxygen non-stoichiometry of hexagonal RMnO{sub 3+{delta}} materials may have important influence on their multiferroic properties.

  4. Strongly correlated perovskite fuel cells

    NASA Astrophysics Data System (ADS)

    Zhou, You; Guan, Xiaofei; Zhou, Hua; Ramadoss, Koushik; Adam, Suhare; Liu, Huajun; Lee, Sungsik; Shi, Jian; Tsuchiya, Masaru; Fong, Dillon D.; Ramanathan, Shriram

    2016-06-01

    Fuel cells convert chemical energy directly into electrical energy with high efficiencies and environmental benefits, as compared with traditional heat engines. Yttria-stabilized zirconia is perhaps the material with the most potential as an electrolyte in solid oxide fuel cells (SOFCs), owing to its stability and near-unity ionic transference number. Although there exist materials with superior ionic conductivity, they are often limited by their ability to suppress electronic leakage when exposed to the reducing environment at the fuel interface. Such electronic leakage reduces fuel cell power output and the associated chemo-mechanical stresses can also lead to catastrophic fracture of electrolyte membranes. Here we depart from traditional electrolyte design that relies on cation substitution to sustain ionic conduction. Instead, we use a perovskite nickelate as an electrolyte with high initial ionic and electronic conductivity. Since many such oxides are also correlated electron systems, we can suppress the electronic conduction through a filling-controlled Mott transition induced by spontaneous hydrogen incorporation. Using such a nickelate as the electrolyte in free-standing membrane geometry, we demonstrate a low-temperature micro-fabricated SOFC with high performance. The ionic conductivity of the nickelate perovskite is comparable to the best-performing solid electrolytes in the same temperature range, with a very low activation energy. The results present a design strategy for high-performance materials exhibiting emergent properties arising from strong electron correlations.

  5. Strongly correlated perovskite fuel cells.

    PubMed

    Zhou, You; Guan, Xiaofei; Zhou, Hua; Ramadoss, Koushik; Adam, Suhare; Liu, Huajun; Lee, Sungsik; Shi, Jian; Tsuchiya, Masaru; Fong, Dillon D; Ramanathan, Shriram

    2016-05-16

    Fuel cells convert chemical energy directly into electrical energy with high efficiencies and environmental benefits, as compared with traditional heat engines. Yttria-stabilized zirconia is perhaps the material with the most potential as an electrolyte in solid oxide fuel cells (SOFCs), owing to its stability and near-unity ionic transference number. Although there exist materials with superior ionic conductivity, they are often limited by their ability to suppress electronic leakage when exposed to the reducing environment at the fuel interface. Such electronic leakage reduces fuel cell power output and the associated chemo-mechanical stresses can also lead to catastrophic fracture of electrolyte membranes. Here we depart from traditional electrolyte design that relies on cation substitution to sustain ionic conduction. Instead, we use a perovskite nickelate as an electrolyte with high initial ionic and electronic conductivity. Since many such oxides are also correlated electron systems, we can suppress the electronic conduction through a filling-controlled Mott transition induced by spontaneous hydrogen incorporation. Using such a nickelate as the electrolyte in free-standing membrane geometry, we demonstrate a low-temperature micro-fabricated SOFC with high performance. The ionic conductivity of the nickelate perovskite is comparable to the best-performing solid electrolytes in the same temperature range, with a very low activation energy. The results present a design strategy for high-performance materials exhibiting emergent properties arising from strong electron correlations.

  6. Strongly correlated perovskite fuel cells.

    PubMed

    Zhou, You; Guan, Xiaofei; Zhou, Hua; Ramadoss, Koushik; Adam, Suhare; Liu, Huajun; Lee, Sungsik; Shi, Jian; Tsuchiya, Masaru; Fong, Dillon D; Ramanathan, Shriram

    2016-06-01

    Fuel cells convert chemical energy directly into electrical energy with high efficiencies and environmental benefits, as compared with traditional heat engines. Yttria-stabilized zirconia is perhaps the material with the most potential as an electrolyte in solid oxide fuel cells (SOFCs), owing to its stability and near-unity ionic transference number. Although there exist materials with superior ionic conductivity, they are often limited by their ability to suppress electronic leakage when exposed to the reducing environment at the fuel interface. Such electronic leakage reduces fuel cell power output and the associated chemo-mechanical stresses can also lead to catastrophic fracture of electrolyte membranes. Here we depart from traditional electrolyte design that relies on cation substitution to sustain ionic conduction. Instead, we use a perovskite nickelate as an electrolyte with high initial ionic and electronic conductivity. Since many such oxides are also correlated electron systems, we can suppress the electronic conduction through a filling-controlled Mott transition induced by spontaneous hydrogen incorporation. Using such a nickelate as the electrolyte in free-standing membrane geometry, we demonstrate a low-temperature micro-fabricated SOFC with high performance. The ionic conductivity of the nickelate perovskite is comparable to the best-performing solid electrolytes in the same temperature range, with a very low activation energy. The results present a design strategy for high-performance materials exhibiting emergent properties arising from strong electron correlations. PMID:27279218

  7. Lattice constant prediction of defective rare earth titanate perovskites

    SciTech Connect

    Letourneau, Steven; Zhen, Zhen; Owens, Josh; Tolman, Kevin; Ubic, Rick; Kriven, Waltraud M.

    2014-11-15

    Engineering defective structures in an attempt to modify properties is an established technique in materials chemistry, yet, no models exist which can predict the structure of perovskite compounds containing extrinsic point defects such as vacancies. An empirically derived predictive model, based solely on chemical composition and published ionic radii has been developed. Effective vacancy sizes were derived both empirically from an existing model for pseudocubic lattice-constants, as well as experimentally, from average bond lengths calculated from neutron diffraction data. Compounds of lanthanum-doped barium titanate and strontium-doped magnesium titanate were synthesized with vacancies engineered on the A and B sites. Effective vacancy sizes were then used in empirical models to predict changes in lattice constants. Experimentally refined bond lengths used in the derivation of an effective vacancy size seemed to overestimate the effect of the point defects. Conversely, using calculated vacancy sizes, derived from a previously reported predictive model, showed significant improvements in the prediction of the pseudocubic perovskite lattice. - Graphical abstract: Atomistic model of Sr{sub 0.3}Nd{sub 0.7}Mg{sub 0.35}Ti{sub 0.65}O{sub 3} and Rietveld refinement of neutron diffraction data. - Highlights: • Defective perovskites were synthesized using the organic steric entrapment method. • Oxygen tilt systems were solved through X-ray, electron, and neutron diffraction. • An effective vacancy size for the cations was calculated from experimental bond lengths. • Discrepancies between Shannon radii and experimental measurements are explored. • An empirical model for predicting a{sub pc}, with an absolute error of 0.20%, was developed.

  8. High-performance perovskite light-emitting diodes via morphological control of perovskite films

    NASA Astrophysics Data System (ADS)

    Yu, Jae Choul; Kim, Da Bin; Jung, Eui Dae; Lee, Bo Ram; Song, Myoung Hoon

    2016-03-01

    Solution-processable perovskite materials have garnered tremendous attention because of their excellent charge carrier mobility, possibility of a tunable optical bandgap, and high photoluminescence quantum efficiency (PLQE). In particular, the uniform morphology of a perovskite film is the most important factor in realizing perovskite light-emitting diodes (PeLEDs) with high efficiency and full-coverage electroluminescence (EL). In this study, we demonstrate highly efficient PeLEDs that contain a perovskite film with a uniform morphology by introducing HBr into the perovskite precursor. The introduction of HBr into the perovskite precursor results in a perovskite film with a uniform, continuous morphology because the HBr increases the solubility of the inorganic component in the perovskite precursor and reduces the crystallization rate of the perovskite film upon spin-coating. Moreover, PeLEDs fabricated using perovskite films with a uniform, continuous morphology, which were deposited using 6 vol% HBr in a dimethylformamide (DMF)/hydrobromic acid (HBr) cosolvent, exhibited full coverage of the green EL emission. Finally, the optimized PeLEDs fabricated with perovskite films deposited using the DMF/HBr cosolvent exhibited a maximum luminance of 3490 cd m-2 (at 4.3 V) and a luminous efficiency of 0.43 cd A-1 (at 4.3 V).Solution-processable perovskite materials have garnered tremendous attention because of their excellent charge carrier mobility, possibility of a tunable optical bandgap, and high photoluminescence quantum efficiency (PLQE). In particular, the uniform morphology of a perovskite film is the most important factor in realizing perovskite light-emitting diodes (PeLEDs) with high efficiency and full-coverage electroluminescence (EL). In this study, we demonstrate highly efficient PeLEDs that contain a perovskite film with a uniform morphology by introducing HBr into the perovskite precursor. The introduction of HBr into the perovskite precursor results in

  9. Iron deficiency and iron deficiency anemia in women.

    PubMed

    Coad, Jane; Pedley, Kevin

    2014-01-01

    Iron deficiency is one of the most common nutritional problems in the world and disproportionately affects women and children. Stages of iron deficiency can be characterized as mild deficiency where iron stores become depleted, marginal deficiency where the production of many iron-dependent proteins is compromised but hemoglobin levels are normal and iron deficiency anemia where synthesis of hemoglobin is decreased and oxygen transport to the tissues is reduced. Iron deficiency anemia is usually assessed by measuring hemoglobin levels but this approach lacks both specificity and sensitivity. Failure to identify and treat earlier stages of iron deficiency is concerning given the neurocognitive implications of iron deficiency without anemia. Most of the daily iron requirement is derived from recycling of senescent erythrocytes by macrophages; only 5-10 % comes from the diet. Iron absorption is affected by inhibitors and enhancers of iron absorption and by the physiological state. Inflammatory conditions, including obesity, can result in iron being retained in the enterocytes and macrophages causing hypoferremia as a strategic defense mechanism to restrict iron availability to pathogens. Premenopausal women usually have low iron status because of iron loss in menstrual blood. Conditions which further increase iron loss, compromise absorption or increase demand, such as frequent blood donation, gastrointestinal lesions, athletic activity and pregnancy, can exceed the capacity of the gastrointestinal tract to upregulate iron absorption. Women of reproductive age are at particularly high risk of iron deficiency and its consequences however there is a controversial argument that evolutionary pressures have resulted in an iron deficient phenotype which protects against infection.

  10. Oxygen Transport Membranes

    SciTech Connect

    S. Bandopadhyay

    2008-08-30

    small polaron conduction mechanism. Scanning transmission electron microscopy (STEM) and electron energy loss spectroscopy (EELS) were used to develop strategies to detect and characterize vacancy creation, dopant segregations and defect association in the oxygen conducting membrane material. The pO{sub 2} and temperature dependence of the conductivity, non-stoichiometry and thermal-expansion behavior of compositions with increasing complexity of substitution on the perovskite A and B sites were studied. Studies with the perovskite structure show anomalous behavior at low oxygen partial pressures (<10{sup -5} atm). The anomalies are due to non-equilibrium effects and can be avoided by using very strict criteria for the attainment of equilibrium. The slowness of the oxygen equilibration kinetics arises from two different mechanisms. In the first, a two phase region occurs between an oxygen vacancy ordered phase such as brownmillerite SrFeO{sub 2.5} and perovskite SrFeO{sub 3-x}. The slow kinetics is associated with crossing the two phase region. The width of the miscibility gap decreases with increasing temperature and consequently the effect is less pronounced at higher temperature. The preferred kinetic pathway to reduction of perovskite ferrites when the vacancy concentration corresponds to the formation of significant concentrations of Fe{sup 2+} is via the formation of a Ruddlesden-Popper (RP) phases as clearly observed in the case of La{sub 0.5}Sr{sub 0.5}FeO{sub 3-x} where LaSrFeO{sub 4} is found together with Fe. In more complex compositions, such as LSFTO, iron or iron rich phases are observed locally with no evidence for the presence of discrete RP phase. Fracture strength of tubular perovskite membranes was determined in air and in reducing atmospheric conditions. The strength of the membrane decreased with temperature and severity of reducing conditions although the strength distribution (Weibull parameter, m) was relatively unaltered. Surface and volume

  11. Bismuth doped lanthanum ferrite perovskites as novel cathodes for intermediate-temperature solid oxide fuel cells.

    PubMed

    Li, Mei; Wang, Yao; Wang, Yunlong; Chen, Fanglin; Xia, Changrong

    2014-07-23

    Bismuth is doped to lanthanum strontium ferrite to produce ferrite-based perovskites with a composition of La(0.8-x)Bi(x)Sr0.2FeO(3-δ) (0 ≤ x ≤ 0.8) as novel cathode material for intermediate-temperature solid oxide fuel cells. The perovskite properties including oxygen nonstoichiometry coefficient (δ), average valence of Fe, sinterability, thermal expansion coefficient, electrical conductivity (σ), oxygen chemical surface exchange coefficient (K(chem)), and chemical diffusion coefficient (D(chem)) are explored as a function of bismuth content. While σ decreases with x due to the reduced Fe(4+) content, D(chem) and K(chem) increase since the oxygen vacancy concentration is increased by Bi doping. Consequently, the electrochemical performance is substantially improved and the interfacial polarization resistance is reduced from 1.0 to 0.10 Ω cm(2) at 700 °C with Bi doping. The perovskite with x = 0.4 is suggested as the most promising composition as solid oxide fuel cell cathode material since it has demonstrated high electrical conductivity and low interfacial polarization resistance.

  12. [Niacin deficiency and cutaneous immunity].

    PubMed

    Ikenouchi-Sugita, Atsuko; Sugita, Kazunari

    2015-01-01

    Niacin, also known as vitamin B3, is required for the synthesis of coenzymes, nicotinamide adenine dinucleotide (NAD) and nicotinamide adenine dinucleotide phosphate (NADP). Niacin binds with G protein-coupled receptor (GPR) 109A on cutaneous Langerhans cells and causes vasodilation with flushing in head and neck area. Niacin deficiency due to excessive alcohol consumption, certain drugs or inadequate uptake in diet causes pellagra, a photosensitivity dermatitis. Recently several studies have revealed the mechanism of photosensitivity in niacin deficiency, which may pave a way for new therapeutic approaches. The expression level of prostaglandin E synthase (PTGES) is up-regulated in the skin of both pellagra patients and niacin deficient pellagra mouse models. In addition, pellagra is mediated through prostaglandin E₂-EP4 (PGE₂-EP4) signaling via reactive oxygen species (ROS) production in keratinocytes. In this article, we have reviewed the role of niacin in immunity and the mechanism of niacin deficiency-induced photosensitivity. PMID:25765687

  13. [Niacin deficiency and cutaneous immunity].

    PubMed

    Ikenouchi-Sugita, Atsuko; Sugita, Kazunari

    2015-01-01

    Niacin, also known as vitamin B3, is required for the synthesis of coenzymes, nicotinamide adenine dinucleotide (NAD) and nicotinamide adenine dinucleotide phosphate (NADP). Niacin binds with G protein-coupled receptor (GPR) 109A on cutaneous Langerhans cells and causes vasodilation with flushing in head and neck area. Niacin deficiency due to excessive alcohol consumption, certain drugs or inadequate uptake in diet causes pellagra, a photosensitivity dermatitis. Recently several studies have revealed the mechanism of photosensitivity in niacin deficiency, which may pave a way for new therapeutic approaches. The expression level of prostaglandin E synthase (PTGES) is up-regulated in the skin of both pellagra patients and niacin deficient pellagra mouse models. In addition, pellagra is mediated through prostaglandin E₂-EP4 (PGE₂-EP4) signaling via reactive oxygen species (ROS) production in keratinocytes. In this article, we have reviewed the role of niacin in immunity and the mechanism of niacin deficiency-induced photosensitivity.

  14. Perovskite thin films via atomic layer deposition.

    PubMed

    Sutherland, Brandon R; Hoogland, Sjoerd; Adachi, Michael M; Kanjanaboos, Pongsakorn; Wong, Chris T O; McDowell, Jeffrey J; Xu, Jixian; Voznyy, Oleksandr; Ning, Zhijun; Houtepen, Arjan J; Sargent, Edward H

    2015-01-01

    A new method to deposit perovskite thin films that benefit from the thickness control and conformality of atomic layer deposition (ALD) is detailed. A seed layer of ALD PbS is place-exchanged with PbI2 and subsequently CH3 NH3 PbI3 perovskite. These films show promising optical properties, with gain coefficients of 3200 ± 830 cm(-1) .

  15. A new kind of line defect in NdTiO3 perovskite

    NASA Astrophysics Data System (ADS)

    Topsakal, Mehmet; Jeong, Jong Seok; Xu, Peng; Jalan, Bharat; Wentzcovitch, Renata; Mkhoyan, Andre

    We report an observation of a new line defect in strained NdTiO3 perovskite. Aberration-corrected analytical scanning transmission electron microscopy and first-principles calculations are used to characterize its atomic structure and electronic properties. The defect represents a shift and rotation of the core Ti-O-Nd unit accommodating the deficiency of Ti-O units in neighboring columns and strain. The core of the defect has considerably different electronic properties resulting from Ti being in different oxidation states. This observation closes the dimensionality gap between previously observed point and planar defects in complex oxides needed to accommodate the alterations of stoichiometry and strain. This new line defect should also exist in other multi-valent perovskites, and could open a new avenue for tailoring unexpected and highly-desirable electronic properties. NSF DMR-0819885, DMR-1420013, NSF DMR-1410888, NSF EAR-134866 and EAR-1319361.

  16. Band offset measurement of oxygen annealed SrTiO3/Si

    NASA Astrophysics Data System (ADS)

    Jin, Eric; Kornblum, Lior; Ahn, Charles; Walker, Fred

    Integration of the perovskite oxide SrTiO3 (STO) with silicon by molecular beam epitaxy (MBE) was initially developed for new high-K gate dielectrics, and more recently as a means to combine the multifunctional properties of oxide heterostructures with the well-established silicon platform. The band alignment at an oxide-semiconductor junction is critical in determining its electrical properties, and control over the conduction band offset is a fundamental goal of materials science. Density functional theory calculations have shown that an interface dipole forms at the STO-Si interface, with the magnitude of this dipole determined by the exact composition of the interface. If the interface is oxygen deficient, the band alignment is type II. If the interface is modified via the addition of a monolayer of oxygen atoms, the predicted heterojunction becomes type-I. We characterize the band alignment of MBE-grown STO-Si films by x-ray photoemission spectroscopy and show that the conduction band offset is negative between STO and Si. We demonstrate an experimental ~0.5 eV increase in the conduction band offset for in-situ oxygen-annealed films, in close agreement with theoretical predictions. By careful control of the interface atomic structure, we show an approach toward tuning the band offset of the STO-Si system to modify electronic transport for a variety of device applications.

  17. Phase transformations in superconducting and non-superconducting perovskites

    SciTech Connect

    Mitchell, T.E.

    1992-01-01

    Most of the high {Tc} superconductors and other perovskite-related cuprates exhibit some kind of structural instability. For example, tetragonal-to-orthorhombic phase transformations occur in the Y-Ba-Cu-O and La-Sr-Cu-O systems while crystal structures in the Bi-Ca-Sr-Cu-O and Tl-Ba-Ca-Cu-O systems have incommensurate periodicities associated with displacements of the heavy cations. In YBa{sub 2}Cu{sub 3}O{sub 7{minus}{delta}}, the transformation is due to the ordering of oxygen vacancies while in La{sub 2-x}Sr{sub x}CuO{sub 4} the transformation is accompanied by tilting of the (CuO{sub 6}) octahedra. Such tilting and distortion of the co-ordination octahedra commonly occur in perovskite-related compounds and transformations between the structures are frequently martensitic. Phase transformations in the superconducting cuprates have been investigated by transmission electron microscopy but none of them appear to be martensitic. The phase transformations are accompanied by twinning and the resulting configurations are used to calculate twin boundary energies.

  18. Phase transformations in superconducting and non-superconducting perovskites

    SciTech Connect

    Mitchell, T.E.

    1992-07-01

    Most of the high {Tc} superconductors and other perovskite-related cuprates exhibit some kind of structural instability. For example, tetragonal-to-orthorhombic phase transformations occur in the Y-Ba-Cu-O and La-Sr-Cu-O systems while crystal structures in the Bi-Ca-Sr-Cu-O and Tl-Ba-Ca-Cu-O systems have incommensurate periodicities associated with displacements of the heavy cations. In YBa{sub 2}Cu{sub 3}O{sub 7{minus}{delta}}, the transformation is due to the ordering of oxygen vacancies while in La{sub 2-x}Sr{sub x}CuO{sub 4} the transformation is accompanied by tilting of the [CuO{sub 6}] octahedra. Such tilting and distortion of the co-ordination octahedra commonly occur in perovskite-related compounds and transformations between the structures are frequently martensitic. Phase transformations in the superconducting cuprates have been investigated by transmission electron microscopy but none of them appear to be martensitic. The phase transformations are accompanied by twinning and the resulting configurations are used to calculate twin boundary energies.

  19. Autothermal reforming of propane over Ni catalysts supported on a variety of perovskites.

    PubMed

    Lim, SeungSoo; Moon, DongJu; Kim, JongHo; Kim, YoungChul; Park, NamCook; Shin, JaeSoon

    2007-11-01

    Autothermal reforming of propane for hydrogen over Ni catalysts supported on a variety of perovskites was performed in an atmospheric flow reactor. Perovskite is known for its higher thermal stability and oxygen storage capacity, but catalytic activity of itself is low. A sites of the ABO3 structured perovskites were occupied by La while B sites by one of Fe, Co, Ni, and Al by citrate method. The composition of the reactant mixture was H2O/C/O2 = 8.96/1.0/1.1. The changes in the states of the catalysts after reaction were analyzed by XRD, TPD, and TGA. Ni/LaAlO3 catalyst maintained the perovskite structure after reaction. It showed higher hydrogen yield and thermal stability compared to those of the catalysts with Fe, Co, or Ni in B sites. Catalysts prepared by deposition-precipitation (DP) method showed higher activity than those prepared by impregnation method, presumably due to the smaller sizes of the NiO crystal particles.

  20. Modeling Anomalous Hysteresis in Perovskite Solar Cells.

    PubMed

    van Reenen, Stephan; Kemerink, Martijn; Snaith, Henry J

    2015-10-01

    Organic-inorganic lead halide perovskites are distinct from most other semiconductors because they exhibit characteristics of both electronic and ionic motion. Accurate understanding of the optoelectronic impact of such properties is important to fully optimize devices and be aware of any limitations of perovskite solar cells and broader optoelectronic devices. Here we use a numerical drift-diffusion model to describe device operation of perovskite solar cells. To achieve hysteresis in the modeled current-voltage characteristics, we must include both ion migration and electronic charge traps, serving as recombination centers. Trapped electronic charges recombine with oppositely charged free electronic carriers, of which the density depends on the bias-dependent ion distribution in the perovskite. Our results therefore show that reduction of either the density of mobile ionic species or carrier trapping at the perovskite interface will remove the adverse hysteresis in perovskite solar cells. This gives a clear target for ongoing research effort and unifies previously conflicting experimental observations and theories.

  1. Ambipolar solution-processed hybrid perovskite phototransistors

    PubMed Central

    Li, Feng; Ma, Chun; Wang, Hong; Hu, Weijin; Yu, Weili; Sheikh, Arif D.; Wu, Tom

    2015-01-01

    Organolead halide perovskites have attracted substantial attention because of their excellent physical properties, which enable them to serve as the active material in emerging hybrid solid-state solar cells. Here we investigate the phototransistors based on hybrid perovskite films and provide direct evidence for their superior carrier transport property with ambipolar characteristics. The field-effect mobilities for triiodide perovskites at room temperature are measured as 0.18 (0.17) cm2 V−1 s−1 for holes (electrons), which increase to 1.24 (1.01) cm2 V−1 s−1 for mixed-halide perovskites. The photoresponsivity of our hybrid perovskite devices reaches 320 A W−1, which is among the largest values reported for phototransistors. Importantly, the phototransistors exhibit an ultrafast photoresponse speed of less than 10 μs. The solution-based process and excellent device performance strongly underscore hybrid perovskites as promising material candidates for photoelectronic applications. PMID:26345730

  2. Perovskite solar cells: from materials to devices.

    PubMed

    Jung, Hyun Suk; Park, Nam-Gyu

    2015-01-01

    Perovskite solar cells based on organometal halide light absorbers have been considered a promising photovoltaic technology due to their superb power conversion efficiency (PCE) along with very low material costs. Since the first report on a long-term durable solid-state perovskite solar cell with a PCE of 9.7% in 2012, a PCE as high as 19.3% was demonstrated in 2014, and a certified PCE of 17.9% was shown in 2014. Such a high photovoltaic performance is attributed to optically high absorption characteristics and balanced charge transport properties with long diffusion lengths. Nevertheless, there are lots of puzzles to unravel the basis for such high photovoltaic performances. The working principle of perovskite solar cells has not been well established by far, which is the most important thing for understanding perovksite solar cells. In this review, basic fundamentals of perovskite materials including opto-electronic and dielectric properties are described to give a better understanding and insight into high-performing perovskite solar cells. In addition, various fabrication techniques and device structures are described toward the further improvement of perovskite solar cells.

  3. Alpha-1 Antitrypsin Deficiency

    MedlinePlus

    ... Liver Disease Information > Alpha-1 Antitrypsin Deficiency Alpha-1 Antitrypsin Deficiency Explore this section to learn more about alpha-1 antitrypsin deficiency, including a description of the disorder ...

  4. Mixed metallic Ba(Co,Mn)X{sub 0.2-x}O{sub 3-{delta}} (X=F, Cl) hexagonal perovskites

    SciTech Connect

    Iorgulescu, Mihaela; Roussel, Pascal; Tancret, Nathalie; Renaut, Nicolas; Tiercelin, Nicolas; Mentre, Olivier

    2013-02-15

    We show here that the incorporation of Mn in Ba-Co-oxohalide, BaCoX{sub 0.2-x}O{sub 3-{delta}}, hexagonal perovskite stabilizes the 6H-form (stacking sequence (chhhch Prime ); c, h=[BaO{sub 3}] and h Prime =[BaOX] layers), with tetramers of face-sharing octahedra) rather than the trimeric 10H-form. On the contrary to previous results on the Fe incorporation in similar system leading to more reduced 10H-compounds, the Mn effect is to increase the mean (Co/Mn) valence better suited to the 6H form. We experienced a poor Mn/Co miscibility during our syntheses leading to great difficulties to isolate mixed Co/Mn single phase materials and/or weak reproducibility. Powder neutron diffraction data shows a mixed Mn/Co octahedral occupancy, while the tetrahedra are filled by Co{sup 3+} cations. Anionic vacancies were refined in the h Prime -[BaO{sub 1-z}X{sub 1-x}] layer and the next c-[BaO{sub 3-z}] layers, while the h-[BaO{sub 3}] layers are not oxygen deficient. Magnetic properties suggest that a part of Mn cations remain paramagnetic until low temperature, while isolated spin clusters (probably driven by AFM Co tetrahedral dimers) behave as low-dimensional AFM systems. Transport measurements reveal a transition from high-temperature metallic to low-temperature semi-conducting states that could occur from defect shallow donor upon the Mn for Co substitution. - Graphical abstract: The incorporation of Mn in Ba-Co-oxohalide, BaCoX{sub 0.2-x}O{sub 3-{delta}}, hexagonal perovskite stabilizes the 6H-form with tetrameric (Co,Mn){sub 4}O{sub 15} face sharing linear chains. This results from a oxidizing Mn effect and particular Mn/Co distribution. Highlights: Black-Right-Pointing-Pointer The incorporation of Mn in BaCoX{sub 0.2-x}O{sub 3-{delta}} (X=F,Cl) hexagonal perovskites stabilizes the 6H-form. Black-Right-Pointing-Pointer It contains tetrameric (Co,Mn){sub 4}O{sub 15} face sharing linear chains. Black-Right-Pointing-Pointer The preference for such chains better than

  5. Multiferroicity in Perovskite Manganite Superlattice

    NASA Astrophysics Data System (ADS)

    Tao, Yong-Mei; Jiang, Xue-Fan; Liu, Jun-Ming

    2016-08-01

    Multiferroic properties of short period perovskite type manganite superlattice ((R1MnO3)n/(R2MnO3)n (n=1,2,3)) are considered within the framework of classical Heisenberg model using Monte Carlo simulation. Our result revealed the interesting behaviors in Mn spins structure in superlattice. Apart from simple plane spin cycloid structure which is shown in all manganites including bulk, film, and superlattice here in low temperature, a non-coplanar spiral spin structure is exhibited in a certain temperature range when n equals 1, 2 or 3. Specific heat, spin-helicity vector, spin correlation function, spin-helicity correlation function, and spin configuration are calculated to confirm this non-coplanar spiral spin structure. These results are associated with the competition among exchange interaction, magnetic anisotropy, and Dzyaloshinskii-Moriya interaction. Supported by the National Natural Science Foundation of China (NSFC) under Grant No. 11447136

  6. Effect of Perovskite Overlayers on TiO2 Electrodes in Perovskite-Sensitized Solar Cells.

    PubMed

    Kim, Kang-Pil; Kim, Jeong-Hwa; Hwang, Dae-Kue

    2016-05-01

    In this paper, we have studied the effect of the thickness of a CH3NH3PbI3 perovskite overlayer on mesoporous TiO2 electrodes in perovskite solar cells. The overlayers were prepared by spin coating PbI2 films on the electrodes, which were subsequently exposed to a CH3NH3I/2-propanol solution. We controlled the thickness of the perovskite overlayer by changing the PbI2 solution concentration. The thicknesses of the overlayers spin-coated from 0.5, 0.75, 0.9, and 1 M PbI2 solutions were approximately 179, 262, 316, and 341 nm, respectively. Perovskite solar cells with an approximately 316-nm-thick overlayer showed the highest efficiency of 9.11%. We conclude that optimization of the perovskite overlayer thickness in the solar cell structure is necessary to improve the cell efficiency. PMID:27483921

  7. First-principles Calculations of Nuclear Magnetic Resonance Chemical Shielding Tensors in Complex Ferroelectric Perovskites

    NASA Astrophysics Data System (ADS)

    Pechkis, Daniel Lawrence

    Nuclear magnetic resonance (NMR) spectroscopy is one of the most important experimental probes of local atomistic structure, chemical ordering, and dynamics. Recently, NMR has increasingly been used to study complex ferroelectric perovskite alloys, where spectra can be difficult to interpret. First-principles calculations of NMR spectra can greatly assist in this task. In this work, oxygen, titanium, and niobium NMR chemical shielding tensors, ŝ , were calculated with first-principles methods for ferroelectric transition metal prototypical ABO3 perovskites [SrTiO3, BaTiO 3, PbTiO3 and PbZrO3] and A(B,B')O3 perovskite alloys Pb(Zr1/2Ti1/2)O3 (PZT) and Pb(Mg1/3Nb2/3)O3 (PMN). The principal findings are 1) a large anisotropy between deshielded sigma xx(O) ≃ sigmayy(O) and shielded sigma zz(O) components; 2) a nearly linear dependence on nearest-distance transition-metal/oxygen bond length, rs, was found for both isotropic deltaiso(O) and axial deltaax(O) chemical shifts ( d̂=ŝ reference- ŝ ), across all the systems studied, with deltaiso(O) varying by ≃ 400 ppm; 3) the demonstration that the anisotropy and linear variation arise from large paramagnetic contributions to sigmaxx(O) and sigmayy(O), due to virtual transitions between O(2p) and unoccupied B(nd) states. Using these results, an argument against Ti clustering in PZT, as conjectured from recent 17O NMR magic-angle-spinning measurements, is made. The linear dependence of the chemical shifts on rs provides a scale for determining transition-metal/oxygen bond lengths from experimental 17O NMR spectra. As such, it can be used to assess the degree of local tetragonality in perovskite solid solutions for piezoelectric applications. Results for transition metal atoms show less structural sensitivity, compared to 17O NMR, in homovalent B-site materials, but could be more useful in heterovalent B-site perovskite alloys. This work shows that both 17O and B-site NMR spectroscopy, coupled with first principles

  8. Making and Breaking of Lead Halide Perovskites.

    PubMed

    Manser, Joseph S; Saidaminov, Makhsud I; Christians, Jeffrey A; Bakr, Osman M; Kamat, Prashant V

    2016-02-16

    A new front-runner has emerged in the field of next-generation photovoltaics. A unique class of materials, known as organic metal halide perovskites, bridges the gap between low-cost fabrication and exceptional device performance. These compounds can be processed at low temperature (typically in the range 80-150 °C) and readily self-assemble from the solution phase into high-quality semiconductor thin films. The low energetic barrier for crystal formation has mixed consequences. On one hand, it enables inexpensive processing and both optical and electronic tunability. The caveat, however, is that many as-formed lead halide perovskite thin films lack chemical and structural stability, undergoing rapid degradation in the presence of moisture or heat. To date, improvements in perovskite solar cell efficiency have resulted primarily from better control over thin film morphology, manipulation of the stoichiometry and chemistry of lead halide and alkylammonium halide precursors, and the choice of solvent treatment. Proper characterization and tuning of processing parameters can aid in rational optimization of perovskite devices. Likewise, gaining a comprehensive understanding of the degradation mechanism and identifying components of the perovskite structure that may be particularly susceptible to attack by moisture are vital to mitigate device degradation under operating conditions. This Account provides insight into the lifecycle of organic-inorganic lead halide perovskites, including (i) the nature of the precursor solution, (ii) formation of solid-state perovskite thin films and single crystals, and (iii) transformation of perovskites into hydrated phases upon exposure to moisture. In particular, spectroscopic and structural characterization techniques shed light on the thermally driven evolution of the perovskite structure. By tuning precursor stoichiometry and chemistry, and thus the lead halide charge-transfer complexes present in solution, crystallization

  9. Magnesium and Titanium Isotopic Compositions of an Unusual Hibonite-Perovskite Refractory Inclusion from Allende: It Is Fun

    NASA Technical Reports Server (NTRS)

    Liu, M.-C.; Keller, L. P.; McKeegan, K. D.

    2016-01-01

    Introduction: Hibonite-rich refractory inclusions are among the first solids that formed in the solar nebula, and thus provide constraints on the earliest environment in the Solar System. An unusual hibonite-perovskite inclusion from Allende, SHAL, consists of a large (approximately 500 by 200 microns) single hibonite crystal and coexisting blocky perovskite (approximately 200 microns in size). The hibonite is characterized by chemical and oxygen isotopic compositions similar to those in the FUN (Fractionated and Unknown Nuclear anomalies) inclusion HAL. However, the rare earth element (REE) patterns measured at different spots of SHAL hibonite are highly variable, ranging from Group II-like (light REEs enriched relative to heavy REEs) to Group III-like (relatively flat with slight Eu depletions), but overall contrast largely with that of HAL, especially in the Ce and Yb abundances. This implies that SHAL hibonite formed and underwent distillation processes under more reducing conditions. Interestingly, the accompanying perovskite has uniform, unfractionated oxygen isotopic compositions (averaging delta (sup 17) O equals delta (sup 18) O equals -7 per mille) and REE abundances that are completely different from those of SHAL hibonite. This has been interpreted that perovskite and hibonite may not be co-genetic. Here we performed Al-Mg and Ti isotopic measurements of SHAL hibonite and perovskite to determine if the FUN characteristics are observed in these two isotope systems, and to further constrain the origin and evolution of SHAL. Results: Isotopic measurements of Al-Mg and Ti in SHAL were performed on the UCLA CAMECA ims-1290 ion microprobe by following the analytical protocols described in [1]. The Al-Mg and Ti data obtained in both terrestrial standards and SHAL hibonite and perovskite are shown below. Both SHAL hibonite and perovskite, despite very high (sup 27) Al to (sup 24) Mg ratios, are devoid of (sup 26) Mg excesses that can be attributed to the decay

  10. X-ray imaging: Perovskites target X-ray detection

    NASA Astrophysics Data System (ADS)

    Heiss, Wolfgang; Brabec, Christoph

    2016-05-01

    Single crystals of perovskites are currently of interest to help fathom fundamental physical parameters limiting the performance of perovskite-based polycrystalline solar cells. Now, such perovskites offer a technology platform for optoelectronic devices, such as cheap and sensitive X-ray detectors.

  11. Efficient Visible Quasi-2D Perovskite Light-Emitting Diodes.

    PubMed

    Byun, Jinwoo; Cho, Himchan; Wolf, Christoph; Jang, Mi; Sadhanala, Aditya; Friend, Richard H; Yang, Hoichang; Lee, Tae-Woo

    2016-09-01

    Efficient quasi-2D-structure perovskite light-emitting diodes (4.90 cd A(-1) ) are demonstrated by mixing a 3D-structured perovskite material (methyl ammonium lead bromide) and a 2D-structured perovskite material (phenylethyl ammonium lead bromide), which can be ascribed to better film uniformity, enhanced exciton confinement, and reduced trap density. PMID:27334788

  12. Efficient Visible Quasi-2D Perovskite Light-Emitting Diodes.

    PubMed

    Byun, Jinwoo; Cho, Himchan; Wolf, Christoph; Jang, Mi; Sadhanala, Aditya; Friend, Richard H; Yang, Hoichang; Lee, Tae-Woo

    2016-09-01

    Efficient quasi-2D-structure perovskite light-emitting diodes (4.90 cd A(-1) ) are demonstrated by mixing a 3D-structured perovskite material (methyl ammonium lead bromide) and a 2D-structured perovskite material (phenylethyl ammonium lead bromide), which can be ascribed to better film uniformity, enhanced exciton confinement, and reduced trap density.

  13. PGK deficiency.

    PubMed

    Beutler, Ernest

    2007-01-01

    Phosphoglycerate kinase (PGK) deficiency is one of the relatively uncommon causes of hereditary non-spherocytic haemolytic anaemia (HNSHA). The gene encoding the erythrocyte enzyme PGK1, is X-linked. Mutations of this gene may cause chronic haemolysis with or without mental retardation and they may cause myopathies, often with episodes of myoglobinuria, or a combination of these clinical manifestations. Twenty-six families have been described and in 20 of these the mutations are known. The reason for different clinical manifestations of mutations of the same gene remains unknown. PMID:17222195

  14. Rational Strategies for Efficient Perovskite Solar Cells.

    PubMed

    Seo, Jangwon; Noh, Jun Hong; Seok, Sang Il

    2016-03-15

    A long-standing dream in the large scale application of solar energy conversion is the fabrication of solar cells with high-efficiency and long-term stability at low cost. The realization of such practical goals depends on the architecture, process and key materials because solar cells are typically constructed from multilayer heterostructures of light harvesters, with electron and hole transporting layers as a major component. Recently, inorganic-organic hybrid lead halide perovskites have attracted significant attention as light absorbers for the fabrication of low-cost and high-efficiency solar cells via a solution process. This mainly stems from long-range ambipolar charge transport properties, low exciton binding energies, and suitable band gap tuning by managing the chemical composition. In our pioneering work, a new photovoltaic platform for efficient perovskite solar cells (PSCs) was proposed, which yielded a high power conversion efficiency (PCE) of 12%. The platform consisted of a pillared architecture of a three-dimensional nanocomposite of perovskites fully infiltrating mesoporous TiO2, resulting in the formation of continuous phases and perovskite domains overlaid with a polymeric hole conductor. Since then, the PCE of our PSCs has been rapidly increased from 3% to over 20% certified efficiency. The unprecedented increase in the PCE can be attributed to the effective integration of the advantageous attributes of the refined bicontinuous architecture, deposition process, and composition of perovskite materials. Specifically, the bicontinuous architectures used in the high efficiency comprise a layer of perovskite sandwiched between mesoporous metal-oxide layer, which is a very thinner than that of used in conventional dye-sensitized solar cells, and hole-conducting contact materials with a metal back contact. The mesoporous scaffold can affect the hysteresis under different scan direction in measurements of PSCs. The hysteresis also greatly depends on

  15. Solid oxide fuel cell composite cathodes based on perovskite and fluorite structures

    NASA Astrophysics Data System (ADS)

    Sadykov, Vladislav; Mezentseva, Natalia; Usoltsev, Vladimir; Sadovskaya, Ekaterina; Ishchenko, Arkady; Pavlova, Svetlana; Bespalko, Yulia; Kharlamova, Tamara; Zevak, Ekaterina; Salanov, Aleksei; Krieger, Tamara; Belyaev, Vladimir; Bobrenok, Oleg; Uvarov, Nikolai; Okhlupin, Yury; Smorygo, Oleg; Smirnova, Alevtina; Singh, Prabhakar; Vlasov, Aleksandr; Korobeynikov, Mikhail; Bryazgin, Aleksandr; Kalinin, Peter; Arzhannikov, Andrei

    This work presents the results related to the functionally graded fluorite (F)-perovskite (P) nanocomposite cathodes for IT SOFC. Nanocrystalline fluorites (GDC, ScCeSZ) and perovskites (LSrMn, LSrFNi) were synthesized by Pechini method. Nanocomposites were prepared by the ultrasonic dispersion of F and P powders in isopropanol with addition of polyvinyl butyral. Different techniques for deposition and sintering of functionally graded cathode materials were applied including traditional approaches as well as original methods, such as radiation-thermal sintering under electron beam or microwave radiation. Morphology, microstructure and elemental composition of nanocomposites was characterized by XRD and HRTEM/SEM with EDX. Even for dense composites, the sizes of perovskite and fluorite domains remain in the nanorange providing developed P-F interfaces. Oxygen isotope heteroexchange and conductivity/weight relaxation studies demonstrated that these interfaces provide a path for fast oxygen diffusion. The redistribution of the elements between P and F phases in nanocomposites occurs without formation of insulating zirconate phases. Button-size fuel cells with nanocomposite functionally graded cathodes, thin YSZ layers and anode Ni/YSZ cermet (either bulk or supported on Ni-Al foam substrates) were manufactured. For optimized composition and functionally graded design of P-F nanocomposite cathodes, a stable performance in the intermediate temperature range with maximum power density up to 0.5 W cm -2 at 700 °C in wet H 2/air feeds was demonstrated.

  16. Perovskites with the Framework-Forming Xenon.

    PubMed

    Britvin, Sergey N; Kashtanov, Sergei A; Krzhizhanovskaya, Maria G; Gurinov, Andrey A; Glumov, Oleg V; Strekopytov, Stanislav; Kretser, Yury L; Zaitsev, Anatoly N; Chukanov, Nikita V; Krivovichev, Sergey V

    2015-11-23

    The Group 18 elements (noble gases) were the last ones in the periodic system to have not been encountered in perovskite structures. We herein report the synthesis of a new group of double perovskites KM(XeNaO6) (M = Ca, Sr, Ba) containing framework-forming xenon. The structures of the new compounds, like other double perovskites, are built up of the alternating sequence of corner-sharing (XeO6) and (NaO6) octahedra arranged in a three-dimensional rocksalt order. The fact that xenon can be incorporated into the perovskite structure provides new insights into the problem of Xe depletion in the atmosphere. Since octahedrally coordinated Xe(VIII) and Si(IV) exhibit close values of ionic radii (0.48 and 0.40 Å, respectively), one could assume that Xe(VIII) can be incorporated into hyperbaric frameworks such as MgSiO3 perovskite. The ability of Xe to form stable inorganic frameworks can further extend the rich and still enigmatic chemistry of this noble gas. PMID:26429762

  17. The Structural Disorder and Lattice Stability of (Ba,Sr)(Co,Fe)O3 Complex Perovskites

    SciTech Connect

    S.N.Rashkeev

    2011-05-01

    The structural disorder and lattice stability of complex perovskite (Ba,Sr)(Co,Fe)O3, a promising cathode material for solid oxide fuel cells and oxygen permeation membranes, is explored by means of first principles DFT calculations. It is predicted that Ba and Sr ions easily exchange their lattice positions (A-cation disorder) similarly to Co and Fe ions (B-cation disorder). The cation antisite defects (exchange of A- and B-type cations) have a relatively high formation energy. The BSCF is predicted to exist in an equilibrium mixture of several phases and can decompose exothermically into the Ba- and Co-rich hexagonal (Ba,Sr)CoO3 and Sr- and Fe-rich cubic (Ba,Sr)FeO3 perovskites.

  18. A Heteroepitaxial Perovskite Metal-Base Transistor

    SciTech Connect

    Yajima, T.; Hikita, Y.; Hwang, H.Y.; /Tokyo U. /JST, PRESTO /SLAC

    2011-08-11

    'More than Moore' captures a concept for overcoming limitations in silicon electronics by incorporating new functionalities in the constituent materials. Perovskite oxides are candidates because of their vast array of physical properties in a common structure. They also enable new electronic devices based on strongly-correlated electrons. The field effect transistor and its derivatives have been the principal oxide devices investigated thus far, but another option is available in a different geometry: if the current is perpendicular to the interface, the strong internal electric fields generated at back-to-back heterojunctions can be used for oxide electronics, analogous to bipolar transistors. Here we demonstrate a perovskite heteroepitaxial metal-base transistor operating at room temperature, enabled by interface dipole engineering. Analysis of many devices quantifies the evolution from hot-electron to permeable-base behaviour. This device provides a platform for incorporating the exotic ground states of perovskite oxides, as well as novel electronic phases at their interfaces.

  19. Autothermal reforming catalyst having perovskite structure

    DOEpatents

    Krumpel, Michael; Liu, Di-Jia

    2009-03-24

    The invention addressed two critical issues in fuel processing for fuel cell application, i.e. catalyst cost and operating stability. The existing state-of-the-art fuel reforming catalyst uses Rh and platinum supported over refractory oxide which add significant cost to the fuel cell system. Supported metals agglomerate under elevated temperature during reforming and decrease the catalyst activity. The catalyst is a perovskite oxide or a Ruddlesden-Popper type oxide containing rare-earth elements, catalytically active firs row transition metal elements, and stabilizing elements, such that the catalyst is a single phase in high temperature oxidizing conditions and maintains a primarily perovskite or Ruddlesden-Popper structure under high temperature reducing conditions. The catalyst can also contain alkaline earth dopants, which enhance the catalytic activity of the catalyst, but do not compromise the stability of the perovskite structure.

  20. Machine learning bandgaps of double perovskites

    NASA Astrophysics Data System (ADS)

    Pilania, Ghanshyam; Mannodi-Kanakkithodi, Arun; Uberuaga, Blas; Ramprasad, Rampi; Gubernatis, James; Lookman, Turab

    The ability to make rapid and accurate predictions of bandgaps for double perovskites is of much practical interest for a range of applications. While quantum mechanical computations for high-fidelity bandgaps are enormously computation-time intensive and thus impractical in high throughput studies, informatics-based statistical learning approaches can be a promising alternative. Here we demonstrate a systematic feature-engineering approach and a robust learning framework for efficient and accurate predictions of electronic bandgaps for double perovskites. After evaluating a set of nearly 1.2 million features, we identify several elemental features of the constituent atomic species as the most crucial and relevant predictors. The developed models are validated and tested using the best practices of data science (on a dataset of more than 1300 double perovskite bandgaps) and further analyzed to rationalize their prediction performance. Los Alamos National Laboratory LDRD program and the U.S. Department of Energy, Office of Science, Basic Energy Sciences.

  1. Nanoimprinted Perovskite Solar Cells With Enhanced Photocurrent

    NASA Astrophysics Data System (ADS)

    Haroldson, Ross; Balachandran, Balasubramaniam?; Ren, Yixin; Zakhidov, Anvar; Hu, Wenchuang; UTD Nanoimprint Team

    We have developed a new method of Nanoimprint Lithography (NIL) to shape the morphology of organolead trihalide perovskite. With this hot stamping process we created ordered gratings or other micro or nanostructures of perovskite resembling 2D photonic crytals on the scale of 200 to 600 nm from a starting small grain spin-coated film of the same scale. With this new method of nanoimprinting, we demonstrate that perovskite PV device performance can be improved and controlled. Initial results comparing flat vs. NIL-PV structure devices show dramatic increase in photocurrent as well as better crystallinity. The origin of Isc enhancement is explained in terms of better morphology and larger grains, resulting in longer diffusion length of carriers, while better light absorption by photonic crystal nanopatterns cannot be excluded.

  2. Metal halide perovskites for energy applications

    NASA Astrophysics Data System (ADS)

    Zhang, Wei; Eperon, Giles E.; Snaith, Henry J.

    2016-06-01

    Exploring prospective materials for energy production and storage is one of the biggest challenges of this century. Solar energy is one of the most important renewable energy resources, due to its wide availability and low environmental impact. Metal halide perovskites have emerged as a class of semiconductor materials with unique properties, including tunable bandgap, high absorption coefficient, broad absorption spectrum, high charge carrier mobility and long charge diffusion lengths, which enable a broad range of photovoltaic and optoelectronic applications. Since the first embodiment of perovskite solar cells showing a power conversion efficiency of 3.8%, the device performance has been boosted up to a certified 22.1% within a few years. In this Perspective, we discuss differing forms of perovskite materials produced via various deposition procedures. We focus on their energy-related applications and discuss current challenges and possible solutions, with the aim of stimulating potential new applications.

  3. Oxygen Therapy

    MedlinePlus

    Oxygen therapy is a treatment that provides you with extra oxygen. Oxygen is a gas that your body needs to function. Normally, your lungs absorb ... in your home. A different kind of oxygen therapy is called hyperbaric oxygen therapy. It uses oxygen ...

  4. Electronic and Ionic Transport Dynamics in Organolead Halide Perovskites.

    PubMed

    Li, Dehui; Wu, Hao; Cheng, Hung-Chieh; Wang, Gongming; Huang, Yu; Duan, Xiangfeng

    2016-07-26

    Ion migration has been postulated as the underlying mechanism responsible for the hysteresis in organolead halide perovskite devices. However, the electronic and ionic transport dynamics and how they impact each other in organolead halide perovskites remain elusive to date. Here we report a systematic investigation of the electronic and ionic transport dynamics in organolead halide perovskite microplate crystals and thin films using temperature-dependent transient response measurements. Our study reveals that thermally activated ionic and electronic conduction coexist in perovskite devices. The extracted activation energies suggest that the electronic transport is easier, but ions migrate harder in microplates than in thin films, demonstrating that the crystalline quality and grain boundaries can fundamentally modify electronic and ionic transport in perovskites. These findings offer valuable insight on the electronic and ionic transport dynamics in organolead halide perovskites, which is critical for optimizing perovskite devices with reduced hysteresis and improved stability and efficiency.

  5. Functionalization of perovskite thin films with moisture-tolerant molecules

    NASA Astrophysics Data System (ADS)

    Yang, Shuang; Wang, Yun; Liu, Porun; Cheng, Yi-Bing; Zhao, Hui Jun; Yang, Hua Gui

    2016-02-01

    Organic-inorganic hybrid perovskites are particularly suited as light-harvesting materials in photovoltaic devices. The power conversion efficiency of perovskite solar cells has reached certified values of over 20% in just a few years. However, one of the major hindrances for application of these materials in real-world devices is the performance degradation in humid conditions, leading to a rapid loss of photovoltaic response. Here, we demonstrate that hydrophobic tertiary and quaternary alkyl ammonium cations can be successfully assembled on the perovskite surface as efficient water-resisting layers via a facile surface functionalization technique. Such layers can protect the perovskite film under high relative humidity (90 ± 5%) over 30 days. More importantly, devices based on such films can retain the photovoltaic capacities of bulk perovskites, with power conversion efficiencies over 15%. Improving the humidity tolerance of perovskite materials is a necessary step towards large-scale production of high-performance perovskite-based devices under ambient humidity.

  6. Water electrolysis on La1−xSrxCoO3−δ perovskite electrocatalysts

    PubMed Central

    Mefford, J. Tyler; Rong, Xi; Abakumov, Artem M.; Hardin, William G.; Dai, Sheng; Kolpak, Alexie M.; Johnston, Keith P.; Stevenson, Keith J.

    2016-01-01

    Perovskite oxides are attractive candidates as catalysts for the electrolysis of water in alkaline energy storage and conversion systems. However, the rational design of active catalysts has been hampered by the lack of understanding of the mechanism of water electrolysis on perovskite surfaces. Key parameters that have been overlooked include the role of oxygen vacancies, B–O bond covalency, and redox activity of lattice oxygen species. Here we present a series of cobaltite perovskites where the covalency of the Co–O bond and the concentration of oxygen vacancies are controlled through Sr2+ substitution into La1−xSrxCoO3−δ. We attempt to rationalize the high activities of La1−xSrxCoO3−δ through the electronic structure and participation of lattice oxygen in the mechanism of water electrolysis as revealed through ab initio modelling. Using this approach, we report a material, SrCoO2.7, with a high, room temperature-specific activity and mass activity towards alkaline water electrolysis. PMID:27006166

  7. Molybdenum doped Pr0.5Ba0.5MnO3-δ (Mo-PBMO) double perovskite as a potential solid oxide fuel cell anode material

    NASA Astrophysics Data System (ADS)

    Sun, Yi-Fei; Zhang, Ya-Qian; Hua, Bin; Behnamian, Yashar; Li, Jian; Cui, Shao-Hua; Li, Jian-Hui; Luo, Jing-Li

    2016-01-01

    A layered Mo doped Pr0.5Ba0.5MnO3-δ (Mo-PBMO) double perovskite oxide was prepared by a modified sol-gel method and the properties of the fabricated material are characterized by various technologies. The results of X-ray diffraction (XRD), H2-temperature programmed reduction (H2-TPR), NH3-temperature programmed desorption (NH3-TPD), and thermogravimetric analysis (TGA) demonstrate that the treatment in reducing atmosphere at high temperature lead to a significant phase transformation of the material to a single cubic phase as well as with the Mo in multiple oxidized states. Such character leads to the production of large amount of oxygen deficiency with facilitated oxygen diffusion. The electrochemical performance tests of half-cell and single cell SOFCs exhibit the promoted effect of Mo on catalytic activity for the oxidation of H2 and CH4, indicating that Mo-PBMO could serve as an anode material candidate for SOFCs.

  8. Research Update: Luminescence in lead halide perovskites

    NASA Astrophysics Data System (ADS)

    Srimath Kandada, Ajay Ram; Petrozza, Annamaria

    2016-09-01

    Efficiency and dynamics of radiative recombination of carriers are crucial figures of merit for optoelectronic materials. Following the recent success of lead halide perovskites in efficient photovoltaic and light emitting technologies, here we review some of the noted literature on the luminescence of this emerging class of materials. After outlining the theoretical formalism that is currently used to explain the carrier recombination dynamics, we review a few significant works which use photoluminescence as a tool to understand and optimize the operation of perovskite based optoelectronic devices.

  9. Nanoscale investigation of organic - inorganic halide perovskites

    NASA Astrophysics Data System (ADS)

    Cacovich, S.; Divitini, G.; Vrućinić, M.; Sadhanala, A.; Friend, R. H.; Sirringhaus, H.; Deschler, F.; Ducati, C.

    2015-10-01

    Over the last few years organic - inorganic halide perovskite-based solar cells have exhibited a rapid evolution, reaching certified power conversion efficiencies now surpassing 20%. Nevertheless the understanding of the optical and electronic properties of such systems on the nanoscale is still an open problem. In this work we investigate two model perovskite systems (based on iodine - CH3NH3PbI3 and bromine - CH3NH3PbBr3), analysing the local elemental composition and crystallinity and identifying chemical inhomogeneities.

  10. Stability of tetravalent actinides in perovskites

    SciTech Connect

    Williams, C.W.; Morss, L.R.; Choi, I.K.

    1983-01-01

    This paper reports the first determination of the enthalpy of formation of a complex actinide(IV) oxide: ..delta..H/sup 0//sub f/ (BaUO/sub 3/, s, 298 K) = -1690 +- 10 kJ mol/sup -1/. The preparation and properties of this and other actinide(IV) complex oxides are described and are compared with other perovskites BaMO/sub 3/. The relative stabilities of tetravalent and hexavalent uranium in various environments are compared in terms of the oxidation-reduction behavior of uranium in geological nuclear waste storage media; in perovskite, uranium(IV) is very unstable in comparison with uranium(VI).

  11. Excited State Properties of Hybrid Perovskites.

    PubMed

    Saba, Michele; Quochi, Francesco; Mura, Andrea; Bongiovanni, Giovanni

    2016-01-19

    Metal halide perovskites have come to the attention of the scientific community for the progress achieved in solar light conversion. Energy sustainability is one of the priorities of our society, and materials advancements resulting in low-cost but efficient solar cells and large-area lighting devices represent a major goal for applied research. From a basic point of view, perovskites are an exotic class of hybrid materials combining some merits of organic and inorganic semiconductors: large optical absorption, large mobilities, and tunable band gap together with the possibility to be processed in solution. When a novel class of promising semiconductors comes into the limelight, lively discussions ensue on the photophysics of band-edge excitations, because just the states close to the band edge are entailed in energy/charge transport and light emission. This was the case several decades ago for III-V semiconductors, it has been up to 10 years ago for organics, and it is currently the case for perovskites. Our aim in this Account is to rationalize the body of experimental evidence on perovskite photophysics in a coherent theoretical framework, borrowing from the knowledge acquired over the years in materials optoelectronics. A crucial question is whether photon absorption leads to a population of unbound, conductive free charges or instead excitons, neutral and insulating bound states created by Coulomb interaction just below the energy of the band gap. We first focus on the experimental estimates of the exciton binding energy (Eb): at room temperature, Eb is comparable to the thermal energy kBT in MAPbI3 and increases up to values 2-3kBT in wide band gap MAPbBr3 and MAPbCl3. Statistical considerations predict that these values, even though comparable to or larger than thermal energy, let free carriers prevail over bound excitons for all levels of excitation densities relevant for devices. The analysis of photophysics evidence confirms that all hybrid halide

  12. Novel Solvent-free Perovskite Deposition in Fabrication of Normal and Inverted Architectures of Perovskite Solar Cells.

    PubMed

    Nejand, Bahram Abdollahi; Gharibzadeh, Saba; Ahmadi, Vahid; Shahverdi, H Reza

    2016-01-01

    We introduced a new approach to deposit perovskite layer with no need for dissolving perovskite precursors. Deposition of Solution-free perovskite (SFP) layer is a key method for deposition of perovskite layer on the hole or electron transport layers that are strongly sensitive to perovskite precursors. Using deposition of SFP layer in the perovskite solar cells would extend possibility of using many electron and hole transport materials in both normal and invert architectures of perovskite solar cells. In the present work, we synthesized crystalline perovskite powder followed by successful deposition on TiO2 and cuprous iodide as the non-sensitve and sensitive charge transport layers to PbI2 and CH3NH3I solution in DMF. The post compressing step enhanced the efficiency of the devices by increasing the interface area between perovskite and charge transport layers. The 9.07% and 7.71% cell efficiencies of the device prepared by SFP layer was achieved in respective normal (using TiO2 as a deposition substrate) and inverted structure (using CuI as deposition substrate) of perovskite solar cell. This method can be efficient in large-scale and low cost fabrication of new generation perovskite solar cells.

  13. Novel Solvent-free Perovskite Deposition in Fabrication of Normal and Inverted Architectures of Perovskite Solar Cells

    PubMed Central

    Nejand, Bahram Abdollahi; Gharibzadeh, Saba; Ahmadi, Vahid; Shahverdi, H. Reza

    2016-01-01

    We introduced a new approach to deposit perovskite layer with no need for dissolving perovskite precursors. Deposition of Solution-free perovskite (SFP) layer is a key method for deposition of perovskite layer on the hole or electron transport layers that are strongly sensitive to perovskite precursors. Using deposition of SFP layer in the perovskite solar cells would extend possibility of using many electron and hole transport materials in both normal and invert architectures of perovskite solar cells. In the present work, we synthesized crystalline perovskite powder followed by successful deposition on TiO2 and cuprous iodide as the non-sensitve and sensitive charge transport layers to PbI2 and CH3NH3I solution in DMF. The post compressing step enhanced the efficiency of the devices by increasing the interface area between perovskite and charge transport layers. The 9.07% and 7.71% cell efficiencies of the device prepared by SFP layer was achieved in respective normal (using TiO2 as a deposition substrate) and inverted structure (using CuI as deposition substrate) of perovskite solar cell. This method can be efficient in large-scale and low cost fabrication of new generation perovskite solar cells. PMID:27640991

  14. Novel Solvent-free Perovskite Deposition in Fabrication of Normal and Inverted Architectures of Perovskite Solar Cells

    NASA Astrophysics Data System (ADS)

    Nejand, Bahram Abdollahi; Gharibzadeh, Saba; Ahmadi, Vahid; Shahverdi, H. Reza

    2016-09-01

    We introduced a new approach to deposit perovskite layer with no need for dissolving perovskite precursors. Deposition of Solution-free perovskite (SFP) layer is a key method for deposition of perovskite layer on the hole or electron transport layers that are strongly sensitive to perovskite precursors. Using deposition of SFP layer in the perovskite solar cells would extend possibility of using many electron and hole transport materials in both normal and invert architectures of perovskite solar cells. In the present work, we synthesized crystalline perovskite powder followed by successful deposition on TiO2 and cuprous iodide as the non-sensitve and sensitive charge transport layers to PbI2 and CH3NH3I solution in DMF. The post compressing step enhanced the efficiency of the devices by increasing the interface area between perovskite and charge transport layers. The 9.07% and 7.71% cell efficiencies of the device prepared by SFP layer was achieved in respective normal (using TiO2 as a deposition substrate) and inverted structure (using CuI as deposition substrate) of perovskite solar cell. This method can be efficient in large-scale and low cost fabrication of new generation perovskite solar cells.

  15. Novel Solvent-free Perovskite Deposition in Fabrication of Normal and Inverted Architectures of Perovskite Solar Cells.

    PubMed

    Nejand, Bahram Abdollahi; Gharibzadeh, Saba; Ahmadi, Vahid; Shahverdi, H Reza

    2016-01-01

    We introduced a new approach to deposit perovskite layer with no need for dissolving perovskite precursors. Deposition of Solution-free perovskite (SFP) layer is a key method for deposition of perovskite layer on the hole or electron transport layers that are strongly sensitive to perovskite precursors. Using deposition of SFP layer in the perovskite solar cells would extend possibility of using many electron and hole transport materials in both normal and invert architectures of perovskite solar cells. In the present work, we synthesized crystalline perovskite powder followed by successful deposition on TiO2 and cuprous iodide as the non-sensitve and sensitive charge transport layers to PbI2 and CH3NH3I solution in DMF. The post compressing step enhanced the efficiency of the devices by increasing the interface area between perovskite and charge transport layers. The 9.07% and 7.71% cell efficiencies of the device prepared by SFP layer was achieved in respective normal (using TiO2 as a deposition substrate) and inverted structure (using CuI as deposition substrate) of perovskite solar cell. This method can be efficient in large-scale and low cost fabrication of new generation perovskite solar cells. PMID:27640991

  16. Static and dynamic optical properties of La1-xSrxFeO3-δ: The effects of A-site and oxygen stoichiometry

    DOE PAGESBeta

    Sergey Y. Smolin; Sfeir, Matthew Y.; Scafetta, Mark D.; Choquette, Amber K.; Baxter, Jason B.; May, Steven J.

    2015-12-09

    Perovskite oxides are a promising material class for photovoltaic and photocatalytic applications due to their visible band gaps, nanosecond recombination lifetimes, and great chemical diversity. However, there is limited understanding of the link between composition and static and dynamic optical properties, despite the critical role these properties play in the design of light-harvesting devices. To clarify these relationships, we systemically studied the optoelectronic properties in La1-xSrxFeO3-δ epitaxial films, uncovering the effects of A-site cation substitution and oxygen stoichiometry. Variable-angle spectroscopic ellipsometry was used to measure static optical properties, revealing a linear increase in absorption coefficient at 1.25 eV and amore » red-shifting of the optical absorption edge with increasing Sr fraction. The absorption spectra can be similarly tuned through the introduction of oxygen vacancies, indicating the critical role that nominal Fe valence plays in optical absorption. Dynamic optoelectronic properties were studied with ultrafast transient reflectance spectroscopy, revealing similar nanosecond photoexcited carrier lifetimes for oxygen deficient and stoichiometric films with the same nominal Fe valence. Furthermore, these results demonstrate that while the static optical absorption is strongly dependent on nominal Fe valence tuned through cation or anion stoichiometry, oxygen vacancies do not appear to play a significantly detrimental role in the recombination kinetics.« less

  17. Oxygen ion-conducting dense ceramic

    DOEpatents

    Balachandran, Uthamalingam; Kleefisch, Mark S.; Kobylinski, Thaddeus P.; Morissette, Sherry L.; Pei, Shiyou

    1996-01-01

    Preparation, structure, and properties of mixed metal oxide compositions containing at least strontium, cobalt, iron and oxygen are described. The crystalline mixed metal oxide compositions of this invention have, for example, structure represented by Sr.sub..alpha. (Fe.sub.1-x Co.sub.x).sub..alpha.+.beta. O.sub..delta. where x is a number in a range from 0.01 to about 1, .alpha. is a number in a range from about 1 to about 4, .beta. is a number in a range upward from 0 to about 20, and .delta. is a number which renders the compound charge neutral, and wherein the composition has a non-perovskite structure. Use of the mixed metal oxides in dense ceramic membranes which exhibit oxygen ionic conductivity and selective oxygen separation, are described as well as their use in separation of oxygen from an oxygen-containing gaseous mixture.

  18. Oxygen ion-conducting dense ceramic

    DOEpatents

    Balachandran, Uthamalingam; Kleefisch, Mark S.; Kobylinski, Thaddeus P.; Morissette, Sherry L.; Pei, Shiyou

    1997-01-01

    Preparation, structure, and properties of mixed metal oxide compositions containing at least strontium, cobalt, iron and oxygen are described. The crystalline mixed metal oxide compositions of this invention have, for example, structure represented by Sr.sub..alpha. (Fe.sub.1-x Co.sub.x).sub..alpha.+.beta. O.sub..delta. where x is a number in a range from 0.01 to about 1, .alpha. is a number in a range from about 1 to about 4, .beta. is a number in a range upward from 0 to about 20, and .delta. is a number which renders the compound charge neutral, and wherein the composition has a non-perovskite structure. Use of the mixed metal oxides in dense ceramic membranes which exhibit oxygen ionic conductivity and selective oxygen separation, are described as well as their use in separation of oxygen from an oxygen-containing gaseous mixture.

  19. Nanostructured Perovskite LaCo1-xMnxO3 as Bifunctional Catalysts for Rechargeable Metal-Air Batteries

    NASA Astrophysics Data System (ADS)

    Ge, Xiaoming; Li, Bing; Wuu, Delvin; Sumboja, Afriyanti; An, Tao; Hor, T. S. Andy; Zong, Yun; Liu, Zhaolin

    2015-09-01

    Bifunctional catalyst that is active for both oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is one of the most important components of rechargeable metal-air batteries. Nanostructured perovskite bifunctional catalysts comprising La, Co and Mn(LaCo1-xMnxO3, LCMO) are synthesized by hydrothermal methods. The morphology, structure and electrochemical activity of the perovskite bifunctional catalysts are characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and rotating disk electrode (RDE) techniques. Nanorod, nanodisc and nanoparticle are typical morphologies of LCMO. The electrocatalytic activity of LCMO is significantly improved by the addition of conductive materials such as carbon nanotube. To demonstrate the practical utilization, LCMO in the composition of LaCo0.8Mn0.2O3(LCMO82) is used as air cathode catalysts for rechargeable zinc-air batteries. The battery prototype can sustain 470 h or 40 discharge-charge cycles equivalent.

  20. - and Perovskite-Sensitised Mesoscopic Solar Cells

    NASA Astrophysics Data System (ADS)

    Grätzel, Michael; Durrant, James R.

    2015-10-01

    The following sections are included: * Introduction * Historical background * Mode of function of dye-sensitised solar cells * DSSC research and development * Solid-state mesoscopic cells based on molecular dyes or perovskite pigments as sensitisers * Pilot production of modules, field tests and commercial DSSC development * Outlook * Acknowledgements * References

  1. Perovskite solar cells: Different facets of performance

    NASA Astrophysics Data System (ADS)

    Eperon, Giles E.; Ginger, David S.

    2016-08-01

    The electronic properties of halide perovskites vary significantly between crystalline grains, but the impact of this heterogeneity on solar cell performance is unclear. Now, this variability is shown to limit the photovoltaic properties of solar cells, and its origins are linked to differing properties between crystal facets.

  2. Structural features and enhanced high-temperature oxygen ion transport in SrFe{sub 1-x}Ta{sub x}O{sub 3-{delta}}

    SciTech Connect

    Markov, Alexey A.; Shalaeva, Elizaveta V.; Tyutyunnik, Alexander P.; Kuchin, Vasily V.; Patrakeev, Mikhail V.; Leonidov, Ilya A.; Kozhevnikov, Victor L.

    2013-01-15

    Structural features, oxygen non-stoichiometry and transport properties are studied in the oxide series SrFe{sub 1-x}Ta{sub x}O{sub 3-{delta}}, where x=0.2, 0.3 and 0.4. X-ray diffraction and electron microscopy data evidence formation of the inhomogeneous materials at x=0.3 and 0.4, which include phase constituents with a cubic perovskite and a double perovskite structure types. The composition, the amount and the typical grain size of the phase inhomogeneities are shown to depend both on doping and oxygen content. The increased oxygen-ion conductivity is observed in oxygen depleted materials, which is explained by the increase in the amount of cubic perovskite-like phase and development of interfacial pathways favorable for enhanced oxygen ion transport. - Graphical abstract: The structural studies, oxygen content and conductivity measurements suggest that oxygen depletion from the double perovskite phase constituent of SrFe{sub 1-x}Ta{sub x}O{sub 3-{delta}} for x>0.2 is accompanied by formation of pathways for fast ion transport. Black-Small-Square Highlights: Black-Right-Pointing-Pointer The double perovskite type regions are shown to exist in SrFe{sub 1-x}Ta{sub x}O{sub 3-{delta}}. Black-Right-Pointing-Pointer The oxygen depletion is accompanied with phase separation. Black-Right-Pointing-Pointer The phase separation favors formation of pathways for enhanced oxygen ion transport.

  3. Improving the Stability and Performance of Perovskite Light-Emitting Diodes by Thermal Annealing Treatment.

    PubMed

    Yu, Jae Choul; Kim, Dae Woo; Kim, Da Bin; Jung, Eui Dae; Park, Jong Hyun; Lee, Ah-Young; Lee, Bo Ram; Di Nuzzo, Daniele; Friend, Richard H; Song, Myoung Hoon

    2016-08-01

    A perovskite LED with a perovskite film treated under optimum thermal annealing conditions exhibits a significantly enhanced long-term stability with full coverage of the green electroluminescence emission due to the highly uniform morphology of the perovskite film.

  4. More Cu, more problems: Decreased CO2 conversion ability by Cu-doped La0.75Sr0.25FeO3 perovskite oxides

    NASA Astrophysics Data System (ADS)

    Daza, Yolanda A.; Maiti, Debtanu; Hare, Bryan J.; Bhethanabotla, Venkat R.; Kuhn, John N.

    2016-06-01

    The effect of Cu doping on the conversion of CO2 to CO was investigated on H2-reduced La0.75Sr0.25FeO3 perovskite oxides. Six La0.75Sr0.25Fe1 -YCuYO3 perovskites, labeled Cu100*Y (with Y = 0, 0.10, 0.25, 0.50, 0.75, and 1) were synthesized and characterized through X-ray diffraction (XRD), temperature-programmed oxygen vacancy formation, and temperature-programmed reduction (TPR). The incorporation of Cu facilitates the formation of oxygen vacancies at lower temperatures but also increased the instability of the perovskite. DFT simulations suggested that the Cu10 sample is favored to produce oxygen vacancies compared to Cu0 and Cu25 samples, which was consistent with experimental oxygen vacancy formation results. For the Cu0, Cu10, and Cu25 samples, temperature-programmed CO2 conversion (TPO-CO2) after isothermal H2-reduction at 450 °C and post-reduction XRD were performed to evaluate the ability of the materials to convert CO2 at low temperatures and to identify the crystalline phases active in the reaction. The peak conversion of CO2 to CO was achieved 30 °C lower on the Cu10 sample versus the Cu0, but less CO was produced, due to a decreased re-oxidation activity of the Cu-doped samples. CO production was inhibited in the Cu25 sample, likely due to a combined effect of poor CO2 dissociative chemisorption energies on metallic Cu and increased thermodynamic stability of the oxygen vacant perovskites. Control experiments (Cu deposited onto La0.75Sr0.25FeO3) indicated the stability of the copper-containing perovskite oxides phases was the primary limiting factor preventing CO formation from CO2.

  5. Interplay of octahedral rotations and breathing distortions in charge-ordering perovskite oxides

    NASA Astrophysics Data System (ADS)

    Balachandran, Prasanna V.; Rondinelli, James M.

    2013-08-01

    We investigate the structure-property relationships in ABO3 perovskites exhibiting octahedral rotations and cooperative octahedral breathing distortions (CBD) using group theoretical methods. Rotations of octahedra are ubiquitous in the perovskite family, while the appearance of breathing distortions—oxygen displacement patterns that lead to approximately uniform dilation and contraction of the BO6 octahedra—are rarer in compositions with a single, chemically unique B site. The presence of a CBD relies on electronic instabilities of the B-site cations, either orbital degeneracies or valence-state fluctuations, and often appear concomitant with charge order metal-insulator transitions or B-site cation ordering. We enumerate the structural variants obtained from rotational and breathing lattice modes and formulate a general Landau functional describing their interaction. We use this information and combine it with statistical correlation techniques to evaluate the role of atomic scale distortions on the critical temperatures in representative charge ordering nickelate and bismuthate perovskites. Our results provide microscopic insights into the underlying structure-property interactions across electronic and magnetic phase boundaries, suggesting plausible routes to tailor the behavior of functional oxides by design.

  6. Catalytic combustion of methane by perovskite-type oxide nanoparticles as pollution prevention strategy

    NASA Astrophysics Data System (ADS)

    Zaza, F.; Luisetto, I.; Serra, E.; Tuti, S.; Pasquali, M.

    2016-06-01

    The transition from the existing brown economy towards the desired green economy drives the research efforts to the development of advanced technologies promoting the efficient utilization of energy sources. Catalysis science offers to combustion technology significant opportunity to increase the fuel efficiency by lowering the internal temperature gradients and reduce the environmental impact by lowering local peak temperature and, consequently, thermodynamically inhibiting the nitrogen oxides formation. Alternative catalytic materials are transition metals oxide, including complex oxides with perovskite crystalline structure. The aim of this work is to synthetize lanthanum ferrite perovskites with lanthanum ions partially substituted by strontium ions in order to study the substitution effects on structural properties and redox activity of the original oxide. Lanthanum ferrite oxides partially substituted with different Strontium amount were synthesized by solution combustion method. The perovskite nanopowders obtained were characterized by XRD, SEM, TPR analyses for defining crystalline structure, morphology and redox properties. Finally, the catalytic activity for methane combustion was tested. The most performing catalysts was La0.6Sr0.4FeO3 having the highest oxygen vacancy concentration as revealed by TPR analysis.

  7. Oxygen Transport Ceramic Membranes

    SciTech Connect

    S. Bandopadhyay; N. Nagabhushana

    2003-08-07

    In the present quarter, experiments are presented on ceramic/metal interactions of Zirconia/ Ni-B-Si system and with a thin Ti coating deposited on zirconia surface. Existing facilities were modified for evaluation of environmental assisted slow crack growth and creep in flexural mode. Processing of perovskites of LSC, LSF and LSCF composition were continued for evaluation of mechanical properties as a function of environment. These studies in parallel to those on the LSFCO composition is expect to yield important information on questions such as the role of cation segregation and the stability of the perovskite structure on crack initiation vs. crack growth. Studies have been continued on the La{sub 1-x}Sr{sub x}FeO{sub 3-d} composition using neutron diffraction and TGA studies. A transition from p-type to n-type of conductor was observed at relative low pO{sub 2}, at which the majority carriers changed from the holes to electrons because of the valence state decreases in Fe due to the further loss of oxygen. Investigation on the thermodynamic properties of the membrane materials are continued to develop a complete model for the membrane transport. Data obtained at 850 C show that the stoichiometry in La{sub 0.2}Sr{sub 0.8}Fe{sub 0.8}Cr{sub 0.2}O{sub 3-x} vary from {approx}2.85 to 2.6 over the pressure range studied. From the stoichiometry a lower limit of 2.6 corresponding to the reduction of all Fe{sup 4+} to Fe{sup 3+} and no reduction of Cr{sup 3+} is expected.

  8. A-site-deficiency facilitated in situ growth of bimetallic Ni-Fe nano-alloys: a novel coking-tolerant fuel cell anode catalyst

    NASA Astrophysics Data System (ADS)

    Sun, Yi-Fei; Li, Jian-Hui; Cui, Lin; Hua, Bin; Cui, Shao-Hua; Li, Jian; Luo, Jing-Li

    2015-06-01

    To date, most investigations of Ni-Fe bimetallic catalysts for solid oxide fuel cells (SOFCs) have focused on materials with micro-scale particle sizes, which severely restrict their catalytic activity. In this study, we fabricated a Ni- and/or Fe-doped A-site-deficient LaSrCrO3 perovskite (A-LSC) bimetallic anode material on which the in situ exsolution of uniformly dispersed nano Ni, Fe and Ni-Fe alloy with an average particle size of 25 to 30 nm was facilitated by the introduction of A-site deficiency under a reducing atmosphere. The dopants were shown to significantly enhance the electrical conductivity of the material by many orders of magnitude. Further characterization of the bimetallic material showed that the addition of Fe changed the reduction behavior and increased the amount of oxygen vacancies in the material. Fuel cell performance tests demonstrated that the prepared bimetallic anode catalyst with a highly catalytically active nano Ni-Fe alloy promoted the electrochemical performance in 5000 ppm H2S-syngas and improved the carbon deposition resistance compared to a monometallic anode catalyst.

  9. Morphology-Controlled Synthesis of Organometal Halide Perovskite Inverse Opals.

    PubMed

    Chen, Kun; Tüysüz, Harun

    2015-11-01

    The booming development of organometal halide perovskites in recent years has prompted the exploration of morphology-control strategies to improve their performance in photovoltaic, photonic, and optoelectronic applications. However, the preparation of organometal halide perovskites with high hierarchical architecture is still highly challenging and a general morphology-control method for various organometal halide perovskites has not been achieved. A mild and scalable method to prepare organometal halide perovskites in inverse opal morphology is presented that uses a polystyrene-based artificial opal as hard template. Our method is flexible and compatible with different halides and organic ammonium compositions. Thus, the perovskite inverse opal maintains the advantage of straightforward structure and band gap engineering. Furthermore, optoelectronic investigations reveal that morphology exerted influence on the conducting nature of organometal halide perovskites. PMID:26376773

  10. Band gap engineering strategy via polarization rotation in perovskite ferroelectrics

    SciTech Connect

    Wang, Fenggong Grinberg, Ilya; Rappe, Andrew M.

    2014-04-14

    We propose a strategy to engineer the band gaps of perovskite oxide ferroelectrics, supported by first principles calculations. We find that the band gaps of perovskites can be substantially reduced by as much as 1.2 eV through local rhombohedral-to-tetragonal structural transition. Furthermore, the strong polarization of the rhombohedral perovskite is largely preserved by its tetragonal counterpart. The B-cation off-center displacements and the resulting enhancement of the antibonding character in the conduction band give rise to the wider band gaps of the rhombohedral perovskites. The correlation between the structure, polarization orientation, and electronic structure lays a good foundation for understanding the physics of more complex perovskite solid solutions and provides a route for the design of photovoltaic perovskite ferroelectrics.

  11. Neutral- and Multi-Colored Semitransparent Perovskite Solar Cells.

    PubMed

    Lee, Kyu-Tae; Guo, L Jay; Park, Hui Joon

    2016-04-11

    In this review, we summarize recent works on perovskite solar cells with neutral- and multi-colored semitransparency for building-integrated photovoltaics and tandem solar cells. The perovskite solar cells exploiting microstructured arrays of perovskite "islands" and transparent electrodes-the latter of which include thin metallic films, metal nanowires, carbon nanotubes, graphenes, and transparent conductive oxides for achieving optical transparency-are investigated. Moreover, the perovskite solar cells with distinctive color generation, which are enabled by engineering the band gap of the perovskite light-harvesting semiconductors with chemical management and integrating with photonic nanostructures, including microcavity, are discussed. We conclude by providing future research directions toward further performance improvements of the semitransparent perovskite solar cells.

  12. Morphology-Controlled Synthesis of Organometal Halide Perovskite Inverse Opals.

    PubMed

    Chen, Kun; Tüysüz, Harun

    2015-11-01

    The booming development of organometal halide perovskites in recent years has prompted the exploration of morphology-control strategies to improve their performance in photovoltaic, photonic, and optoelectronic applications. However, the preparation of organometal halide perovskites with high hierarchical architecture is still highly challenging and a general morphology-control method for various organometal halide perovskites has not been achieved. A mild and scalable method to prepare organometal halide perovskites in inverse opal morphology is presented that uses a polystyrene-based artificial opal as hard template. Our method is flexible and compatible with different halides and organic ammonium compositions. Thus, the perovskite inverse opal maintains the advantage of straightforward structure and band gap engineering. Furthermore, optoelectronic investigations reveal that morphology exerted influence on the conducting nature of organometal halide perovskites.

  13. Oxygen Transport Ceramic Membranes

    SciTech Connect

    S. Bandopadhyay; T. Nithyanantham; X.-D Zhou; Y-W. Sin; H.U. Anderson; Alan Jacobson; C.A. Mims

    2005-08-01

    The present quarterly report describes some of the investigations on the structural properties of dense OTM bars provided by Praxair and studies on newer composition of Ti doped LSF. In the previous research, the reference point of oxygen occupancy was determined and verified. In the current research, the oxygen occupancy was investigated at 1200 C as a function of oxygen activity and compared with that at 1000 C. The cause of bumps at about 200 C was also investigated by using different heating and cooling rates during TGA. The fracture toughness of LSFT and dual phase membranes at room temperature is an important mechanical property. Vicker's indentation method was used to evaluate this toughness. Through this technique, a K{sub Ic} (Mode-I Fracture Toughness) value is attained by means of semi-empirical correlations between the indentation load and the length of the cracks emanating from the corresponding Vickers indentation impression. In the present investigation, crack propagation behavior was extensively analyzed in order to understand the strengthening mechanisms involved in the non-transforming La based ceramic composites. Cracks were generated using Vicker's indenter and used to identify and evaluate the toughening mechanisms involved. Preliminary results of an electron microscopy study of the origin of the slow kinetics on reduction of ferrites have been obtained. The slow kinetics appear to be related to a non-equilibrium reduction pathway that initially results in the formation of iron particles. At long times, equilibrium can be reestablished with recovery of the perovskite phase. Modeling of the isotopic transients on operating membranes (LSCrF-2828 at 900 C) and a ''frozen'' isotope profile have been analyzed in conjunction with a 1-D model to reveal the gradient in oxygen diffusivity through the membrane under conditions of high chemical gradients.

  14. Oxygen Transport Ceramic Membranes

    SciTech Connect

    S. Bandopadhyay; T. Nithyanantham; X.-D Zhou; Y-W. Sin; H.U. Anderson; Alan Jacobson; C.A. Mims

    2005-02-01

    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. The in situ electrical conductivity and Seebeck coefficient measurements were made on LSFT at 1000 and 1200 C over the oxygen activity range from air to 10{sup -15} atm. The electrical conductivity measurements exhibited a p to n type transition at an oxygen activity of 1 x 10{sup -10} at 1000 C and 1 x 10{sup -6} at 1200 C. Thermogravimetric studies were also carried out over the same oxygen activities and temperatures. Based on the results of these measurements, the chemical and mechanical stability range of LSFT were determined and defect structure was established. The studies on the fracture toughness of the LSFT and dual phase membranes exposed to air and N{sub 2} at 1000 C was done and the XRD and SEM analysis of the specimens were carried out to understand the structural and microstructural changes. The membranes that are exposed to high temperatures at an inert and a reactive atmosphere undergo many structural and chemical changes which affect the mechanical properties. A complete transformation of fracture behavior was observed in the N{sub 2} treated LSFT samples. Further results to investigate the origin of the slow kinetics on reduction of ferrites have been obtained. The slow kinetics appear to be related to a non-equilibrium reduction pathway that initially results in the formation of iron particles. At long times, equilibrium can be reestablished with recovery of the perovskite phase. Recent results on transient kinetic data are presented. The 2-D modeling of oxygen movement has been undertaken in order to fit isotope data. The model is used to study ''frozen'' profiles in patterned or composite membranes.

  15. OXYGEN TRANSPORT CERAMIC MEMBRANES

    SciTech Connect

    Dr. Sukumar Bandopadhyay; Dr. Nagendra Nagabhushana

    2000-10-01

    This is the third quarterly report on oxygen Transport Ceramic Membranes. In the following, the report describes the progress made by our university partners in Tasks 1 through 6, experimental apparatus that was designed and built for various tasks of this project, thermodynamic calculations, where applicable and work planned for the future. (Task 1) Design, fabricate and evaluate ceramic to metal seals based on graded ceramic powder/metal braze joints. (Task 2) Evaluate the effect of defect configuration on ceramic membrane conductivity and long term chemical and structural stability. (Task 3) Determine materials mechanical properties under conditions of high temperatures and reactive atmospheres. (Task 4) Evaluate phase stability and thermal expansion of candidate perovskite membranes and develop techniques to support these materials on porous metal structures. (Task 5) Assess the microstructure of membrane materials to evaluate the effects of vacancy-impurity association, defect clusters, and vacancy-dopant association on the membrane performance and stability. (Task 6) Measure kinetics of oxygen uptake and transport in ceramic membrane materials under commercially relevant conditions using isotope labeling techniques.

  16. Photovoltaic Performance of Perovskite Solar Cells with Different Grain Sizes.

    PubMed

    Kim, Hyung Do; Ohkita, Hideo; Benten, Hiroaki; Ito, Shinzaburo

    2016-02-01

    Perovskite solar cells exhibit improved photovoltaic parameters with increasing perovskite grain size. The larger photocurrent is due to the enhanced absorption efficiency for thicker perovskite layers. The larger open-circuit voltage (VOC ) is ascribed to the reduced trap-assisted recombination for the larger grains. As a result, the power conversion efficiency exceeds 19% at best. Further improvement in VOC would be possible if the trap density were reduced.

  17. Characterization of La1-xSrxMnO3 perovskite catalysts for hydrogen peroxide reduction.

    PubMed

    Yunphuttha, C; Porntheeraphat, S; Wongchaisuwat, A; Tangbunsuk, S; Marr, D W M; Viravathana, P

    2016-06-22

    We investigated the crystalline phase and electronic structure of perovskite-type La1-xSrxMnO3 (0.0 ≤ x ≤ 1.0) (LSMx) catalysts synthesized via the citric sol-gel route, for H2O2 reduction. The resulting materials were characterized by XRD, XANES, TR-XANES, and TPO and, after calcination, consisted of cubic perovskite for 0.0 ≤ x ≤ 0.8 and hexagonal perovskite for x = 1.0. Mn species in the precalcined catalysts were oxidized to Mn(3+) for x = 0.0 to 0.6 and to Mn(2+) for x = 0.8 and 1.0. After calcination, Mn species were present in a mixed oxidation state of Mn(3+)/Mn(4+), while Sr(2+) and La(3+) were not altered. TR-XANES and TPO showed that Mn species were oxidized at 210-220 °C and formed active perovskites LSM0.4 and LSM0.0 at 580 °C and 640 °C. This shows that Sr doping can reduce the oxidation temperature of LSMx with 0.2 ≤ x ≤ 0.4. However, the concentration of Mn(4+) in LSMx is increased which is useful for enhancing their catalytic activity and stability. When tested in an alkaline electrolyte, LSM0.6 containing the optimum Mn(4+)/Mn(3+) ratio promoted the formation of hydroxyl via the oxygen intercalation reaction and exhibited low polarization resistance and the highest catalytic activity for H2O2 reduction. PMID:27271119

  18. Characterization of La1-xSrxMnO3 perovskite catalysts for hydrogen peroxide reduction.

    PubMed

    Yunphuttha, C; Porntheeraphat, S; Wongchaisuwat, A; Tangbunsuk, S; Marr, D W M; Viravathana, P

    2016-06-22

    We investigated the crystalline phase and electronic structure of perovskite-type La1-xSrxMnO3 (0.0 ≤ x ≤ 1.0) (LSMx) catalysts synthesized via the citric sol-gel route, for H2O2 reduction. The resulting materials were characterized by XRD, XANES, TR-XANES, and TPO and, after calcination, consisted of cubic perovskite for 0.0 ≤ x ≤ 0.8 and hexagonal perovskite for x = 1.0. Mn species in the precalcined catalysts were oxidized to Mn(3+) for x = 0.0 to 0.6 and to Mn(2+) for x = 0.8 and 1.0. After calcination, Mn species were present in a mixed oxidation state of Mn(3+)/Mn(4+), while Sr(2+) and La(3+) were not altered. TR-XANES and TPO showed that Mn species were oxidized at 210-220 °C and formed active perovskites LSM0.4 and LSM0.0 at 580 °C and 640 °C. This shows that Sr doping can reduce the oxidation temperature of LSMx with 0.2 ≤ x ≤ 0.4. However, the concentration of Mn(4+) in LSMx is increased which is useful for enhancing their catalytic activity and stability. When tested in an alkaline electrolyte, LSM0.6 containing the optimum Mn(4+)/Mn(3+) ratio promoted the formation of hydroxyl via the oxygen intercalation reaction and exhibited low polarization resistance and the highest catalytic activity for H2O2 reduction.

  19. Trace Element Abundances in an Unusual Hibonite-Perovskite Refractory Inclusion from Allende

    NASA Technical Reports Server (NTRS)

    Mane, Prajkta; Wadhwa, M.; Keller, L. P.

    2013-01-01

    Calcium-aluminum-rich refractory inclusions (CAIs) are thought to be the first-formed solids in the Solar protoplanetary disk and can provide information about the earliest Solar System processes (e.g., [1]). A hibonite-perovskitebearing CAI from the Allende CV3 chondrite (SHAL, [2]) contains a single of 500 micrometers hibonite grain and coarse-grained perovskite. The mineralogy and oxygen isotopic composition of this CAI shows similarities with FUN inclusions, especially HAL [2]. Here we present trace element abundances in SHAL.

  20. Predominant Intermediate-Spin Ferrous Iron in Lowermost Mantle Post-Perovskite and Perovskite

    NASA Astrophysics Data System (ADS)

    Lin, J.; Watson, H. C.; Vanko, G.; Alp, E. E.; Prakapenka, V.; Dera, P.; Struzhkin, V. V.; Kubo, A.; Zhao, J.; McCammon, C.; Evans, W. J.

    2008-12-01

    Silicate post-perovskite and perovskite are believed to be the dominant minerals of the lowermost mantle and the lower mantle, respectively, and their properties, which can be strongly influenced by the electronic state of iron in these phases, affect our understanding of the nature of the deep Earth. To date, in these minerals the electronic spin state of iron remains unknown under lowermost-mantle pressure-temperature conditions, although recent studies have showed an electronic spin crossover from high-spin to low-spin in ferropericlase over an extended pressure-temperature range of the lower mantle (i.e., Lin et al., Science, 2007) and from high-spin to intermediate-spin in silicate perovskite near the top of the lower mantle (McCammon et al., Nature Geoscience, 2008). Here we report the spin and valence states of iron in post-perovskite and perovskite at pressure-temperature conditions relevant to the lowermost mantle using in situ X-ray emission, X-ray diffraction, and synchrotron Mossbauer spectroscopies in a laser-heated diamond cell. Perovskite and post-perovskite display extremely high quadrupole splitting (QS) of approximately 4 mm/s and relatively high center shift in the synchrotron Mossbauer spectra at 110 GPa and 134 GPa, respectively. Our results show that Fe2+ exists predominantly in the intermediate-spin state with a total spin number of one in both phases (Lin et al., Nature Geoscience, 2008). Together with recent results on the effects of the spin transition in the lower-mantle ferropericlase (see a recent review by Lin and Tsuchiya, PEPI, 2008), here we will address how the electronic spin states in lower-mantle phases and their associated effects affect our understanding on the composition, geophysics, and dynamics of the lower mantle.. References: 1. Lin, J. F., H. C. Watson, G. Vanko, E. E. Alp, V. B. Prakapenka, P. Dera, V. V. Struzhkin, A. Kubo, J. Zhao, C. McCammon, W. J. Evans, Intermediate-spin ferrous iron in lowermost mantle post-perovskite

  1. Mixed metallic Ba(Co,Fe)X(0.2)O(3-δ) (X = F, Cl) hexagonal perovskites: drastic effect of Fe-incorporation on structural and electronic features.

    PubMed

    Iorgulescu, Mihaela; Roussel, Pascal; Tancret, Nathalie; Renault, Nicolas; Porcher, Florence; André, Gilles; Kabbour, Houria; Mentré, Olivier

    2012-07-16

    Starting from the parent 10H-Ba(5)Co(5)X(1-x)O(13-δ) (trimeric strings of face-sharing CoO(6) octahedra with terminal CoO(4) tetrahedra, stacking sequence (chhch')(2)) and 6H-Ba(6)Co(6)X(1-x)O(16-δ) (similar with tetrameric strings, stacking sequence chhhch') hexagonal perovskites forms (X = F, Cl; c, h = [BaO(3)] layers ; h' = [BaOX(1-y)] layers), we show here that the Fe incorporation leads to large domains of solid solutions for both X = F and Cl but exclusively stabilizes the 10H-form independently of the synthesis method. In this form, the lowest concentration of h-layers is stabilized by a sensitive metal reduction with increasing the Fe ratio. In a more general context of competition between several hexagonal perovskite polymorphs available for most of the transition metals, this redox change is most probably the key factor driving 1D (face-sharing chains) to 3D (corner-sharing) connectivities. Strikingly, ND data evidence the location of oxygen deficiencies in the tetrahedral (Co/Fe) coordination. This effect is exaggerated at high temperature, while (Co/Fe)O(4-δ) coordinations are completed by the displacement of X(-) anions toward the (Co/Fe) sphere of coordination following a "push-and-pull" mechanism within h'-[BaOX(1-y)] layers. The Fe-incorporation is also accompanied by increasing conduction gaps with predominant 1D variable range hopping. The full series show antiferromagnetic behavior with increasing T(N) as [Fe] increases. For Fe-rich compounds T(N) is estimated about 600 K, as rarely observed for hexagonal perovskite compounds. Finally, magnetic structures of all iron-doped compounds show a site-to-site AFM ordering, different of the magnetic structure of Co-only parent compounds. Here, DFT calculations predict low-spin octahedral Co configurations, but high-spin Fe species in the same sites.

  2. Organohalide Perovskites for Solar Energy Conversion.

    PubMed

    Lin, Qianqian; Armin, Ardalan; Burn, Paul L; Meredith, Paul

    2016-03-15

    Lead-based organohalide perovskites have recently emerged as arguably the most promising of all next generation thin film solar cell technologies. Power conversion efficiencies have reached 20% in less than 5 years, and their application to other optoelectronic device platforms such as photodetectors and light emitting diodes is being increasingly reported. Organohalide perovskites can be solution processed or evaporated at low temperatures to form simple thin film photojunctions, thus delivering the potential for the holy grail of high efficiency, low embedded energy, and low cost photovoltaics. The initial device-driven "perovskite fever" has more recently given way to efforts to better understand how these materials work in solar cells, and deeper elucidation of their structure-property relationships. In this Account, we focus on this element of organohalide perovskite chemistry and physics in particular examining critical electro-optical, morphological, and architectural phenomena. We first examine basic crystal and chemical structure, and how this impacts important solar-cell related properties such as the optical gap. We then turn to deeper electronic phenomena such as carrier mobilities, trap densities, and recombination dynamics, as well as examining ionic and dielectric properties and how these two types of physics impact each other. The issue of whether organohalide perovskites are predominantly nonexcitonic at room temperature is currently a matter of some debate, and we summarize the evidence for what appears to be the emerging field consensus: an exciton binding energy of order 10 meV. Having discussed the important basic chemistry and physics we turn to more device-related considerations including processing, morphology, architecture, thin film electro-optics and interfacial energetics. These phenomena directly impact solar cell performance parameters such as open circuit voltage, short circuit current density, internal and external quantum efficiency

  3. Organohalide Perovskites for Solar Energy Conversion.

    PubMed

    Lin, Qianqian; Armin, Ardalan; Burn, Paul L; Meredith, Paul

    2016-03-15

    Lead-based organohalide perovskites have recently emerged as arguably the most promising of all next generation thin film solar cell technologies. Power conversion efficiencies have reached 20% in less than 5 years, and their application to other optoelectronic device platforms such as photodetectors and light emitting diodes is being increasingly reported. Organohalide perovskites can be solution processed or evaporated at low temperatures to form simple thin film photojunctions, thus delivering the potential for the holy grail of high efficiency, low embedded energy, and low cost photovoltaics. The initial device-driven "perovskite fever" has more recently given way to efforts to better understand how these materials work in solar cells, and deeper elucidation of their structure-property relationships. In this Account, we focus on this element of organohalide perovskite chemistry and physics in particular examining critical electro-optical, morphological, and architectural phenomena. We first examine basic crystal and chemical structure, and how this impacts important solar-cell related properties such as the optical gap. We then turn to deeper electronic phenomena such as carrier mobilities, trap densities, and recombination dynamics, as well as examining ionic and dielectric properties and how these two types of physics impact each other. The issue of whether organohalide perovskites are predominantly nonexcitonic at room temperature is currently a matter of some debate, and we summarize the evidence for what appears to be the emerging field consensus: an exciton binding energy of order 10 meV. Having discussed the important basic chemistry and physics we turn to more device-related considerations including processing, morphology, architecture, thin film electro-optics and interfacial energetics. These phenomena directly impact solar cell performance parameters such as open circuit voltage, short circuit current density, internal and external quantum efficiency

  4. Oxygen transport in nanostructured lanthanum manganites.

    PubMed

    Rossetti, Ilenia; Allieta, Mattia; Biffi, Cesare; Scavini, Marco

    2013-10-21

    Methods and models describing oxygen diffusion and desorption in oxides have been developed for slightly defective and well crystallised bulky materials. Does nanostructuring change the mechanism of oxygen mobility? In such a case, models should be properly checked and adapted to take into account new material properties. In order to do so, temperature programmed oxygen desorption and thermogravimetric analysis, either in isothermal or ramp mode, have been used to investigate some nanostructured La1-xAxMnO3±δ samples (A = Sr and Ce, 20-60 nm particle size) with perovskite-like structure. The experimental data have been elaborated by means of different models to define a set of kinetic parameters able to describe oxygen release properties and oxygen diffusion through the bulk. Different rate-determining steps have been identified, depending on the temperature range and oxygen depletion of the material. In particular, oxygen diffusion was shown to be rate-limiting at low temperature and at low defect concentration, whereas oxygen recombination at the surface seems to be the rate-controlling step at high temperature. However, the oxygen recombination step is characterised by an activation energy much lower than that for diffusion. In the present paper oxygen transport in nanosized materials is quantified by making use of widely diffused experimental techniques and by critically adapting to nanoparticles suitably chosen models developed for bulk materials.

  5. Hole-Transporting Materials with a Two-Dimensionally Expanded π-System around an Azulene Core for Efficient Perovskite Solar Cells.

    PubMed

    Nishimura, Hidetaka; Ishida, Naoki; Shimazaki, Ai; Wakamiya, Atsushi; Saeki, Akinori; Scott, Lawrence T; Murata, Yasujiro

    2015-12-23

    Two-dimensionally expanded π-systems, consisting of partially oxygen-bridged triarylamine skeletons that are connected to an azulene (1-3) or biphenyl core (4), were synthesized and characterized. When tetra-substituted azulene 1 was used as a hole-transporting material (HTM) in perovskite solar cells, the observed performance (power conversion efficiency = 16.5%) was found to be superior to that of the current HTM standard Spiro-OMeTAD. A comparison of the hole mobility, the ability to control the HOMO and LUMO levels, and the hole-collection efficiency at the perovskite/HTM interface in 1 with reference compounds (2-4 and Spiro-OMeTAD) led to the elucidation of key factors required for HTMs to act efficiently in perovskite solar cells.

  6. Defect Chemistry and Microstructure of Complex Perovskite Barium Zinc Niobate

    NASA Astrophysics Data System (ADS)

    Peng, Ping

    1991-02-01

    This dissertation presents a systematic study of the characterization of the phase transitions, microstructures, defects and transport properties of undoped and doped complex perovskite barium zinc niobate (BZN). Complex perovskite BZN is a paraelectric material while its parent material barium titanate is ferroelectric. With codoping of (Zn + 2Nb) into Ti site, BaTiO_3 shows three distinguished features. First, the Curie temperature is lowered; second, the three phase transitions (cubic-tetragonal-orthorhombic-rhombohedral) coalesce; and lastly, the transition becomes diffuse showing a typical 2nd order phase transition compared with 1st order in undoped BaTiO_3. Complex microchemical ordering is another characteristic of BZN. Stoichiometric BZN shows a mixture of two types of ordering schemes. 1:1, 1:2 ordered microdomains and the disordered matrix co-exist. The 1:1 type ordering involves an internal charge imbalance which inhibits the growth of 1:1 type of ordered microdomains. The 1:2 type ordering is consistent with the chemical composition of BZN. These ordering patterns can be modified by either adjustment of the Zn/Nb ratio or by doping. The defect structure of the stoichiometric BZN is closely related to that of BaTiO_3. Stoichiometric BZN is an insulator with wide band gap (~ 3.70 eV). Undoped BZN has a high oxygen vacancy concentration which comes from three possible sources, such as unavoidable acceptor impurities, due to their natural abundance, Zn/Nb ratio uncertainty due to processing limitations, and high temperature ZnO loss due to sintering process. The oxygen vacancy concentration for undoped BZN lays in the neighborhood of 1500 ppm (atm.). The compensation defects for various dopants have also been identified. Both electrons and holes conduct by a small polaron mechanism. Various thermodynamic parameters, such as enthalpies of oxidation and reduction, mass action constants for intrinsic electronic disorder, oxidation and reduction have been

  7. Identifying the Molecular Structures of Intermediates for Optimizing the Fabrication of High-Quality Perovskite Films.

    PubMed

    Cao, Jing; Jing, Xiaojing; Yan, Juanzhu; Hu, Chengyi; Chen, Ruihao; Yin, Jun; Li, Jing; Zheng, Nanfeng

    2016-08-10

    During the past two years, the introduction of DMSO has revolutionized the fabrication of high-quality pervoskite MAPbI3 (MA = CH3NH3) films for solar cell applications. In the developed DMSO process, the formation of (MA)2Pb3I8·2DMSO (shorted as Pb3I8) has well recognized as a critical factor to prepare high-quality pervoskite films and thus accomplish excellent performances in perovskite solar cells. However, Pb3I8 is an I-deficient intermediate and must further react with methylammonium iodide (MAI) to be fully converted into MAPbI3. By capturing and solving the molecular structures of several intermediates involved in the fabrication of perovskite films, we report in this work that the importance of DMSO is NOT due to the formation of Pb3I8. The use of different PbI2-DMSO ratios leads to two different structures of PbI2-DMSO precursors (PbI2·DMSO and PbI2·2DMSO), thus dramatically influencing the quality of fabricated perovskite films. However, such an influence can be minimized when the PbI2-DMSO precursor films are thermally treated to create mesoporous PbI2 films before reacting with MAI. Such a development makes the fabrication of high-quality pervoskite films highly reproducible without the need to precisely control the PbI2:DMSO ratio. Moreover, the formation of ionic compound (MA)4PbI6 is observed when excess MAI is used in the preparation of perovskite film. This I-rich phase heavily induces the hysteresis in PSCs, but is readily removed by isopropanol treatment. On the basis of all these findings, we develop a new effective protocol to fabricate high-performance PSCs. In the new protocol, high-quality perovskite films are prepared by simply treating the mesoporous PbI2 films (made from PbI2-DMSO precursors) with an isopropanol solution of MAI, followed by isopropanol washing. The best efficiency of fabricated MAPbI3 PSCs is up to 19.0%. As compared to the previously reported DMSO method, the devices fabricated by the method reported in this work

  8. Post-perovskite transitions in CaB4+O3 at high pressure

    NASA Astrophysics Data System (ADS)

    Akaogi, M.; Shirako, Y.; Kojitani, H.; Takamori, S.; Yamaura, K.; Takayama-Muromachi, E.

    2010-03-01

    High-pressure phase transitions in CaRhO3 were examined using a multianvil apparatus up to 27 GPa and 1930 oC. CaRhO3 perovskite transforms to post-perovskite via a monoclinic intermediate phase with increasing pressure. Volume changes for the transitions of perovskite - intermediate phase and of intermediate phase - post-perovskite are -1.1 and -0.7 %, respectively. CaRhO3 post-perovskite is the fourth quenchable post-perovskite oxide found so far. By high-temperature calorimetric experiments, enthalpy of the perovskite - post-perovskite transition in CaRuO3 was measured as 15.2±3.3 kJ/mol. Combining the datum with those of CaIrO3, it is shown that CaIrO3 perovskite is energetically less stable than CaRuO3 perovskite. This is consistent with the fact that orthorhombic distortion of CaIrO3 perovskite is larger than CaRuO3, as indicated with the tilt-angle of octahedral framework of perovskite structure. The transition pressure from perovskite to post-perovskite in CaBO3 (B = Ru, Rh, Ir) increases almost linearly with decreasing the tilt-angle, suggesting that the perovskite - post-perovskite transition may result from instability of the perovskite structure with pressure.

  9. Machine learning bandgaps of double perovskites

    NASA Astrophysics Data System (ADS)

    Pilania, G.; Mannodi-Kanakkithodi, A.; Uberuaga, B. P.; Ramprasad, R.; Gubernatis, J. E.; Lookman, T.

    2016-01-01

    The ability to make rapid and accurate predictions on bandgaps of double perovskites is of much practical interest for a range of applications. While quantum mechanical computations for high-fidelity bandgaps are enormously computation-time intensive and thus impractical in high throughput studies, informatics-based statistical learning approaches can be a promising alternative. Here we demonstrate a systematic feature-engineering approach and a robust learning framework for efficient and accurate predictions of electronic bandgaps of double perovskites. After evaluating a set of more than 1.2 million features, we identify lowest occupied Kohn-Sham levels and elemental electronegativities of the constituent atomic species as the most crucial and relevant predictors. The developed models are validated and tested using the best practices of data science and further analyzed to rationalize their prediction performance.

  10. Machine learning bandgaps of double perovskites

    DOE PAGESBeta

    Pilania, G.; Mannodi-Kanakkithodi, A.; Uberuaga, B. P.; Ramprasad, R.; Gubernatis, J. E.; Lookman, T.

    2016-01-19

    The ability to make rapid and accurate predictions on bandgaps of double perovskites is of much practical interest for a range of applications. While quantum mechanical computations for high-fidelity bandgaps are enormously computation-time intensive and thus impractical in high throughput studies, informatics-based statistical learning approaches can be a promising alternative. Here we demonstrate a systematic feature-engineering approach and a robust learning framework for efficient and accurate predictions of electronic bandgaps of double perovskites. After evaluating a set of more than 1.2 million features, we identify lowest occupied Kohn-Sham levels and elemental electronegativities of the constituent atomic species as the mostmore » crucial and relevant predictors. As a result, the developed models are validated and tested using the best practices of data science and further analyzed to rationalize their prediction performance.« less

  11. Machine learning bandgaps of double perovskites

    PubMed Central

    Pilania, G.; Mannodi-Kanakkithodi, A.; Uberuaga, B. P.; Ramprasad, R.; Gubernatis, J. E.; Lookman, T.

    2016-01-01

    The ability to make rapid and accurate predictions on bandgaps of double perovskites is of much practical interest for a range of applications. While quantum mechanical computations for high-fidelity bandgaps are enormously computation-time intensive and thus impractical in high throughput studies, informatics-based statistical learning approaches can be a promising alternative. Here we demonstrate a systematic feature-engineering approach and a robust learning framework for efficient and accurate predictions of electronic bandgaps of double perovskites. After evaluating a set of more than 1.2 million features, we identify lowest occupied Kohn-Sham levels and elemental electronegativities of the constituent atomic species as the most crucial and relevant predictors. The developed models are validated and tested using the best practices of data science and further analyzed to rationalize their prediction performance. PMID:26783247

  12. The photophysics of perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Sum, Tze Chien

    2014-09-01

    Solution-processed hybrid organic-inorganic perovskite solar cells, a newcomer to the photovoltaic arena, have taken the field by storm with their extraordinary power conversion efficiencies exceeding 17%. In this paper, the photophysics and the latest findings on the carrier dynamics and charge transfer mechanisms in this new class of photovoltaic material will be examined and distilled. Some open photophysics questions will also be discussed.

  13. Light-trapping in perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Du, Qing Guo; Shen, Guansheng; John, Sajeev

    2016-06-01

    We numerically demonstrate enhanced light harvesting efficiency in both CH3NH3PbI3 and CH(NH2)2PbI3-based perovskite solar cells using inverted vertical-cone photonic-crystal nanostructures. For CH3NH3PbI3 perovskite solar cells, the maximum achievable photocurrent density (MAPD) reaches 25.1 mA/cm2, corresponding to 92% of the total available photocurrent in the absorption range of 300 nm to 800 nm. Our cell shows 6% absorption enhancement compared to the Lambertian limit (23.7 mA/cm2) and has a projected power conversion efficiency of 12.9%. Excellent solar absorption is numerically demonstrated over a broad angular range from 0 to 60 degree for both S- and P- polarizations. For the corresponding CH(NH2)2PbI3 based perovskite solar cell, with absorption range of 300 nm to 850 nm, we find a MAPD of 29.1 mA/cm2, corresponding to 95.4% of the total available photocurrent. The projected power conversion efficiency of the CH(NH2)2PbI3 based photonic crystal solar cell is 23.4%, well above the current world record efficiency of 20.1%.

  14. Perovskite-related oxynitrides in photocatalysis.

    PubMed

    Pokrant, Simone; Maegli, Alexandra E; Chiarello, Gian Luca; Weidenkaff, Anke

    2013-01-01

    Over the last decades photocatalytic water splitting has become of increasing importance for fundamental and applied research, since the direct conversion of sunlight into chemical energy via the production of H2 has the potential to contribute to the world's energy needs without CO2 generation. One of the unsolved challenges consists of finding a highly efficient photocatalyst that is cheap, environmentally friendly, contains exclusively abundant elements, is (photo)chemically stable and absorbs visible light. Photocatalytic efficiency is closely connected to both structural properties like crystallinity, particle size and surface area and to electronic properties like the band gap and the quantum efficiency. Hence extensive control over a large parameter field is necessary to design a good photocatalyst. A material class where the structure-composition-property relations and the influence of substitution effects are well studied is the perovskite-type family of compounds. The perovskite-related oxynitrides belong to this very flexible compound family where many of the necessary characteristics for a photocatalyst are already given and some of the intrinsic properties like the band gap can be tuned within the same crystal structure by substitution. In this work we present materials' design concepts to improve the photocatalytic efficiency of a perovskite-type catalyst and describe their effects on the photocatalytic activity. PMID:23574956

  15. A-site ordered quadruple perovskite oxides

    NASA Astrophysics Data System (ADS)

    Youwen, Long

    2016-07-01

    The A-site ordered perovskite oxides with chemical formula display many intriguing physical properties due to the introduction of transition metals at both A‧ and B sites. Here, research on the recently discovered intermetallic charge transfer occurring between A‧-site Cu and B-site Fe ions in LaCu3Fe4O12 and its analogues is reviewed, along with work on the magnetoelectric multiferroicity observed in LaMn3Cr4O12 with cubic perovskite structure. The Cu-Fe intermetallic charge transfer leads to a first-order isostructural phase transition accompanied by drastic variations in magnetism and electrical transport properties. The LaMn3Cr4O12 is a novel spin-driven multiferroic system with strong magnetoelectric coupling effects. The compound is the first example of cubic perovskite multiferroics to be found. It opens up a new arena for studying unexpected multiferroic mechanisms. Project supported by the National Basic Research Program of China (Grant No. 2014CB921500), the Strategic Priority Research Program of the Chinese Academy of Sciences (Grant No. XDB07030300), and the National Natural Science Foundation of China (Grant No. 11574378).

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

    DOE PAGESBeta

    Ramasamy, Madhumidha; Baumann, Stefan; Palisaitis, Justinas; Schulze-Küppers, Falk; Balaguer, Maria; Kim, Daejin; Meulenberg, Wilhelm A.; Mayer, Jochim; Bhave, Ramesh; Guillon, Olivier; et al

    2015-09-24

    In dual-phase oxygen transport membranes we noticed that there is fast-growing interest in research for oxyfuel combustion process application. One such potential candidate is CGO-FCO (60wt% Ce0.8Gd0.2O2-δ-40wt% FeCo2O4) identified to provide good oxygen permeation flux with substantial stability in harsh atmosphere. Dense CGO-FCO membranes of 1mm thickness were fabricated by sintering dry pellets pressed from powders synthesized by one-pot method (modified Pechini process) at 1200 degrees C for 10h. Microstructure analysis indicates presence of a third orthorhombic perovskite phase in the sintered composite. We also identified that the spinel phase tends to form an oxygen deficient phase at the grainmore » boundary of spinel and CGO phases. Surface exchange limitation of the membranes was overcome by La0.6Sr0.4Co0.2Fe0.8O3-δ (LSCF) porous layer coating over the composite. Moreover, the oxygen permeation flux of the CGO-FCO screen printed with a porous layer of 10mthick LSCF is 0.11mL/cm2 per minute at 850 degrees C with argon as sweep and air as feed gas at the rates of 50 and 250mL/min.« less

  17. Static and dynamic optical properties of La1-xSrxFeO3-δ: The effects of A-site and oxygen stoichiometry

    SciTech Connect

    Sergey Y. Smolin; Sfeir, Matthew Y.; Scafetta, Mark D.; Choquette, Amber K.; Baxter, Jason B.; May, Steven J.

    2015-12-09

    Perovskite oxides are a promising material class for photovoltaic and photocatalytic applications due to their visible band gaps, nanosecond recombination lifetimes, and great chemical diversity. However, there is limited understanding of the link between composition and static and dynamic optical properties, despite the critical role these properties play in the design of light-harvesting devices. To clarify these relationships, we systemically studied the optoelectronic properties in La1-xSrxFeO3-δ epitaxial films, uncovering the effects of A-site cation substitution and oxygen stoichiometry. Variable-angle spectroscopic ellipsometry was used to measure static optical properties, revealing a linear increase in absorption coefficient at 1.25 eV and a red-shifting of the optical absorption edge with increasing Sr fraction. The absorption spectra can be similarly tuned through the introduction of oxygen vacancies, indicating the critical role that nominal Fe valence plays in optical absorption. Dynamic optoelectronic properties were studied with ultrafast transient reflectance spectroscopy, revealing similar nanosecond photoexcited carrier lifetimes for oxygen deficient and stoichiometric films with the same nominal Fe valence. Furthermore, these results demonstrate that while the static optical absorption is strongly dependent on nominal Fe valence tuned through cation or anion stoichiometry, oxygen vacancies do not appear to play a significantly detrimental role in the recombination kinetics.

  18. Lanthanoid-free perovskite oxide catalyst for dehydrogenation of ethylbenzene working with redox mechanism.

    PubMed

    Watanabe, Ryo; Ikushima, Maiko; Mukawa, Kei; Sumomozawa, Fumitaka; Ogo, Shuhei; Sekine, Yasushi

    2013-01-01

    For the development of highly active and robust catalysts for dehydrogenation of ethylbenzene (EBDH) to produce styrene; an important monomer for polystyrene production, perovskite-type oxides were applied to the reaction. Controlling the mobility of lattice oxygen by changing the structure of Ba1 - x SrxFe y Mn1 - y O3 - δ (0 ≤ x ≤ 1, 0.2 ≤ y ≤ 0.8), perovskite catalyst showed higher activity and stability on EBDH. The optimized Ba/Sr and Fe/Mn molar ratios were 0.4/0.6 and 0.6/0.4, respectively. Comparison of the dehydrogenation activity of Ba0.4Sr0.6Fe0.6Mn0.4O3 - δ catalyst with that of an industrial potassium promoted iron (Fe-K) catalyst revealed that the Ba0.4Sr0.6Fe0.6Mn0.4O3 - δ catalyst showed higher initial activity than the industrial Fe-K oxide catalyst. Additionally, the Ba0.4Sr0.6Fe0.6Mn0.4O3 - δ catalyst showed high activity and stability under severe conditions, even at temperatures as low as 783 K, or at the low steam/EB ratio of 2, while, the Fe-K catalyst showed low activity in such conditions. Comparing reduction profiles of the Ba0.4Sr0.6Fe0.6Mn0.4O3 - δ and the Fe-K catalysts in a H2O/H2 atmosphere, reduction was suppressed by the presence of H2O over the Ba0.4Sr0.6Fe0.6Mn0.4O3 - δ catalyst while the Fe-K catalyst was reduced. In other words, Ba0.4Sr0.6Fe0.6Mn0.4O3 - δ catalyst had higher potential for activating the steam than the Fe-K catalyst. The lattice oxygen in perovskite-structure was consumed by H2, subsequently the consumed lattice oxygen was regenerated by H2O. So the catalytic performance of Ba0.4Sr0.6Fe0.6Mn0.4O3 - δ was superior to that of Fe-K catalyst thanks to the high redox property of the Ba0.4Sr0.6Fe0.6Mn0.4O3 - δ perovskite oxide.

  19. Lanthanoid-free perovskite oxide catalyst for dehydrogenation of ethylbenzene working with redox mechanism

    NASA Astrophysics Data System (ADS)

    Watanabe, Ryo; Ikushima, Maiko; Mukawa, Kei; Sumomozawa, Fumitaka; Ogo, Shuhei; Sekine, Yasushi

    2013-10-01

    For the development of highly active and robust catalysts for dehydrogenation of ethylbenzene (EBDH) to produce styrene; an important monomer for polystyrene production, perovskite-type oxides were applied to the reaction. Controlling the mobility of lattice oxygen by changing the structure of Ba1-xSrxFeyMn1-yO3-d(0 ≤ x≤ 1, 0.2 ≤ y≤ 0.8), perovskite catalyst showed higher activity and stability on EBDH. The optimized Ba/Sr and Fe/Mn molar ratios were 0.4/0.6 and 0.6/0.4, respectively. Comparison of the dehydrogenation activity of Ba0.4Sr0.6Fe0.6Mn0.4O3-d catalyst with that of an industrial potassium promoted iron (Fe-K) catalyst revealed that the Ba0.4Sr0.6Fe0.6Mn0.4O3-d catalyst showed higher initial activity than the industrial Fe-K oxide catalyst. Additionally, the Ba0.4Sr0.6Fe0.6Mn0.4O3-d catalyst showed high activity and stability under severe conditions, even at temperatures as low as 783 K, or at the low steam/EB ratio of 2, while, the Fe-K catalyst showed low activity in such conditions. Comparing reduction profiles of the Ba0.4Sr0.6Fe0.6Mn0.4O3-d and the Fe-K catalysts in aH2O/H2 atmosphere, reduction was suppressed by the presence of H2O over the Ba0.4Sr0.6Fe0.6Mn0.4O3-d catalyst while the Fe-K catalyst was reduced. In other words, Ba0.4Sr0.6Fe0.6Mn0.4O3-d catalyst had higher potential for activating the steam than the Fe-K catalyst. The lattice oxygen in perovskite-structure was consumed by H2, subsequently the consumed lattice oxygen was regenerated by H2O. So the catalytic performance of Ba0.4Sr0.6Fe0.6Mn0.4O3-d was superior to that of Fe-K catalyst thanks to the high redox property of the Ba0.4Sr0.6Fe0.6Mn0.4O3-d perovskite oxide.

  20. Lanthanoid-free perovskite oxide catalyst for dehydrogenation of ethylbenzene working with redox mechanism

    PubMed Central

    Watanabe, Ryo; Ikushima, Maiko; Mukawa, Kei; Sumomozawa, Fumitaka; Ogo, Shuhei; Sekine, Yasushi

    2013-01-01

    For the development of highly active and robust catalysts for dehydrogenation of ethylbenzene (EBDH) to produce styrene; an important monomer for polystyrene production, perovskite-type oxides were applied to the reaction. Controlling the mobility of lattice oxygen by changing the structure of Ba1 − xSrxFeyMn1 − yO3 − δ (0 ≤ x ≤ 1, 0.2 ≤ y ≤ 0.8), perovskite catalyst showed higher activity and stability on EBDH. The optimized Ba/Sr and Fe/Mn molar ratios were 0.4/0.6 and 0.6/0.4, respectively. Comparison of the dehydrogenation activity of Ba0.4Sr0.6Fe0.6Mn0.4O3 − δ catalyst with that of an industrial potassium promoted iron (Fe–K) catalyst revealed that the Ba0.4Sr0.6Fe0.6Mn0.4O3 − δ catalyst showed higher initial activity than the industrial Fe–K oxide catalyst. Additionally, the Ba0.4Sr0.6Fe0.6Mn0.4O3 − δ catalyst showed high activity and stability under severe conditions, even at temperatures as low as 783 K, or at the low steam/EB ratio of 2, while, the Fe–K catalyst showed low activity in such conditions. Comparing reduction profiles of the Ba0.4Sr0.6Fe0.6Mn0.4O3 − δ and the Fe–K catalysts in a H2O/H2 atmosphere, reduction was suppressed by the presence of H2O over the Ba0.4Sr0.6Fe0.6Mn0.4O3 − δ catalyst while the Fe–K catalyst was reduced. In other words, Ba0.4Sr0.6Fe0.6Mn0.4O3 − δ catalyst had higher potential for activating the steam than the Fe–K catalyst. The lattice oxygen in perovskite-structure was consumed by H2, subsequently the consumed lattice oxygen was regenerated by H2O. So the catalytic performance of Ba0.4Sr0.6Fe0.6Mn0.4O3 − δ was superior to that of Fe–K catalyst thanks to the high redox property of the Ba0.4Sr0.6Fe0.6Mn0.4O3 − δ perovskite oxide. PMID:24790949

  1. Cobalt based layered perovskites as cathode material for intermediate temperature Solid Oxide Fuel Cells: A brief review

    NASA Astrophysics Data System (ADS)

    Pelosato, Renato; Cordaro, Giulio; Stucchi, Davide; Cristiani, Cinzia; Dotelli, Giovanni

    2015-12-01

    Nowadays, the cathode is the most studied component in Intermediate Temperature-Solid Oxide Fuel Cells (IT-SOFCs). Decreasing SOFCs operating temperature implies slow oxygen reduction kinetics and large polarization losses. Double perovskites with general formula REBaCo2O5+δ are promising mixed ionic-electronic conductors, offering a remarkable enhancement of the oxygen diffusivity and surface exchange respect to disordered perovskites. In this review, more than 250 compositions investigated in the literature were analyzed. The evaluation was performed in terms of electrical conductivity, Area Specific Resistance (ASR), chemical compatibility with electrolytes and Thermal Expansion Coefficient (TEC). The most promising materials have been identified as those bearing the mid-sized rare earths (Pr, Nd, Sm, Gd). Doping strategies have been analyzed: Sr doping on A site promotes higher electrical conductivity, but worsen ASR and TECs; B-site doping (Fe, Ni, Mn) helps lowering TECs, but is detrimental for the electrochemical properties. A promising boost of the electrochemical activity is obtained by simply introducing a slight Ba under-stoichiometry. Still, the high sensitivity of the electrochemical properties against slight changes in the stoichiometry hamper a conclusive comparison of all the investigated compounds. Opportunities for an improvement of double perovskite cathodes performance is tentatively foreseen in combining together the diverse effective doping strategies.

  2. Two Dimensional Organometal Halide Perovskite Nanorods with Tunable Optical Properties.

    PubMed

    Aharon, Sigalit; Etgar, Lioz

    2016-05-11

    Organo-metal halide perovskite is an efficient light harvester in photovoltaic solar cells. Organometal halide perovskite is used mainly in its "bulk" form in the solar cell. Confined perovskite nanostructures could be a promising candidate for efficient optoelectronic devices, taking advantage of the superior bulk properties of organo-metal halide perovskite, as well as the nanoscale properties. In this paper, we present facile low-temperature synthesis of two-dimensional (2D) lead halide perovskite nanorods (NRs). These NRs show a shift to higher energies in the absorbance and in the photoluminescence compared to the bulk material, which supports their 2D structure. X-ray diffraction (XRD) analysis of the NRs demonstrates their 2D nature combined with the tetragonal 3D perovskite structure. In addition, by alternating the halide composition, we were able to tune the optical properties of the NRs. Fast Fourier transform, and electron diffraction show the tetragonal structure of these NRs. By varying the ligands ratio (e.g., octylammonium to oleic acid) in the synthesis, we were able to provide the formation mechanism of these novel 2D perovskite NRs. The 2D perovskite NRs are promising candidates for a variety of optoelectronic applications, such as light-emitting diodes, lasing, solar cells, and sensors. PMID:27089497

  3. Solution Chemistry Engineering toward High-Efficiency Perovskite Solar Cells.

    PubMed

    Zhao, Yixin; Zhu, Kai

    2014-12-01

    Organic and inorganic hybrid perovskites (e.g., CH3NH3PbI3) have emerged as a revolutionary class of light-absorbing semiconductors that has demonstrated a rapid increase in efficiency within a few years of active research. Controlling perovskite morphology and composition has been found critical to developing high-performance perovskite solar cells. The recent development of solution chemistry engineering has led to fabrication of greater than 15-17%-efficiency solar cells by multiple groups, with the highest certified 17.9% efficiency that has significantly surpassed the best-reported perovskite solar cell by vapor-phase growth. In this Perspective, we review recent progress on solution chemistry engineering processes and various control parameters that are critical to the success of solution growth of high-quality perovskite films. We discuss the importance of understanding the impact of solution-processing parameters and perovskite film architectures on the fundamental charge carrier dynamics in perovskite solar cells. The cost and stability issues of perovskite solar cells will also be discussed.

  4. Solution Chemistry Engineering toward High-Efficiency Perovskite Solar Cells.

    PubMed

    Zhao, Yixin; Zhu, Kai

    2014-12-01

    Organic and inorganic hybrid perovskites (e.g., CH3NH3PbI3) have emerged as a revolutionary class of light-absorbing semiconductors that has demonstrated a rapid increase in efficiency within a few years of active research. Controlling perovskite morphology and composition has been found critical to developing high-performance perovskite solar cells. The recent development of solution chemistry engineering has led to fabrication of greater than 15-17%-efficiency solar cells by multiple groups, with the highest certified 17.9% efficiency that has significantly surpassed the best-reported perovskite solar cell by vapor-phase growth. In this Perspective, we review recent progress on solution chemistry engineering processes and various control parameters that are critical to the success of solution growth of high-quality perovskite films. We discuss the importance of understanding the impact of solution-processing parameters and perovskite film architectures on the fundamental charge carrier dynamics in perovskite solar cells. The cost and stability issues of perovskite solar cells will also be discussed. PMID:26278951

  5. Self-Assembled PbSe Nanowire:Perovskite Hybrids.

    PubMed

    Yang, Zhenyu; Yassitepe, Emre; Voznyy, Oleksandr; Janmohamed, Alyf; Lan, Xinzheng; Levina, Larissa; Comin, Riccardo; Sargent, Edward H

    2015-12-01

    Inorganic semiconductor nanowires are of interest in nano- and microscale photonic and electronic applications. Here we report the formation of PbSe nanowires based on directional quantum dot alignment and fusion regulated by hybrid organic-inorganic perovskite surface ligands. All material synthesis is carried out at mild temperatures. Passivation of PbSe quantum dots was achieved via a new perovskite ligand exchange. Subsequent in situ ammonium/amine substitution by butylamine enables quantum dots to be capped by butylammonium lead iodide, and this further drives the formation of a PbSe nanowire superlattice in a two-dimensional (2D) perovskite matrix. The average spacing between two adjacent nanowires agrees well with the thickness of single atomic layer of 2D perovskite, consistent with the formation of a new self-assembled semiconductor nanowire:perovskite heterocrystal hybrid.

  6. Highly efficient light management for perovskite solar cells

    PubMed Central

    Wang, Dong-Lin; Cui, Hui-Juan; Hou, Guo-Jiao; Zhu, Zhen-Gang; Yan, Qing-Bo; Su, Gang

    2016-01-01

    Organic-inorganic halide perovskite solar cells have enormous potential to impact the existing photovoltaic industry. As realizing a higher conversion efficiency of the solar cell is still the most crucial task, a great number of schemes were proposed to minimize the carrier loss by optimizing the electrical properties of the perovskite solar cells. Here, we focus on another significant aspect that is to minimize the light loss by optimizing the light management to gain a high efficiency for perovskite solar cells. In our scheme, the slotted and inverted prism structured SiO2 layers are adopted to trap more light into the solar cells, and a better transparent conducting oxide layer is employed to reduce the parasitic absorption. For such an implementation, the efficiency and the serviceable angle of the perovskite solar cell can be promoted impressively. This proposal would shed new light on developing the high-performance perovskite solar cells. PMID:26733112

  7. Highly efficient light management for perovskite solar cells.

    PubMed

    Wang, Dong-Lin; Cui, Hui-Juan; Hou, Guo-Jiao; Zhu, Zhen-Gang; Yan, Qing-Bo; Su, Gang

    2016-01-06

    Organic-inorganic halide perovskite solar cells have enormous potential to impact the existing photovoltaic industry. As realizing a higher conversion efficiency of the solar cell is still the most crucial task, a great number of schemes were proposed to minimize the carrier loss by optimizing the electrical properties of the perovskite solar cells. Here, we focus on another significant aspect that is to minimize the light loss by optimizing the light management to gain a high efficiency for perovskite solar cells. In our scheme, the slotted and inverted prism structured SiO2 layers are adopted to trap more light into the solar cells, and a better transparent conducting oxide layer is employed to reduce the parasitic absorption. For such an implementation, the efficiency and the serviceable angle of the perovskite solar cell can be promoted impressively. This proposal would shed new light on developing the high-performance perovskite solar cells.

  8. Perovskite-fullerene hybrid materials suppress hysteresis in planar diodes.

    PubMed

    Xu, Jixian; Buin, Andrei; Ip, Alexander H; Li, Wei; Voznyy, Oleksandr; Comin, Riccardo; Yuan, Mingjian; Jeon, Seokmin; Ning, Zhijun; McDowell, Jeffrey J; Kanjanaboos, Pongsakorn; Sun, Jon-Paul; Lan, Xinzheng; Quan, Li Na; Kim, Dong Ha; Hill, Ian G; Maksymovych, Peter; Sargent, Edward H

    2015-05-08

    Solution-processed planar perovskite devices are highly desirable in a wide variety of optoelectronic applications; however, they are prone to hysteresis and current instabilities. Here we report the first perovskite-PCBM hybrid solid with significantly reduced hysteresis and recombination loss achieved in a single step. This new material displays an efficient electrically coupled microstructure: PCBM is homogeneously distributed throughout the film at perovskite grain boundaries. The PCBM passivates the key PbI3(-) antisite defects during the perovskite self-assembly, as revealed by theory and experiment. Photoluminescence transient spectroscopy proves that the PCBM phase promotes electron extraction. We showcase this mixed material in planar solar cells that feature low hysteresis and enhanced photovoltage. Using conductive AFM studies, we reveal the memristive properties of perovskite films. We close by positing that PCBM, by tying up both halide-rich antisites and unincorporated halides, reduces electric field-induced anion migration that may give rise to hysteresis and unstable diode behaviour.

  9. Engineering electrocatalytic activity in nanosized perovskite cobaltite through surface spin-state transition

    PubMed Central

    Zhou, Shiming; Miao, Xianbing; Zhao, Xu; Ma, Chao; Qiu, Yuhao; Hu, Zhenpeng; Zhao, Jiyin; Shi, Lei; Zeng, Jie

    2016-01-01

    The activity of electrocatalysts exhibits a strongly dependence on their electronic structures. Specifically, for perovskite oxides, Shao-Horn and co-workers have reported a correlation between the oxygen evolution reaction activity and the eg orbital occupation of transition-metal ions, which provides guidelines for the design of highly active catalysts. Here we demonstrate a facile method to engineer the eg filling of perovskite cobaltite LaCoO3 for improving the oxygen evolution reaction activity. By reducing the particle size to ∼80 nm, the eg filling of cobalt ions is successfully increased from unity to near the optimal configuration of 1.2 expected by Shao-Horn's principle. Consequently, the activity is significantly enhanced, comparable to those of recently reported cobalt oxides with eg∼1.2 configurations. This enhancement is ascribed to the emergence of spin-state transition from low-spin to high-spin states for cobalt ions at the surface of the nanoparticles, leading to more active sites with increased reactivity. PMID:27187067

  10. Engineering electrocatalytic activity in nanosized perovskite cobaltite through surface spin-state transition.

    PubMed

    Zhou, Shiming; Miao, Xianbing; Zhao, Xu; Ma, Chao; Qiu, Yuhao; Hu, Zhenpeng; Zhao, Jiyin; Shi, Lei; Zeng, Jie

    2016-01-01

    The activity of electrocatalysts exhibits a strongly dependence on their electronic structures. Specifically, for perovskite oxides, Shao-Horn and co-workers have reported a correlation between the oxygen evolution reaction activity and the eg orbital occupation of transition-metal ions, which provides guidelines for the design of highly active catalysts. Here we demonstrate a facile method to engineer the eg filling of perovskite cobaltite LaCoO3 for improving the oxygen evolution reaction activity. By reducing the particle size to ∼80 nm, the eg filling of cobalt ions is successfully increased from unity to near the optimal configuration of 1.2 expected by Shao-Horn's principle. Consequently, the activity is significantly enhanced, comparable to those of recently reported cobalt oxides with eg(∼1.2) configurations. This enhancement is ascribed to the emergence of spin-state transition from low-spin to high-spin states for cobalt ions at the surface of the nanoparticles, leading to more active sites with increased reactivity. PMID:27187067

  11. Water-Gas Shift and Methane Reactivity on Reducible Perovskite-Type Oxides

    PubMed Central

    2015-01-01

    Comparative (electro)catalytic, structural, and spectroscopic studies in hydrogen electro-oxidation, the (inverse) water-gas shift reaction, and methane conversion on two representative mixed ionic–electronic conducting perovskite-type materials La0.6Sr0.4FeO3−δ (LSF) and SrTi0.7Fe0.3O3−δ (STF) were performed with the aim of eventually correlating (electro)catalytic activity and associated structural changes and to highlight intrinsic reactivity characteristics as a function of the reduction state. Starting from a strongly prereduced (vacancy-rich) initial state, only (inverse) water-gas shift activity has been observed on both materials beyond ca. 450 °C but no catalytic methane reforming or methane decomposition reactivity up to 600 °C. In contrast, when starting from the fully oxidized state, total methane oxidation to CO2 was observed on both materials. The catalytic performance of both perovskite-type oxides is thus strongly dependent on the degree/depth of reduction, on the associated reactivity of the remaining lattice oxygen, and on the reduction-induced oxygen vacancies. The latter are clearly more reactive toward water on LSF, and this higher reactivity is linked to the superior electrocatalytic performance of LSF in hydrogen oxidation. Combined electron microscopy, X-ray diffraction, and Raman measurements in turn also revealed altered surface and bulk structures and reactivities. PMID:26045733

  12. Incorporation effect of nanosized perovskite LaFe₀.₇Co₀.₃O₃ on the electrochemical activity of Pt nanoparticles-multi walled carbon nanotube composite toward methanol oxidation

    SciTech Connect

    Noroozifar, Meissam; Khorasani-Motlagh, Mozhgan; Khaleghian-Moghadam, Roghayeh; Ekrami-Kakhki, Mehri-Saddat; Shahraki, Mohammad

    2013-05-01

    Nanosized perovskite LaFe₀.₇Co₀.₃O₃ (LFCO) is synthesized through conventional co-precipitation method and characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive X-ray (EDX) techniques. The incorporation effect of the mentioned perovskite to catalytic activity of the PtNPs-MWCNTs-nafion (or -chitosan) catalyst toward methanol oxidation has been studied by cyclic voltammetry. Based on the electrochemical studies, all MWCNTs-PtNPs-nafion (or chitosan) and MWCNTs-PtNPs-LFCO-nafion (or chitosan) catalysts show a considerable activity for methanol oxidation. However, a synergistic effect is observed when LFCO is added to the catalyst by decreasing the poisoning rate of the Pt catalyst. - Graphical abstract: Nanosized perovskite LaFe₀.₇Co₀.₃O₃ is synthesized and characterized. The incorporation effect of the mentioned perovskite to catalytic activity of the PtNPS-MWCNTs-nafion (or -chitosan) catalyst toward methanol oxidation is studied. Highlights: • Nanocrystalline LaFe₀.₇Co₀.₃O₃ (LFCO) is prepared by a new simple co-precipitation method. • Effect of LFCO to catalytic activity of PtNPS for methanol oxidation is studied. • A synergistic effect is observed when LFCO is added to the Pt catalyst. • Oxygen of LFCO could be considered as active oxygen to remove CO intermediates.

  13. Weakening of Calcium Iridate During its Transformation from Perovskite to Post-Perovskite

    SciTech Connect

    Hunt, S.; Weidner, D; Li, L; Wang, L; Walte, N; Brodholt, J; Dobson, D

    2009-01-01

    The lowermost part of the Earth's mantle - the {approx}200-km-thick D{double_prime} layer - shows anomalous seismic properties, and is rheologically distinct from the rest of the lower mantle. The difference is thought to result from a phase transition from silicate perovskite to silicate post-perovskite. However, the rheology of the latter phase remains to be documented owing to experimental difficulties in reproducing pressures equivalent to those in the lowermost mantle. Here we address this problem by conducting laboratory experiments that use calcium iridate, which has been shown to be an appropriate low-pressure analogue. We find that the post-perovskite phase of this analogue is approximately five times weaker than its perovskite phase, and that it further weakens by a factor of two during the phase transformation; these are minimum estimates. If, as is likely, a similar weakening occurs in lower-mantle magnesium - silicate compositions, this could provide an explanation for the behaviour of the lowermost mantle as inferred from geophysical data.

  14. Oxygen Therapy

    MedlinePlus

    ... 85-95% pure oxygen. The concentrator runs on electricity or a battery. A concentrator for home usually ... systems deliver 100% oxygen, and do not require electricity. A small canister can be filled from the ...

  15. Oxygen analyzer

    DOEpatents

    Benner, William H.

    1986-01-01

    An oxygen analyzer which identifies and classifies microgram quantities of oxygen in ambient particulate matter and for quantitating organic oxygen in solvent extracts of ambient particulate matter. A sample is pyrolyzed in oxygen-free nitrogen gas (N.sub.2), and the resulting oxygen quantitatively converted to carbon monoxide (CO) by contact with hot granular carbon (C). Two analysis modes are made possible: (1) rapid determination of total pyrolyzable oxygen obtained by decomposing the sample at 1135.degree. C., or (2) temperature-programmed oxygen thermal analysis obtained by heating the sample from room temperature to 1135.degree. C. as a function of time. The analyzer basically comprises a pyrolysis tube containing a bed of granular carbon under N.sub.2, ovens used to heat the carbon and/or decompose the sample, and a non-dispersive infrared CO detector coupled to a mini-computer to quantitate oxygen in the decomposition products and control oven heating.

  16. An experimental study of perovskite-structured mixed ionic- electronic conducting oxides and membranes

    NASA Astrophysics Data System (ADS)

    Zeng, Pingying

    In recent decades, ceramic membranes based on mixed ionic and electronic conducting (MIEC) perovskite-structured oxides have received many attentions for their applications for air separation, or as a membrane reactor for methane oxidation. While numerous perovskite oxide materials have been explored over the past two decades; there are hardly any materials with sufficient practical economic value and performance for large scale applications, which justifies continuing the search for new materials. The main purposes of this thesis study are: (1) develop several novel SrCoO3-delta based MIEC oxides, SrCoCo1-xMxO3-delta, based on which membranes exhibit excellent oxygen permeability; (2) investigate the significant effects of the species and concentration of the dopants M (metal ions with fixed valences) on the various properties of these membranes; (3) investigate the significant effects of sintering temperature on the microstructures and performance of oxygen permeation membranes; and (4) study the performance of oxygen permeation membranes as a membrane reactor for methane combustion. To stabilize the cubic phase structure of the SrCoO3-delta oxide, various amounts of scandium was doped into the B-site of SrCoO 3-delta to form a series of new perovskite oxides, SrScxCoCo 1-xO3-delta (SSCx, x = 0-0.7). The significant effects of scandium-doping concentration on the phase structure, electrical conductivity, sintering performance, thermal and structural stability, cathode performance, and oxygen permeation performance of the SSCx membranes, were systematically studied. Also for a more in-depth understanding, the rate determination steps for the oxygen transport process through the membranes were clarified by theoretical and experimental investigation. It was found that only a minor amount of scandium (5 mol%) doping into the B-site of SrCoO3-delta can effectively stabilize the cubic phase structure, and thus significantly improve the electrical conductivity and

  17. Generalized trends in the formation energies of perovskite oxides.

    PubMed

    Zeng, ZhenHua; Calle-Vallejo, Federico; Mogensen, Mogens B; Rossmeisl, Jan

    2013-05-28

    Generalized trends in the formation energies of several families of perovskite oxides (ABO3) and plausible explanations to their existence are provided in this study through a combination of DFT calculations, solid-state physics analyses and simple physical/chemical descriptors. The studied elements at the A site of perovskites comprise rare-earth, alkaline-earth and alkaline metals, whereas 3d and 5d metals were studied at the B site. We also include ReO3-type compounds, which have the same crystal structure of cubic ABO3 perovskites except without A-site elements. From the observations we extract the following four conclusions for the perovskites studied in the present paper: for a given cation at the B site, (I) perovskites with cations of identical oxidation state at the A site possess close formation energies; and (II) perovskites with cations of different oxidation states at the A site usually have quite different but ordered formation energies. On the other hand, for a given A-site cation, (III) the formation energies of perovskites vary linearly with respect to the atomic number of the elements at the B site within the same period of the periodic table, and the slopes depend systematically on the oxidation state of the A-site cation; and (IV) the trends in formation energies of perovskites with elements from different periods at the B site depend on the oxidation state of A-site cations. Since the energetics of perovskites is shown to be the superposition of the individual contributions of their constituent oxides, the trends can be rationalized in terms of A-O and B-O interactions in the ionic crystal. These findings reveal the existence of general systematic trends in the formation energies of perovskites and provide further insight into the role of ion-ion interactions in the properties of ternary compounds.

  18. Generalized trends in the formation energies of perovskite oxides.

    PubMed

    Zeng, ZhenHua; Calle-Vallejo, Federico; Mogensen, Mogens B; Rossmeisl, Jan

    2013-05-28

    Generalized trends in the formation energies of several families of perovskite oxides (ABO3) and plausible explanations to their existence are provided in this study through a combination of DFT calculations, solid-state physics analyses and simple physical/chemical descriptors. The studied elements at the A site of perovskites comprise rare-earth, alkaline-earth and alkaline metals, whereas 3d and 5d metals were studied at the B site. We also include ReO3-type compounds, which have the same crystal structure of cubic ABO3 perovskites except without A-site elements. From the observations we extract the following four conclusions for the perovskites studied in the present paper: for a given cation at the B site, (I) perovskites with cations of identical oxidation state at the A site possess close formation energies; and (II) perovskites with cations of different oxidation states at the A site usually have quite different but ordered formation energies. On the other hand, for a given A-site cation, (III) the formation energies of perovskites vary linearly with respect to the atomic number of the elements at the B site within the same period of the periodic table, and the slopes depend systematically on the oxidation state of the A-site cation; and (IV) the trends in formation energies of perovskites with elements from different periods at the B site depend on the oxidation state of A-site cations. Since the energetics of perovskites is shown to be the superposition of the individual contributions of their constituent oxides, the trends can be rationalized in terms of A-O and B-O interactions in the ionic crystal. These findings reveal the existence of general systematic trends in the formation energies of perovskites and provide further insight into the role of ion-ion interactions in the properties of ternary compounds. PMID:23579382

  19. Factor V deficiency

    MedlinePlus

    ... in blood plasma. These proteins are called blood coagulation factors. Factor V deficiency is caused by a ... Gailani D, Neff AT. Rare coagulation factor deficiencies. In: ... HE, Weitz JI, Anastasi J, eds. Hematology: Basic Principles and ...

  20. Alpha-1 Antitrypsin Deficiency

    MedlinePlus

    ... from the NHLBI on Twitter. What Is Alpha-1 Antitrypsin Deficiency? Alpha-1 antitrypsin (an-tee-TRIP-sin) deficiency, or AAT ... as it relates to lung disease. Overview Alpha-1 antitrypsin, also called AAT, is a protein made ...

  1. Ordering of ionic Vacancies in the BaCoO 2.94Hexagonal Related Perovskite

    NASA Astrophysics Data System (ADS)

    Varela, A.; Parras, M.; Boulahya, K.; González-Calbet, J. M.

    1997-01-01

    An electron diffraction and high-resolution electron microscopy study shows that oxygen vacancies in BaCoO 2.94lead to a threefold superstructure along the (11 overline20) 2Hdirection, the …hhh… hexagonal sequence characteristic of the 2H type being maintained. ording to compositional and structural data, the most probable structural model should be formed by three AO 3layers intergrowing with one AO 2.67layer along the c-axis. In such oxygen-deficient layers, one of each six oxygen atoms in every oxygen row is removed, leading to the observed superstructure.

  2. CH3 NH3 PbBr3 -CH3 NH3 PbI3 Perovskite-Perovskite Tandem Solar Cells with Exceeding 2.2 V Open Circuit Voltage.

    PubMed

    Heo, Jin Hyuck; Im, Sang Hyuk

    2016-07-01

    Perovskite-perovskite tandem solar cells with open-circuit voltages of over 2.2 V are reported. These cost-effective, solution-processible perovskite hybrid tandem solar cells with high open-circuit voltages are fabricated by the simple lamination of a front planar MAPbBr3 perovskite cell and a back MAPbI3 planar perovskite solar cell.

  3. DOCK8 Deficiency

    MedlinePlus

    ... on ClinicalTrials.gov . Related Links Primary Immune Deficiency Diseases (PIDDs) Immune System ​​​​​​​ Javascript Error Your browser JavaScript is turned ... Scientists Identify Genetic Cause of Previously Undefined Primary Immune Deficiency Disease Signs and Symptoms DOCK8 deficiency causes persistent skin ...

  4. Iron-Deficiency Anemia

    MedlinePlus

    ... the NHLBI on Twitter. What Is Iron-Deficiency Anemia? Español Iron-deficiency anemia is a common, easily ... Featured Video Living With and Managing Iron-Deficiency Anemia 05/18/2011 This video—presented by the ...

  5. Chemical and electronic characterization of cobalt in a lanthanum perovskite. Effects of strontium substitution

    SciTech Connect

    Hueso, Jose L.; Holgado, Juan P.; Pereniguez, Rosa; Mun, Simon; Salmeron, Miquel; Caballero, Alfonso

    2010-01-15

    Two different cobaltites, LaCoO{sub 3} and La{sub 0.5}Sr{sub 0.5}CoO{sub 3-{delta}}, have been prepared and characterized by means of high energy Co K-edge and low energy O K-edge X-ray absorption spectroscopy (XAS). Even though half of the La(III) is substituted by Sr(II), little or no changes can be detected in the formal oxidation state of cobalt atoms. The presence of strontium cations induces two main effects in the chemical and electronic state of the perovskite. The charge balance with Sr(II) species is reached by the formation of oxygen vacancies throughout the network, which explains the well-known increase in the reactivity of this substituted perovskite. O K-edge XAS experiments show that the Sr(II) species induce the transitions of d electrons of cobalt cations from low to high spin configuration. We propose that this change in spin multiplicity is induced by two cooperative effects: the oxygen vacancies, creating five coordinated cobalt atoms, and the bigger size of Sr(II) cations, aligning the Co-O-Co atoms, and favoring the overlapping of pi-symmetry cobalt and oxygen orbitals, reducing the splitting energy of e{sub g} and t{sub 2g} levels. - Graphical abstract: Change in spin multiplicity induced by the bigger size of Sr(II) cations, aligning the Co-O-Co atoms, and favoring the overlapping of pi-symmetry cobalt and oxygen orbitals.

  6. Ferroelectricity in d0 double perovskite fluoroscandates

    NASA Astrophysics Data System (ADS)

    Charles, Nenian; Rondinelli, James M.

    2015-08-01

    Ferroelectricity in strain-free and strained double perovskite fluorides, Na3ScF6 and K2NaScF6 , is investigated using first-principles density functional theory. Although the experimental room temperature crystal structures of these fluoroscandates are centrosymmetric, i.e., Na3ScF6 (P 21/n ) and K2NaScF6 (F m 3 ¯m ), lattice dynamical calculations reveal that soft polar instabilities exist in each prototypical cubic phase and that the modes harden as the tolerance factor approaches unity. Thus the double fluoroperovskites bear some similarities to A B O3 perovskite oxides; however, in contrast, these fluorides exhibit large acentric displacements of alkali metal cations (Na, K) rather than polar displacements of the transition metal cations. Biaxial strain investigations of the centrosymmetric and polar Na3ScF6 and K2NaScF6 phases reveal that the paraelectric structures are favored under compressive strain, whereas polar structures with in-plane electric polarizations (˜5 -18 μ C cm-2 ) are realized at sufficiently large tensile strains. The electric polarization and stability of the polar structures for both chemistries are found to be further enhanced and stabilized by a coexisting single octahedral tilt system. Our results suggest that polar double perovskite fluorides may be realized by suppression of octahedral rotations about more than one Cartesian axis; structures exhibiting in- or out-of-phase octahedral rotations about the c axis are more susceptible to polar symmetries.

  7. Oxygen analyzer

    DOEpatents

    Benner, W.H.

    1984-05-08

    An oxygen analyzer which identifies and classifies microgram quantities of oxygen in ambient particulate matter and for quantitating organic oxygen in solvent extracts of ambient particulate matter. A sample is pyrolyzed in oxygen-free nitrogen gas (N/sub 2/), and the resulting oxygen quantitatively converted to carbon monoxide (CO) by contact with hot granular carbon (C). Two analysis modes are made possible: (1) rapid determination of total pyrolyzable obtained by decomposing the sample at 1135/sup 0/C, or (2) temperature-programmed oxygen thermal analysis obtained by heating the sample from room temperature to 1135/sup 0/C as a function of time. The analyzer basically comprises a pyrolysis tube containing a bed of granular carbon under N/sub 2/, ovens used to heat the carbon and/or decompose the sample, and a non-dispersive infrared CO detector coupled to a mini-computer to quantitate oxygen in the decomposition products and control oven heating.

  8. Piezoelectric activity in Perovskite ferroelectric crystals.

    PubMed

    Li, Fei; Wang, Linghang; Jin, Li; Lin, Dabin; Li, Jinglei; Li, Zhenrong; Xu, Zhuo; Zhang, Shujun

    2015-01-01

    Perovskite ferroelectrics (PFs) have been the dominant piezoelectric materials for various electromechanical applications, such as ultrasonic transducers, sensors, and actuators, to name a few. In this review article, the development of PF crystals is introduced, focusing on the crystal growth and piezoelectric activity. The critical factors responsible for the high piezoelectric activity of PFs (i.e., phase transition, monoclinic phase, domain size, relaxor component, dopants, and piezoelectric anisotropy) are surveyed and discussed. A general picture of the present understanding on the high piezoelectricity of PFs is described. At the end of this review, potential approaches to further improve the piezoelectricity of PFs are proposed.

  9. OXYGEN TRANSPORT CERAMIC MEMBRANES

    SciTech Connect

    Dr. Sukumar Bandopadhyay; Dr. Nagendra Nagabhushana

    2001-12-01

    Conversion of natural gas to liquid fuels and chemicals is a major goal for the Nation as it enters the 21st Century. Technically robust and economically viable processes are needed to capture the value of the vast reserves of natural gas on Alaska's North Slope, and wean the Nation from dependence on foreign petroleum sources. Technologies that are emerging to fulfill this need are all based syngas as an intermediate. Syngas (a mixture of hydrogen and carbon monoxide) is a fundamental building block from which chemicals and fuels can be derived. Lower cost syngas translates directly into more cost-competitive fuels and chemicals. The currently practiced commercial technology for making syngas is either steam methane reforming (SMR) or a two-step process involving cryogenic oxygen separation followed by natural gas partial oxidation (POX). These high-energy, capital-intensive processes do not always produce syngas at a cost that makes its derivatives competitive with current petroleum-based fuels and chemicals. This project has the following 6 main tasks: Task 1--Design, fabricate and evaluate ceramic to metal seals based on graded ceramic powder/metal braze joints. Task 2--Evaluate the effect of defect configuration on ceramic membrane conductivity and long term chemical and structural stability. Task 3--Determine materials mechanical properties under conditions of high temperatures and reactive atmospheres. Task 4--Evaluate phase stability and thermal expansion of candidate perovskite membranes and develop techniques to support these materials on porous metal structures. Task 5--Assess the microstructure of membrane materials to evaluate the effects of vacancy-impurity association, defect clusters, and vacancy-dopant association on the membrane performance and stability. Task 6--Measure kinetics of oxygen uptake and transport in ceramic membrane materials under commercially relevant conditions using isotope labeling techniques.

  10. Deciphering Halogen Competition in Organometallic Halide Perovskite Growth.

    PubMed

    Yang, Bin; Keum, Jong; Ovchinnikova, Olga S; Belianinov, Alex; Chen, Shiyou; Du, Mao-Hua; Ivanov, Ilia N; Rouleau, Christopher M; Geohegan, David B; Xiao, Kai

    2016-04-20

    Organometallic halide perovskites (OHPs) hold great promise for next-generation, low-cost optoelectronic devices. During the chemical synthesis and crystallization of OHP thin films, a major unresolved question is the competition between multiple halide species (e.g., I(-), Cl(-), Br(-)) in the formation of the mixed-halide perovskite crystals. Whether Cl(-) ions are successfully incorporated into the perovskite crystal structure or, alternatively, where they are located is not yet fully understood. Here, in situ X-ray diffraction measurements of crystallization dynamics are combined with ex situ TOF-SIMS chemical analysis to reveal that Br(-) or Cl(-) ions can promote crystal growth, yet reactive I(-) ions prevent them from incorporating into the lattice of the final perovskite crystal structure. The Cl(-) ions are located in the grain boundaries of the perovskite films. These findings significantly advance our understanding of the role of halogens during synthesis of hybrid perovskites and provide an insightful guidance to the engineering of high-quality perovskite films, essential for exploring superior-performing and cost-effective optoelectronic devices. PMID:26931634

  11. Anion order in perovskites: a group-theoretical analysis.

    PubMed

    Talanov, M V; Shirokov, V B; Talanov, V M

    2016-03-01

    Anion ordering in the structure of cubic perovskite has been investigated by the group-theoretical method. The possibility of the existence of 261 ordered low-symmetry structures, each with a unique space-group symmetry, is established. These results include five binary and 14 ternary anion superstructures. The 261 idealized anion-ordered perovskite structures are considered as aristotypes, giving rise to different derivatives. The structures of these derivatives are formed by tilting of BO6 octahedra, distortions caused by the cooperative Jahn-Teller effect and other physical effects. Some derivatives of aristotypes exist as real substances, and some as virtual ones. A classification of aristotypes of anion superstructures in perovskite is proposed: the AX class (the simultaneous ordering of A cations and anions in cubic perovskite structure), the BX class (the simultaneous ordering of B cations and anions) and the X class (the ordering of anions only in cubic perovskite structure). In most perovskites anion ordering is accompanied by cation ordering. Therefore, the main classes of anion order in perovskites are the AX and BX classes. The calculated structures of some anion superstructures are reported. Comparison of predictions and experimentally investigated anion superstructures shows coherency of theoretical and experimental results. PMID:26919374

  12. Modeling of optical losses in perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Taghavi, M. Javad; Houshmand, Mohammad; Zandi, M. Hossein; Gorji, Nima E.

    2016-09-01

    The optical losses within the structure of hybrid perovskite solar cells are investigated using only the optical properties of each layer e.g. refractive index and extinction coefficient. This model allows calculating the transmission/reflection rates at the interfaces and absorption loss within any layer. Then, the short circuit current density and loss percentage are calculated versus the perovskite and TiO2 thicknesses from 50 nm to 150 nm. To make our calculations closer to reality, we extracted the optical properties of each device component from the literature reports on glass/TCO/TiO2/perovskite/metal. The simulations were fitted with the experimental results of some relevant references. Our simulations show that ITO transmits the light better than SnO2 as the TCO front electrode, and the light reflection at both sides of the perovskite layer, e.g. at TiO2/perovskite and perovskite/Spiro-OMeTAD, is lower than 25%. The light interference and multiple reflections have been accounted in our calculations and finally we showed that a thicker TiO2 and perovskite cause more optical loss in current density due to stronger absorption.

  13. Deciphering Halogen Competition in Organometallic Halide Perovskite Growth

    DOE PAGESBeta

    Keum, Jong Kahk; Ovchinnikova, Olga S.; Chen, Shiyou; Du, Mao-Hua; Ivanov, Ilia N; Rouleau, Christopher; Geohegan, David B.; Xiao, Kai

    2016-03-01

    Organometallic halide perovskites (OHPs) hold great promise for next-generation, low-cost optoelectronic devices. During the chemical synthesis and crystallization of OHP thin films a major unresolved question is the competition between multiple halide species (e.g. I-, Cl-, Br-) in the formation of the mixed halide perovskite crystals. Whether Cl- ions are successfully incorporated into the perovskite crystal structure or alternatively, where they are located, is not yet fully understood. Here, in situ X-ray diffraction measurements of crystallization dynamics are combined with ex situ TOF-SIMS chemical analysis to reveal that Br- or Cl- ions can promote crystal growth, yet reactive I- ionsmore » prevent them from incorporating into the lattice of the final perovskite crystal structure. The Cl- ions are located in the grain boundaries of the perovskite films. These findings significantly advance our understanding of the role of halogens during synthesis of hybrid perovskites, and provide an insightful guidance to the engineering of high-quality perovskite films, essential for exploring superior-performance and cost-effective optoelectronic devices.« less

  14. Perovskite Materials for Light-Emitting Diodes and Lasers.

    PubMed

    Veldhuis, Sjoerd A; Boix, Pablo P; Yantara, Natalia; Li, Mingjie; Sum, Tze Chien; Mathews, Nripan; Mhaisalkar, Subodh G

    2016-08-01

    Organic-inorganic hybrid perovskites have cemented their position as an exceptional class of optoelectronic materials thanks to record photovoltaic efficiencies of 22.1%, as well as promising demonstrations of light-emitting diodes, lasers, and light-emitting transistors. Perovskite materials with photoluminescence quantum yields close to 100% and perovskite light-emitting diodes with external quantum efficiencies of 8% and current efficiencies of 43 cd A(-1) have been achieved. Although perovskite light-emitting devices are yet to become industrially relevant, in merely two years these devices have achieved the brightness and efficiencies that organic light-emitting diodes accomplished in two decades. Further advances will rely decisively on the multitude of compositional, structural variants that enable the formation of lower-dimensionality layered and three-dimensional perovskites, nanostructures, charge-transport materials, and device processing with architectural innovations. Here, the rapid advancements in perovskite light-emitting devices and lasers are reviewed. The key challenges in materials development, device fabrication, operational stability are addressed, and an outlook is presented that will address market viability of perovskite light-emitting devices.

  15. Random lasing actions in self-assembled perovskite nanoparticles

    NASA Astrophysics Data System (ADS)

    Liu, Shuai; Sun, Wenzhao; Li, Jiankai; Gu, Zhiyuan; Wang, Kaiyang; Xiao, Shumin; Song, Qinghai

    2016-05-01

    Solution-based perovskite nanoparticles have been intensively studied in the past few years due to their applications in both photovoltaic and optoelectronic devices. Here, based on the common ground between solution-based perovskite and random lasers, we have studied the mirrorless lasing actions in self-assembled perovskite nanoparticles. After synthesis from a solution, discrete lasing peaks have been observed from optically pumped perovskites without any well-defined cavity boundaries. We have demonstrated that the origin of the random lasing emissions is the scattering between the nanostructures in the perovskite microplates. The obtained quality (Q) factors and thresholds of random lasers are around 500 and 60 μJ/cm2, respectively. Both values are comparable to the conventional perovskite microdisk lasers with polygon-shaped cavity boundaries. From the corresponding studies on laser spectra and fluorescence microscope images, the lasing actions are considered random lasers that are generated by strong multiple scattering in random gain media. In additional to conventional single-photon excitation, due to the strong nonlinear effects of perovskites, two-photon pumped random lasers have also been demonstrated for the first time. We believe this research will find its potential applications in low-cost coherent light sources and biomedical detection.

  16. Perovskite Materials for Light-Emitting Diodes and Lasers.

    PubMed

    Veldhuis, Sjoerd A; Boix, Pablo P; Yantara, Natalia; Li, Mingjie; Sum, Tze Chien; Mathews, Nripan; Mhaisalkar, Subodh G

    2016-08-01

    Organic-inorganic hybrid perovskites have cemented their position as an exceptional class of optoelectronic materials thanks to record photovoltaic efficiencies of 22.1%, as well as promising demonstrations of light-emitting diodes, lasers, and light-emitting transistors. Perovskite materials with photoluminescence quantum yields close to 100% and perovskite light-emitting diodes with external quantum efficiencies of 8% and current efficiencies of 43 cd A(-1) have been achieved. Although perovskite light-emitting devices are yet to become industrially relevant, in merely two years these devices have achieved the brightness and efficiencies that organic light-emitting diodes accomplished in two decades. Further advances will rely decisively on the multitude of compositional, structural variants that enable the formation of lower-dimensionality layered and three-dimensional perovskites, nanostructures, charge-transport materials, and device processing with architectural innovations. Here, the rapid advancements in perovskite light-emitting devices and lasers are reviewed. The key challenges in materials development, device fabrication, operational stability are addressed, and an outlook is presented that will address market viability of perovskite light-emitting devices. PMID:27214091

  17. Syntheses, structures, and ionic conductivities of perovskite-structured lithium–strontium–aluminum/gallium–tantalum-oxides

    SciTech Connect

    Phraewphiphat, Thanya; Iqbal, Muhammad; Suzuki, Kota; Matsuda, Yasuaki; Yonemura, Masao; Hirayama, Masaaki; Kanno, Ryoji

    2015-05-15

    The ionic conductivities of new perovskite-structured lithium–strontium–aluminum/gallium–tantalum oxides were investigated. Solid solutions of the new perovskite oxides, (Li{sub x}Sr{sub 1−x})(Al{sub (1−x)/2}Ta{sub (1+x)/2})O{sub 3} and (Li{sub x}Sr{sub 1−x})(Ga{sub (1−x)/2}Ta{sub (1+x)/2})O{sub 3}, were synthesized using a ball-milled-assisted solid-state method. The partial substitution of the smaller Ga{sup +3} for Ta{sup +5} resulted in new compositions, the structures of which were determined by neutron diffraction measurements using a cubic perovskite structural model with the Pm−3m space group. Vacancies were introduced into the Sr(Li) sites by the formation of solid solutions with compositions (Li{sub x}Sr{sub 1−x−y}☐{sub y})(Ga{sub [(1−x)/2]−y}Ta{sub [(1+x)/2]+y})O{sub 3}, where the composition range of 0≤y≤0.20 was examined for x=0.2 and 0.25. The highest conductivity, 1.85×10{sup −3} S cm{sup −1} at 250 °C, was obtained for (Li{sub 0.25}Sr{sub 0.625}☐{sub 0.125})(Ga{sub 0.25}Ta{sub 0.75})O{sub 3} (x=0.25, y=0.125). Enhanced ionic conductivities were achieved by the introduction of vacancies at the A-sites. - Graphical abstract: Novel lithium-conducting oxides with the cubic perovskite structure (Li{sub x}Sr{sub 1−x−y}☐{sub y})(Ga{sub [(1−x)/2]−y}Ta{sub [(1+x)/2]+y})O{sub 3} provide a specific solid-solution region with various x and y values, exhibiting the highest ionic conductivity (1.85 S cm{sup −1} at 250 °C) for (Li{sub 0.25}Sr{sub 0.625}☐{sub 0.125})(Ga{sub 0.25}Ta{sub 0.75})O{sub 3} (x=0.25, y=0.125 in (Li{sub x}Sr{sub 1−x−y}☐{sub y})(Ga{sub [(1−x)/2]−y}Ta{sub [(1+x)/2]+y})O{sub 3}). The vacancies (☐) introduced into the A-sites contribute to the enhancement of lithium diffusion in the perovskite structure because of the enlargement of the bottleneck size and suppression of the interaction between lithium and oxygen. - Highlights: • The perovskite-structured novel Li

  18. When did oxygenic photosynthesis evolve?

    PubMed

    Buick, Roger

    2008-08-27

    The atmosphere has apparently been oxygenated since the 'Great Oxidation Event' ca 2.4 Ga ago, but when the photosynthetic oxygen production began is debatable. However, geological and geochemical evidence from older sedimentary rocks indicates that oxygenic photosynthesis evolved well before this oxygenation event. Fluid-inclusion oils in ca 2.45 Ga sandstones contain hydrocarbon biomarkers evidently sourced from similarly ancient kerogen, preserved without subsequent contamination, and derived from organisms producing and requiring molecular oxygen. Mo and Re abundances and sulphur isotope systematics of slightly older (2.5 Ga) kerogenous shales record a transient pulse of atmospheric oxygen. As early as ca 2.7 Ga, stromatolites and biomarkers from evaporative lake sediments deficient in exogenous reducing power strongly imply that oxygen-producing cyanobacteria had already evolved. Even at ca 3.2 Ga, thick and widespread kerogenous shales are consistent with aerobic photoautrophic marine plankton, and U-Pb data from ca 3.8 Ga metasediments suggest that this metabolism could have arisen by the start of the geological record. Hence, the hypothesis that oxygenic photosynthesis evolved well before the atmosphere became permanently oxygenated seems well supported. PMID:18468984

  19. When did oxygenic photosynthesis evolve?

    PubMed

    Buick, Roger

    2008-08-27

    The atmosphere has apparently been oxygenated since the 'Great Oxidation Event' ca 2.4 Ga ago, but when the photosynthetic oxygen production began is debatable. However, geological and geochemical evidence from older sedimentary rocks indicates that oxygenic photosynthesis evolved well before this oxygenation event. Fluid-inclusion oils in ca 2.45 Ga sandstones contain hydrocarbon biomarkers evidently sourced from similarly ancient kerogen, preserved without subsequent contamination, and derived from organisms producing and requiring molecular oxygen. Mo and Re abundances and sulphur isotope systematics of slightly older (2.5 Ga) kerogenous shales record a transient pulse of atmospheric oxygen. As early as ca 2.7 Ga, stromatolites and biomarkers from evaporative lake sediments deficient in exogenous reducing power strongly imply that oxygen-producing cyanobacteria had already evolved. Even at ca 3.2 Ga, thick and widespread kerogenous shales are consistent with aerobic photoautrophic marine plankton, and U-Pb data from ca 3.8 Ga metasediments suggest that this metabolism could have arisen by the start of the geological record. Hence, the hypothesis that oxygenic photosynthesis evolved well before the atmosphere became permanently oxygenated seems well supported.

  20. NREL Studies Carrier Separation and Transport in Perovskite Solar Cells

    SciTech Connect

    2016-01-01

    NREL scientists studied charge separation and transport in perovskite solar cells by determining the junction structure across the solar device using the nanoelectrical characterization technique of Kelvin probe force microscopy. The distribution of electrical potential across both planar and porous devices demonstrates a p-n junction structure at the interface between titanium dioxide and perovskite. In addition, minority-carrier transport within the devices operates under diffusion/drift. Clarifying the fundamental junction structure provides significant guidance for future research and development. This NREL study points to the fact that improving carrier mobility is a critical factor for continued efficiency gains in perovskite solar cells.