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Sample records for manganese oxide films

  1. Manganese oxide nanowires, films, and membranes and methods of making

    SciTech Connect

    Suib, Steven Lawrence; Yuan, Jikang

    2011-02-15

    Nanowires, films, and membranes comprising ordered porous manganese oxide-based octahedral molecular sieves and methods of making the same are disclosed. A method for forming nanowires includes hydrothermally treating a chemical precursor composition in a hydrothermal treating solvent to form the nanowires, wherein the chemical precursor composition comprises a source of manganese cations and a source of counter cations, and wherein the nanowires comprise ordered porous manganese oxide-based octahedral molecular sieves.

  2. Manganese oxide nanowires, films, and membranes and methods of making

    DOEpatents

    Suib, Steven Lawrence; Yuan, Jikang

    2008-10-21

    Nanowires, films, and membranes comprising ordered porous manganese oxide-based octahedral molecular sieves, and methods of making, are disclosed. A single crystal ultra-long nanowire includes an ordered porous manganese oxide-based octahedral molecular sieve, and has an average length greater than about 10 micrometers and an average diameter of about 5 nanometers to about 100 nanometers. A film comprises a microporous network comprising a plurality of single crystal nanowires in the form of a layer, wherein a plurality of layers is stacked on a surface of a substrate, wherein the nanowires of each layer are substantially axially aligned. A free standing membrane comprises a microporous network comprising a plurality of single crystal nanowires in the form of a layer, wherein a plurality of layers is aggregately stacked, and wherein the nanowires of each layer are substantially axially aligned.

  3. Growth and Dissolution of Iron and Manganese Oxide Films

    SciTech Connect

    Scot T. Martin

    2008-12-22

    Growth and dissolution of Fe and Mn oxide films are key regulators of the fate and transport of heavy metals in the environment, especially during changing seasonal conditions of pH and dissolved oxygen. The Fe and Mn are present at much higher concentrations than the heavy metals, and, when Fe and Mn precipitate as oxide films, heavy metals surface adsorb or co-precipitate and are thus essentially immobilized. Conversely, when the Fe and Mn oxide films dissolve, the heavy metals are released to aqueous solution and are thus mobilized for transport. Therefore, understanding the dynamics and properties of Fe and Mn oxide films and thus on the uptake and release of heavy metals is critically important to any attempt to develop mechanistic, quantitative models of the fate, transport, and bioavailablity of heavy metals. A primary capability developed in our earlier work was the ability to grow manganese oxide (MnO{sub x}) films on rhodochrosite (MnCO{sub 3}) substrate in presence of dissolved oxygen under mild alkaline conditions. The morphology of the films was characterized using contact-mode atomic force microscopy. The initial growth began by heteroepitaxial nucleation. The resulting films had maximum heights of 1.5 to 2 nm as a result of thermodynamic constraints. Over the three past years, we have investigated the effects of MnO{sub x} growth on the interactions of MnCO{sub 3} with charged ions and microorganisms, as regulated by the surface electrical properties of the mineral. In 2006, we demonstrated that MnO{sub x} growth could induce interfacial repulsion and surface adhesion on the otherwise neutral MnCO{sub 3} substrate under environmental conditions. Using force-volume microscopy (FVM), we measured the interfacial and adhesive forces on a MnO{sub x}/MnCO{sub 3} surface with a negatively charged silicon nitride tip in a 10-mM NaNO3 solution at pH 7.4. The interfacial force and surface adhesion of MnOx were approximately 40 pN and 600 pN, respectively

  4. Chemical and optical properties of thermally evaporated manganese oxide thin films

    SciTech Connect

    Al-Kuhaili, M. F.

    2006-09-15

    Manganese oxide thin films were deposited using thermal evaporation from a tungsten boat. Films were deposited under an oxygen atmosphere, and the effects of thickness, substrate temperature, and deposition rate on their properties were investigated. The chemical properties of the films were studied using x-ray photoelectron spectroscopy and x-ray fluorescence. The optical properties were determined from normal-incidence transmittance and reflectance. Based on the chemical and optical characterizations, the optimum conditions for the deposition of the films were investigated. Subsequently, the optical properties (refractive index, extinction coefficient, and band gap) of these films were determined.

  5. Manganese oxide helices, rings, strands, and films, and methods for their preparation

    DOEpatents

    Suib, Steven L.; Giraldo, Oscar; Marquez, Manuel; Brock, Stephanie

    2003-01-07

    Methods for the preparation of mixed-valence manganese oxide compositions with quaternary ammonium ions are described. The compositions self-assemble into helices, rings, and strands without any imposed concentration gradient. These helices, rings, and strands, as well as films having the same composition, undergo rapid ion exchange to replace the quaternary ammonium ions with various metal ions. And the metal-ion-containing manganese oxide compositions so formed can be heat treated to form semi-conducting materials with high surface areas.

  6. Electrochromic performance, wettability and optical study of copper manganese oxide thin films: Effect of annealing temperature

    NASA Astrophysics Data System (ADS)

    Falahatgar, S. S.; Ghodsi, F. E.; Tepehan, F. Z.; Tepehan, G. G.; Turhan, İ.

    2014-01-01

    In the present work, the nanostructured copper manganese oxide (CMO) thin films were prepared from acetate based sol-gel precursors and deposited on glass and indium tin oxide (ITO) substrates by dip-coating technique. The films were annealed at 300, 400 and 500 °C in ambient atmosphere. The effects of annealing temperature on structural, morphological, wettability, electrochromic and optical properties of CMO thin films were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), energy dispersive spectroscopy (EDX), water contact angle measurement (WCA), cyclic voltammetry (CV) measurements and ultraviolet-visible (UV-vis) spectrophotometery. The presence of mixed oxide phases comprising of copper manganese oxide (CuMn2O4) and manganese oxide at different annealing temperature was confirmed by XRD patterns. The results showed that the Mn3O4 phase has been changed to Mn2O3 when the annealing temperature is increased from 300 to 500 °C. The FESEM images indicated that the granular surface morphology was sensitive to annealing temperature. EDX studies indicated that the thin films contained O, Mn and Cu species. Wettability studies showed that the water contact angle of the nanostructured CMO thin films coated on glass substrates was influenced by the variation of annealing temperature and the surface nature of thin films was changed from hydrophilic to hydrophobic. The results of CVs measurement indicated that the anodic and cathodic charge density and capacitance of all CMO samples decreased with increasing scan rate in potential range of -1-1 eV. Also, the annealed CMO thin film at 500 °C showed better electrochromic performance with respect to other samples at lower scan rate. The thickness, refractive index, extinction coefficient and optical band gap of thin films coated on glass substrates were calculated from reflectance and transmittance spectra using an iterative numerical method. The optical band gap of

  7. Sodium manganese oxide thin films as cathodes for Na-ion batteries

    SciTech Connect

    Baggetto, Loic; Carroll, Kyler J; Unocic, Raymond R; Bridges, Craig A; Meng, Ying Shirley; Veith, Gabriel M

    2014-01-01

    This paper presents the fabrication and characterization of sodium manganese oxide cathode thin films for rechargeable Na-ion batteries. Layered oxide compounds of nominal compositions Na0.6MnO2 and Na1.0MnO2 have been prepared by radio frequency magnetron sputtering and post-annealing at high temperatures under various conditions. The Na0.6MnO2 thin films possess either a hexagonal or orthorhombic structure while the Na1.0MnO2 films crystallize in a monoclinic structure, as shown by X-ray diffraction and X-ray absorption spectroscopy results. The potential profiles of the film cathodes are characterized by features similar to those measured for the powders and exhibit reversible storage capacities in the range of 50-60 Ah cm-2 m-1, which correspond to about 120-140 mAh g-1, and are maintained over 80 cycles.

  8. Solid-phase photocatalytic degradation of polyethylene film with manganese oxide OMS-2

    NASA Astrophysics Data System (ADS)

    Liu, Guanglong; Liao, Shuijiao; Zhu, Duanwei; Cui, Jingzhen; Zhou, Wenbing

    2011-01-01

    Solid-phase photocatalytic degradation of polyethylene (PE) film with cryptomelane-type manganese oxide (OMS-2) as photocatalyst was investigated in the ambient air under ultraviolet and visible light irradiation. The properties of the composite films were compared with those of the pure PE film through performing weight loss monitoring, IR spectroscopy, scanning electron microscopic (SEM) and X-ray photoelectron spectroscopy (XPS). The photoinduced degradation of PE-OMS-2 composite films was higher than that of the pure films, while there has been little change under the visible light irradiation. The weight loss of PE-OMS-2 (1.0 wt%) composite films steadily decreased and reached 16.5% in 288 h under UV light irradiation. Through SEM observation there were some cavities on the surface of composite films, but few change except some surface chalking phenomenon occurred in pure PE film. The degradation rate with ultraviolet irradiation is controllable by adjusting the content of OMS-2 particles in PE plastic. Finally, the mechanism of photocatalytic degradation of the composite films was briefly discussed.

  9. Synthesis and pseudocapacitive studies of composite films of polyaniline and manganese oxide nanoparticles

    NASA Astrophysics Data System (ADS)

    Chen, Liang; Sun, Li-Jie; Luan, Feng; Liang, Ying; Li, Yat; Liu, Xiao-Xia

    We report the synthesis and pseudocapacitive studies of a composite film (PANI-ND-MnO 2) of polyaniline (PANI) and manganese oxide (MnO 2) nanoparticles. To enhance the interaction of MnO 2 and PANI, the surfaces of MnO 2 nanoparticles were modified by a silane coupling reagent, triethoxysilylmethyl N-substituted aniline (ND42). The composite film was obtained via controlled electro-co-polymerization of aniline and N-substituted aniline grafted on surfaces of MnO 2 nanoparticles (ND-MnO 2) on a carbon cloth in a electrolyte of 0.5 M H 2SO 4 and 0.6 M (NaPO 3) 6. In comparison to similarly prepared PANI film, the incorporation of MnO 2 nanoparticles substantially increases the effective surface area of the film by reducing the size of rod-like PANI aggregates and avoiding the entanglement of these PANI nanorods. Significantly, we observed significant enhancement of specific capacitance in PANI-ND-MnO 2 film compared to PANI-MnO 2 film prepared in a similar condition, indicating that the presence of the coupling reagent can improve the electrochemical performance of PANI composite film. A symmetric model capacitor has been fabricated by using two PANI-ND-MnO 2 nanocomposite films as electrodes. The PANI-ND-MnO 2 capacitor showed an average specific capacitance of ∼80 F g -1 and a stable coulombic efficiency of ∼98% over 1000 cycles. The results demonstrated that PANI-ND-MnO 2 nanocomposites are promising materials for supercapacitor electrode and the importance of designing and manipulating the interaction between PANI and MnO 2 for fundamentally improving capacitive properties.

  10. Growth of different phases of yttrium manganese oxide thin films by pulsed laser deposition

    SciTech Connect

    Kumar, Manish; Choudhary, R. J.; Phase, D. M.

    2012-06-05

    Various phases of yttrium manganese oxide (YMO) thin films have been synthesized on different substrates from a single target of h-YMnO{sub 3}. It is observed that the phase stability and crystallinity of YMO thin films depend on the substrate used and oxygen partial pressure (OPP). (110) oriented and polycrystalline growth of h-YMnO{sub 3} are observed on the Al{sub 2}O{sub 3} (0001) and NGO (110) substrates respectively, when grown in OPP {approx_equal} 10{sup -6} Torr. While for similar OPP value, growth of mixed phases (h-YMnO{sub 3} and o-YMn{sub 2}O{sub 5}) is observed on Si (001) substrate. Oriented growth of O-YMn{sub 2}O{sub 5} phase film on Si (001) substrate is observed first time, when deposited at OPP value of 225 and 350 mTorr. +3 and mixed oxidation states (+3 and +4) of Mn were confirmed by x-ray photoelectron spectroscopy in pure YMnO{sub 3} phase and YMn{sub 2}O{sub 5} phase respectively.

  11. Investigation of the influence of cadmium processing on zinc gallium oxide:manganese thin films for photoluminescent and thin film electroluminescent applications

    NASA Astrophysics Data System (ADS)

    Flynn, Michael John

    concentration left by the sublimed material, which aided the incorporation and activation of the manganese. The cadmium in the sputtering targets also impacted the crystal structure of the films. Films from cadmium free targets exhibited a strong (111) x-ray diffraction peak, while those from cadmium processed targets more closely resembled the powder structure. The optimum thin film electroluminescent performance was obtained for films sputtered from targets processed with between 5% and 15% cadmium substituted for zinc. This was the result of improved diffusion during the anneals, due to the sublimation of cadmium oxide and the resulting large vacancy concentration. The best performance was obtained for films annealed at between 875°C and 900°C for 6--12 hours. These films exhibited both the maximum luminance (55 cd/m2 at 60 Hz) and the lowest transferred charge (˜20 muC/cm2). This combined for a peak efficiency of 0.5 lm/W at 60 Hz). Beyond 12 hours at 900°C or temperatures higher than this, EL performance degraded due to the decomposition of the thin film. It was concluded that the luminescent performance of this material is strongly influenced by the loss of cadmium during processing. The enhanced diffusion afforded by the cadmium sublimation results in improved EL performance at annealing temperature lower that that of pure zinc gallate.

  12. Controlled Synthesis of Hollow Manganese Oxide Nanocrystals.

    PubMed

    Nam, Ki Min; Oh, Kyung Hee; Ham, Kyung-Sik

    2016-02-01

    Carbon spheres have been prepared from glucose under hydrothermal conditions to facilitate the synthesis of hollow manganese oxides. The phases of manganese oxide are controlled by changing annealing temperature of the manganese monoxide on a carbon sphere template. The particles on the carbon surface get an agglomeration and make dense oxide shell during the calcination step, which result in typical hollow structures. The electrochemical properties of hollow manganese oxides have been investigated to elucidate their relative catalytic activities. PMID:27433689

  13. Surface chemistry of coated lithium manganese nickel oxide thin film cathodes studied by XPS

    SciTech Connect

    Baggetto, Loic; Dudney, Nancy J; Veith, Gabriel M

    2013-01-01

    The effect of coating high voltage LiMn1.5Ni0.5O4 spinel cathode thin films with three metal oxide thin layers is discussed. The changes in surface chemistry of the electrodes are measured by X-ray photoelectron spectroscopy. ZnO is found to decompose during the first charge whereas Al2O3 and ZrO2 are stable for more than 100 cycles. ZrO2, however, importantly limits the available Li storage capacity of the electrochemical reaction due to poorer kinetics. Al2O3 offers the best results in term of capacity retention. Upon cycling, the evidence of a signal at 75.4 eV in the Al2p binding energy spectrum indicates the partial conversion of Al2O3 into Al2O2F2. Moreover, the continuous formation of PEO , esters and LixPOyFz compounds on the surface of the electrodes is found for all coating materials.

  14. AFM Nanolithography of Lanthanum Barium Manganese Oxide (LaBaMnO3)Thin Films: The Effect of Oxygen Pressure Variations During Film Growth

    NASA Astrophysics Data System (ADS)

    Stumpf, Christoper; Schaefer, David; Kolagani, Rajeswari; Yong, Grace; Warecki, Zoey

    2014-03-01

    In AFM nanolithography, a bias voltage applied between the tip of an atomic force microscope (AFM) and a sample is used to produce nanoscale modifications of material surfaces. AFM nanolithography has been studied extensively on a variety of materials, but limited studies have been performed on perovskite manganites such as Lanthanum Barium Manganese Oxide (LBMO). Studying such materials is important because of their potential applications for room-temperature nanoscale spintronic devices. Previous research on LBMO by our group has focused on how parameters such as applied tip voltage, temperature, and humidity affect the creation of nanopatterns. This paper reports on the influence of growth pressure of the LBMO films grown by pulsed laser deposition. Films grown on (100) SrTiO3 were studied for growth pressures ranging between 100 mTorr to 400 mTorr. Our studies indicate that the type of nanopatterns induced by AFM and the relaxation dynamics of these patterns are sensitive to the film growth pressure. The growth pressure is mainly known to affect the oxygen concentration and the surface roughness, but possible variations in cationic stoichiometry could also contribute to these results. RK and GY acknowledge support from the National Science Foundation Grant ECCS 1128586.

  15. Giant negative magnetoresistance in Manganese-substituted Zinc Oxide

    PubMed Central

    Wang, X. L.; Shao, Q.; Zhuravlyova, A.; He, M.; Yi, Y.; Lortz, R.; Wang, J. N.; Ruotolo, A.

    2015-01-01

    We report a large negative magnetoresistance in Manganese-substituted Zinc Oxide thin films. This anomalous effect was found to appear in oxygen-deficient films and to increase with the concentration of Manganese. By combining magnetoresistive measurements with magneto-photoluminescence, we demonstrate that the effect can be explained as the result of a magnetically induced transition from hopping to band conduction where the activation energy is caused by the sp-d exchange interaction. PMID:25783664

  16. Effects of Post-Deposition Annealing on the Properties of Calcium Manganese Oxide Thin Films

    NASA Astrophysics Data System (ADS)

    Ferrone, Natalie; Chaudhry, Adeel; Hart, Cacie; Lawson, Bridget; Houston, David; Neubauer, Samuel; Johnson, Anthony; Schaefer, David; Kolagani, Rajeswari

    We will present our results on the effects of post-deposition annealing on the structural and electrical properties of CaMnO3-d thin films grown by Pulsed Laser deposition. The thin films are epitaxially grown on (100) LaAlO3 which has larger in-plane lattice parameters than that of bulk CaMnO3, which leads to bi-axial tensile strain in the thin films. Results from our laboratory show that bi-axial tensile strain leads to low resistivity in thinner films, the resistivity increasing with increasing thickness. These results are suggestive of a coupling between strain and oxygen stoichiometry in the thin films. We have investigated the effects of post-deposition annealing in various gas ambients towards the goal of understanding the effects of relaxation and oxygen stoichiometric changes. We will present a comparison of the structural and electrical properties of as-grown and post-annealed films over a range of thicknesses. Support from Towson University Office of Undergraduate Research, Fisher Endowment Grant & Undergraduate Research Grant from the Fisher College of Science & Mathematics, Seed Funding Grant from the School of Emerging technologies, & NSF Grant ECCS 112856.

  17. Thermal chemistry of Mn{sub 2}(CO){sub 10} during deposition of thin manganese films on silicon oxide and on copper surfaces

    SciTech Connect

    Qin Xiangdong; Sun Huaxing; Zaera, Francisco

    2012-01-15

    The surface chemistry of dimanganese decacarbonyl on the native oxide of Si(100) wafers was characterized with the aid of x-ray photoelectron spectroscopy. Initial experiments in a small stainless-steel reactor identified a narrow range of temperatures, between approximately 445 and 465 K, in which the deposition of manganese could be achieved in a self-limiting fashion, as is desirable for atomic layer deposition. Deposition at higher temperatures leads to multilayer growth, but the extent of this Mn deposition reverses at even higher temperatures (about 625 K), and also ifhydrogen is added to the reaction mixture. Extensive decarbonylation takes place below room temperature, but limited C-O bond dissociation and carbon deposition are still seen after high exposures at 625 K. The films deposited at low ({approx}450 K) temperatures are mostly in the form of MnO, but at 625 K that converts to a manganese silicate, and upon higher doses a manganese silicide forms at the SiO{sub 2}/Si(100) interface as well. No metallic manganese could be deposited with this precursor on either silicon dioxide or copper surfaces.

  18. Manganese oxidation by Leptothrix discophora.

    PubMed

    Boogerd, F C; de Vrind, J P

    1987-02-01

    Cells of Leptothrix discophora SS1 released Mn2+-oxidizing factors into the medium during growth in batch culture. Manganese was optimally oxidized when the medium was buffered with HEPES (N-2-hydroxyethylpiperazine-N'-2-ethanesulfonic acid) at pH 7.5. Manganese-oxidizing activity in the culture medium in which this strain had been grown previously was sensitive to heat, phosphate, Tris, NaN3, HgCl2 NaCl, sodium dodecyl sulfate, and pronase; 0.5 mol of O2 was consumed per mol of MnO2 formed. During Mn2+ oxidation, protons were liberated. With sodium dodecyl sulfate-polyacrylamide gel electrophoresis, two protein-containing bands were detected in the spent culture medium. One band had an apparent molecular weight of 110,000 and was predominant in Mn2+-oxidizing activity. The second product (Mr 85,000) was only detected in some cases and probably represents a proteolytic breakdown moiety of the 110,000-Mr protein. The Mn2+-oxidizing factors were associated with the MnO2 aggregates that had been formed in spent culture medium. After solubilization of this MnO2 with ascorbate, Mn2+-oxidizing activity could be recovered. PMID:3804969

  19. Biomimetic Water-Oxidation Catalysts: Manganese Oxides.

    PubMed

    Kurz, Philipp

    2016-01-01

    The catalytic oxidation of water to molecular oxygen is a key process for the production of solar fuels. Inspired by the biological manganese-based active site for this reaction in the enzyme Photosystem II, researchers have made impressive progress in the last decades regarding the development of synthetic manganese catalysts for water oxidation. For this, it has been especially fruitful to explore the many different types of known manganese oxides MnOx. This chapter first offers an overview of the structural, thermodynamic, and mechanistic aspects of water-oxidation catalysis by MnOx. The different test systems used for catalytic studies are then presented together with general reactivity trends. As a result, it has been possible to identify layered, mixed Mn (III/IV)-oxides as an especially promising class of bio-inspired catalysts and an attempt is made to give structure-based reasons for the good performances of these materials. In the outlook, the challenges of catalyst screenings (and hence the identification of a "best MnOx catalyst") are discussed. There is a great variety of reaction conditions which might be relevant for the application of manganese oxide catalysts in technological solar fuel-producing devices, and thus catalyst improvements are currently still addressing a very large parameter space. Nonetheless, detailed knowledge about the biological catalyst and a solid experimental basis concerning the syntheses and water-oxidation reactivities of MnOx materials have been established in the last decade and thus this research field is well positioned to make important contributions to solar fuel research in the future. PMID:25980320

  20. Environmental Controls of Biological Manganese Oxidation

    NASA Astrophysics Data System (ADS)

    Belz, A. P.; Ahn, C. C.; Nealson, K. H.

    2001-12-01

    Biological catalysis of manganese oxidation represents an important contribution to global manganese cycling; biological oxidation rates are several orders of magnitude higher than those of abiotic processes. Despite recent genetics advances, ongoing behavioral studies, and a large pool of knowledge regarding manganese chemistry, the links between biology and environmental chemistry remain unresolved. We have performed experiments on batch cultures of Leptothrix discophora SS-1 to explore the physiology of biological manganese oxidation. We have further conducted spectroscopic and microscopic studies of the mechanism as manganese proceeds from the soluble Mn2+ species to the insoluble Mn(III) and Mn(IV) phases. These investigations suggest roles for aqueous chemistry, mineralogy, and microbial physiology in controlling manganese fluxes in metal-rich environments.

  1. Synthesis, characterization, optical and sensing property of manganese oxide nanoparticles

    SciTech Connect

    Manigandan, R.; Suresh, R.; Giribabu, K.; Narayanan, V.; Vijayalakshmi, L.; Stephen, A.

    2014-01-28

    Manganese oxide nanoparticles were prepared by thermal decomposition of manganese oxalate. Manganese oxalate was synthesized by reacting 1:1 mole ratio of manganese acetate and ammonium oxalate along with sodium dodecyl sulfate (SDS). The structural characterization of manganese oxalate and manganese oxide nanoparticles was analyzed by XRD. The XRD spectrum confirms the crystal structure of the manganese oxide and manganese oxalate. In addition, the average grain size, lattice parameter values were also calculated using XRD spectrum. Moreover, the diffraction peaks were broadened due to the smaller size of the particle. The band gap of manganese oxide was calculated from optical absorption, which was carried out by DRS UV-Visible spectroscopy. The morphology of manganese oxide nanoparticles was analyzed by SEM images. The FT-IR analysis confirms the formation of the manganese oxide from manganese oxalate nanoparticles. The electrochemical sensing behavior of manganese oxide nanoparticles were investigated using hydrogen peroxide by cyclic voltammetry.

  2. Kinetic patterns in the formation of nanosized manganese-manganese oxide systems

    NASA Astrophysics Data System (ADS)

    Surovoi, E. P.; Bugerko, L. N.; Surovaya, V. E.; Zaikonnikova, T. M.

    2016-03-01

    Transformations in nanosized manganese films are studied by means of optical spectroscopy, microscopy, and gravimetry at different film thicknesses ( d = 4-108 nm) and temperatures of heat treatment ( T = 373-673 K). It is found that the kinetic curves of conversion are satisfactorily described in the terms of linear, inverse logarithmic, cubic, and logarithmic laws. The contact potential difference is measured for Mn and MnO films, and photo EMF is measured for Mn-MnO systems. An energy band diagram is constructed for Mn-MnO systems. A model for the thermal transformation of Mn films is proposed that includes stages of oxygen adsorption, the redistribution of charge carriers in the contact field of Mn-MnO, and manganese(II) oxide formation.

  3. Manganese oxidation model for rivers

    USGS Publications Warehouse

    Hess, Glen W.; Kim, Byung R.; Roberts, Philip J.W.

    1989-01-01

    The presence of manganese in natural waters (>0.05 mg/L) degrades water-supply quality. A model was devised to predict the variation of manganese concentrations in river water released from an impoundment with the distance downstream. The model is one-dimensional and was calibrated using dissolved oxygen, biochemical oxygen demand, pH, manganese, and hydraulic data collected in the Duck River, Tennessee. The results indicated that the model can predict manganese levels under various conditions. The model was then applied to the Chattahoochee River, Georgia. Discrepancies between observed and predicted may be due to inadequate pH data, precipitation of sediment particles, unsteady flow conditions in the Chattahoochee River, inaccurate rate expressions for the low pH conditions, or their combinations.

  4. The Products of Manganese (II) Oxidation

    SciTech Connect

    Perkins, A.

    2004-09-03

    Manganese, the second most abundant transition metal in the earth's crust, exists in a number of oxidation states, among which the II, III, and IV oxidation states are of greatest environmental importance. Produced through microbial activity, manganese oxides help to mediate redox reactions with organic and inorganic compounds and help to sequester a variety of metals. The mechanism by which Manganese (II) is oxidized to Manganese (IV) is a biologically catalyzed process. There are at least three different pathways by which Mn(II) can be bacterially oxidized to Mn(IV); the first in which states that Mn(II) can be oxidized to mixed Mn(III, IV), and Mn(IV) oxides and oxyhydroxides. The second of these pathways is that Mn(II) can be directly oxidized to Mn(IV) and the last of these pathways is that Mn(II) follows an enzymatic bond with a Mn(III) intermediate in which Mn(II) oxidizes to Mn(III) and then to Mn(IV). The pathways of focus for this research are the latter two pathways.

  5. Silver manganese oxide electrodes for lithium batteries

    DOEpatents

    Thackeray, Michael M.; Vaughey, John T.; Dees, Dennis W.

    2006-05-09

    This invention relates to electrodes for non-aqueous lithium cells and batteries with silver manganese oxide positive electrodes, denoted AgxMnOy, in which x and y are such that the manganese ions in the charged or partially charged electrodes cells have an average oxidation state greater than 3.5. The silver manganese oxide electrodes optionally contain silver powder and/or silver foil to assist in current collection at the electrodes and to improve the power capability of the cells or batteries. The invention relates also to a method for preparing AgxMnOy electrodes by decomposition of a permanganate salt, such as AgMnO4, or by the decomposition of KMnO4 or LiMnO4 in the presence of a silver salt.

  6. Widespread distribution of ability to oxidize manganese among freshwater bacteria.

    PubMed

    Gregory, E; Staley, J T

    1982-08-01

    Manganese-oxidizing heterotrophic bacteria were found to comprise a significant proportion of the bacterial community of Lake Washington (Seattle, Wash.) and Lake Virginia (Winter Park, Fla.). Identification of these freshwater bacteria showed that members of a variety of genera are capable of oxidizing manganese. Isolates maintained in the laboratory spontaneously lost the ability to oxidize manganese. A direct correlation was found between the presence of plasmid DNA and the ability of the organism to oxidize manganese. PMID:16346084

  7. Fabrication and characterization of lithium manganese nickel oxide sputtered thin film cathodes for lithium-ion batteries

    SciTech Connect

    Baggetto, Loic; Unocic, Raymond R; Dudney, Nancy J; Veith, Gabriel M

    2012-01-01

    Li-rich and stoichiometric Li1Mn1.5Ni0.5O4 (LMNO) cathode films have been prepared by magnetron sputtering. Sputtering from a Li stoichiometric target yields Li-rich films composed of spinel, layered and monoclinic phases. Films obtained from a Li deficient target are mostly made of a spinel phase and little layered material. The resulting cathode thin films have good capacity retention and very high rate capability. The reaction mechanism has been investigated by XRD and HRTEM and evidences the reversible formation of a spinel phase, as is also found for the powder samples. The film geometry enables to understand the effect of coatings (ZnO or LiPON). Coating high voltage cathodes reduces the coulombic losses but at the price of rate performance. Nonetheless, these coated sputtered electrode thin films offer a higher rate capability than other LMNO thin films obtained by other physical vapor deposition techniques.

  8. Manganese oxide cathodes for rechargeable batteries

    NASA Astrophysics Data System (ADS)

    Im, Dongmin

    Manganese oxides are considered as promising cathodes for rechargeable batteries due to their low cost and low toxicity as well as the abundant natural resources. In this dissertation, manganese oxides have been investigated as cathodes for both rechargeable lithium and alkaline batteries. Nanostructured lithium manganese oxides designed for rechargeable lithium cells have been synthesized by reducing lithium permanganate with methanol or hydrogen in various solvents followed by firing at moderate temperatures. The samples have been characterized by wet-chemical analyses, thermal methods, spectroscopic methods, and electron microscopy. It has been found that chemical residues in the oxides such as carboxylates and hydroxyl groups, which could be controlled by varying the reaction medium, reducing agents, and additives, make a significant influence on the electrochemical properties. The Li/Mn ratio in the material has also been found to be a critical factor in determining the rechargeability of the cathodes. The optimized samples exhibit a high capacity of close to 300 mAh/g with good cyclability and charge efficiency. The high capacity with a lower discharge voltage may make these nanostructured oxides particularly attractive for lithium polymer batteries. The research on the manganese oxide cathodes for alkaline batteries is focused on an analysis of the reaction products generated during the charge/discharge processes or by some designed chemical reactions mimicking the electrochemical processes. The factors influencing the formation of Mn3O4 in the two-electron redox process of delta-MnO2 have been studied with linear sweep voltammetry combined with X-ray diffraction. The presence of bismuth, the discharge rate, and the microstructure of the electrodes are found to affect the formation of Mn3O4, which is known to be electrochemically inactive. A faster voltage sweep and a more intimate mixing of the manganese oxide and carbon in the cathode are found to suppress

  9. Electrochromic properties of manganese oxide (MnO{sub x}) thin films made by electron beam deposition

    SciTech Connect

    Erlandsson, O.; Lindvall, J.; Nguyen Ngoc Toan; Nguyen Van Hung; Vu Thi Bich; Nguyen Nang Dinh

    1993-12-31

    In recent years, considerable attention has been given to both the theoretical and the experimental investigation of the physical and physico-chemical properties of the chromogenics materials due their favorable and promising applications such as electrochromic devices, energy-efficient smart windows, automobile mirrors and building glazings. Electrochromic MnO{sub x} thin films were prepared by using an electron beam technique followed by annealing post-treatment. Electrochromic properties of the films were studied in three different solutions: 1M LiClO{sub 4} in propylene carbonate, KOH (pH = 10.5) and natrium borate (pH = 9.2). The transmittance spectra of the colored films combined with their cyclic voltammograms have showed that the enhancement of the electrochromic behavior of these films can be attributed to the insertion (or extraction) of the OH{sup {minus}} anions into (or from) the MnO{sub x} films. The best electrochromic efficiency of the films was obtained in the borate electrolyte.

  10. Nanostructured manganese oxides as highly active water oxidation catalysts: a boost from manganese precursor chemistry.

    PubMed

    Menezes, Prashanth W; Indra, Arindam; Littlewood, Patrick; Schwarze, Michael; Göbel, Caren; Schomäcker, Reinhard; Driess, Matthias

    2014-08-01

    We present a facile synthesis of bioinspired manganese oxides for chemical and photocatalytic water oxidation, starting from a reliable and versatile manganese(II) oxalate single-source precursor (SSP) accessible through an inverse micellar molecular approach. Strikingly, thermal decomposition of the latter precursor in various environments (air, nitrogen, and vacuum) led to the three different mineral phases of bixbyite (Mn2 O3 ), hausmannite (Mn3 O4 ), and manganosite (MnO). Initial chemical water oxidation experiments using ceric ammonium nitrate (CAN) gave the maximum catalytic activity for Mn2 O3 and MnO whereas Mn3 O4 had a limited activity. The substantial increase in the catalytic activity of MnO in chemical water oxidation was demonstrated by the fact that a phase transformation occurs at the surface from nanocrystalline MnO into an amorphous MnOx (1oxidizing agent. Photocatalytic water oxidation in the presence of [Ru(bpy)3 ](2+) (bpy=2,2'-bipyridine) as a sensitizer and peroxodisulfate as an electron acceptor was carried out for all three manganese oxides including the newly formed amorphous MnOx . Both Mn2 O3 and the amorphous MnOx exhibit tremendous enhancement in oxygen evolution during photocatalysis and are much higher in comparison to so far known bioinspired manganese oxides and calcium-manganese oxides. Also, for the first time, a new approach for the representation of activities of water oxidation catalysts has been proposed by determining the amount of accessible manganese centers. PMID:25044528

  11. Oxidation state of marine manganese nodules

    USGS Publications Warehouse

    Piper, D.Z.; Basler, J.R.; Bischoff, J.L.

    1984-01-01

    Analyses of the bulk oxidation state of marine manganese nodules indicates that more than 98% of the Mn in deep ocean nodules is present as Mn(IV). The samples were collected from three quite different areas: the hemipelagic environment of the Guatemala Basin, the pelagic area of the North Pacific, and seamounts in the central Pacific. Results of the study suggest that todorokite in marine nodules is fully oxidized and has the following stoichiometry: (K, Na, Ca, Ba).33(Mg, Cu, Ni).76Mn5O22(H2O)3.2. ?? 1984.

  12. Thermochemistry of iron manganese oxide spinels

    SciTech Connect

    Guillemet-Fritsch, Sophie; Navrotsky, Alexandra . E-mail: anavrotsky@ucdavis.edu; Tailhades, Philippe; Coradin, Herve; Wang Miaojun

    2005-01-15

    Oxide melt solution calorimetry has been performed on iron manganese oxide spinels prepared at high temperature. The enthalpy of formation of (Mn{sub x}Fe{sub 1-x}){sub 3}O{sub 4} at 298K from the oxides, tetragonal Mn{sub 3}O{sub 4} (hausmannite) and cubic Fe{sub 3}O{sub 4} (magnetite), is negative from x=0 to x=0.67 and becomes slightly positive for 0.670.6) spinels of intermediate compositions. The enthalpies of formation are discussed in terms of three factors: oxidation-reduction relative to the end-members, cation distribution, and tetragonality. A combination of measured enthalpies and Gibbs free energies of formation in the literature provides entropies of mixing. {delta}S{sub mix}, consistent with a cation distribution in which all trivalent manganese is octahedral and all other ions are randomly distributed for x>0.5, but the entropy of mixing appears to be smaller than these predicted values for x<0.4.

  13. [Characterization of manganese oxidation by Pseudomonas sp. QJX-1].

    PubMed

    Zhou, Na-Na; Bai, Yao-Hui; Liang, Jin-Song; Luo, Jin-Ming; Liu, Rui-Ping; Hu, Cheng-Zhi; Yuan, Lin-Jiang

    2014-02-01

    A manganese-oxidizing bacteria (QJX-1) was isolated from the soil of a manganese mine. It was identified as Pseudomonas sp. QJX-1 by 16S rDNA sequencing. Experimental results showed that the Pseudomonas sp. QJX-1 has a multi-copper oxidase gene CumA, which is an essential component for manganese oxidation by Pseudomonas sp. Under the condition of low initial inoculum level (D600, 0.020), 5.05 mg x L(-1 Mn2+ could be oxidized by QJX-1 within 48 h with a conversion rate of as high as 99.4%. In comparison with the eutrophic conditions, the oligotrophic condition dramatically increased the biological manganese oxidation rate. Biofilm formation by employing the quartz sand could further improve the oxidation rate of Mn2+. Based on these results, it is speculated that biological manganese oxidation in underground water treatment is comparatively high. PMID:24812972

  14. 40 CFR 721.10201 - Cobalt lithium manganese nickel oxide.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Cobalt lithium manganese nickel oxide... Specific Chemical Substances § 721.10201 Cobalt lithium manganese nickel oxide. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as cobalt lithium...

  15. 40 CFR 721.10201 - Cobalt lithium manganese nickel oxide.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Cobalt lithium manganese nickel oxide... Specific Chemical Substances § 721.10201 Cobalt lithium manganese nickel oxide. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as cobalt lithium...

  16. 40 CFR 721.10201 - Cobalt lithium manganese nickel oxide.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Cobalt lithium manganese nickel oxide... Specific Chemical Substances § 721.10201 Cobalt lithium manganese nickel oxide. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as cobalt lithium...

  17. Biological Superoxide In Manganese Oxide Formation

    NASA Astrophysics Data System (ADS)

    Hansel, C.; Learman, D.; Zeiner, C.; Santelli, C. M.

    2011-12-01

    Manganese (Mn) oxides are among the strongest sorbents and oxidants within the environment, controlling the fate and transport of numerous elements and the degradation of recalcitrant carbon. Both bacteria and fungi mediate the oxidation of Mn(II) to Mn(III/IV) oxides but the genetic and biochemical mechanisms responsible remain poorly understood. Furthermore, the physiological basis for microbial Mn(II) oxidation remains an enigma. We have recently reported that a common marine bacterium (Roseobacter sp. AzwK-3b) oxidizes Mn(II) via reaction with extracellular superoxide (O2-) produced during exponential growth. Here we expand this superoxide-mediated Mn(II) oxidation pathway to fungi, introducing a surprising homology between prokaryotic and eukaryotic metal redox processes. For instance, Stibella aciculosa, a common soil Ascomycete filamentous fungus, precipitates Mn oxides at the base of asexual reproductive structures (synnemata) used to support conidia (Figure 1). This distribution is a consequence of localized production of superoxide (and it's dismutation product hydrogen peroxide, H2O2), leading to abiotic oxidation of Mn(II) by superoxide. Disruption of NADPH oxidase activity using the oxidoreductase inhibitor DPI leads to diminished cell differentiation and subsequent Mn(II) oxidation inhibition. Addition of Cu(II) (an effective superoxide scavenger) leads to a concentration dependent decrease in Mn oxide formation. We predict that due to the widespread production of extracellular superoxide within the fungal and likely bacterial kingdoms, biological superoxide may be an important contributor to the cycling of Mn, as well as other metals (e.g., Hg, Fe). Current and future explorations of the genes and proteins involved in superoxide production and Mn(II) oxidation will ideally lend insight into the physiological and biochemical basis for these processes.

  18. Real-Time Manganese Phase Dynamics during Biological and Abiotic Manganese Oxide Reduction.

    PubMed

    Johnson, Jena E; Savalia, Pratixa; Davis, Ryan; Kocar, Benjamin D; Webb, Samuel M; Nealson, Kenneth H; Fischer, Woodward W

    2016-04-19

    Manganese oxides are often highly reactive and easily reduced, both abiotically, by a variety of inorganic chemical species, and biologically during anaerobic respiration by microbes. To evaluate the reaction mechanisms of these different reduction routes and their potential lasting products, we measured the sequence progression of microbial manganese(IV) oxide reduction mediated by chemical species (sulfide and ferrous iron) and the common metal-reducing microbe Shewanella oneidensis MR-1 under several endmember conditions, using synchrotron X-ray spectroscopic measurements complemented by X-ray diffraction and Raman spectroscopy on precipitates collected throughout the reaction. Crystalline or potentially long-lived phases produced in these experiments included manganese(II)-phosphate, manganese(II)-carbonate, and manganese(III)-oxyhydroxides. Major controls on the formation of these discrete phases were alkalinity production and solution conditions such as inorganic carbon and phosphate availability. The formation of a long-lived Mn(III) oxide appears to depend on aqueous Mn(2+) production and the relative proportion of electron donors and electron acceptors in the system. These real-time measurements identify mineralogical products during Mn(IV) oxide reduction, contribute to understanding the mechanism of various Mn(IV) oxide reduction pathways, and assist in interpreting the processes occurring actively in manganese-rich environments and recorded in the geologic record of manganese-rich strata. PMID:27018915

  19. Bacterial manganese reduction and growth with manganese oxide as the sole electron acceptor

    NASA Technical Reports Server (NTRS)

    Myers, Charles R.; Nealson, Kenneth H.

    1988-01-01

    Microbes that couple growth to the reduction of manganese could play an important role in the biogeochemistry of certain anaerobic environments. Such a bacterium, Alteromonas putrefaciens MR-1, couples its growth to the reduction of manganese oxides only under anaerobic conditions. The characteristics of this reduction are consistent with a biological, and not an indirect chemical, reduction of manganese, which suggest that this bacterium uses manganic oxide as a terminal electron acceptor. It can also utilize a large number of other compounds as terminal electron acceptors; this versatility could provide a distinct advantage in environments where electron-acceptor concentrations may vary.

  20. 40 CFR 721.10011 - Barium calcium manganese strontium oxide.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Barium calcium manganese strontium... Specific Chemical Substances § 721.10011 Barium calcium manganese strontium oxide. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as barium...

  1. 40 CFR 721.10011 - Barium calcium manganese strontium oxide.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Barium calcium manganese strontium... Specific Chemical Substances § 721.10011 Barium calcium manganese strontium oxide. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as barium...

  2. 40 CFR 721.10011 - Barium calcium manganese strontium oxide.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Barium calcium manganese strontium... Specific Chemical Substances § 721.10011 Barium calcium manganese strontium oxide. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as barium...

  3. 40 CFR 721.10011 - Barium calcium manganese strontium oxide.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Barium calcium manganese strontium... Specific Chemical Substances § 721.10011 Barium calcium manganese strontium oxide. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as barium...

  4. 40 CFR 721.10011 - Barium calcium manganese strontium oxide.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Barium calcium manganese strontium... Specific Chemical Substances § 721.10011 Barium calcium manganese strontium oxide. (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as barium...

  5. Structural and surface changes of copper modified manganese oxides

    NASA Astrophysics Data System (ADS)

    Gac, Wojciech; Słowik, Grzegorz; Zawadzki, Witold

    2016-05-01

    The structural and surface properties of manganese and copper-manganese oxides were investigated. The oxides were prepared by the redox-precipitation method. X-ray diffraction and electron microscopy studies evidenced transformation of cryptomelane-type nanoparticles with 1-D channel structure into the large MnO crystallites with regular rippled-like surface patterns under reduction conditions. The development of Cu/CuO nanorods from strongly dispersed species was evidenced. Coper-modified manganese oxides showed good catalytic performance in methanol steam reforming reaction for hydrogen production. Low selectivity to CO was observed in the wide range of temperatures.

  6. Three manganese oxide-rich marine sediments harbor similar communities of acetate-oxidizing manganese-reducing bacteria.

    PubMed

    Vandieken, Verona; Pester, Michael; Finke, Niko; Hyun, Jung-Ho; Friedrich, Michael W; Loy, Alexander; Thamdrup, Bo

    2012-11-01

    Dissimilatory manganese reduction dominates anaerobic carbon oxidation in marine sediments with high manganese oxide concentrations, but the microorganisms responsible for this process are largely unknown. In this study, the acetate-utilizing manganese-reducing microbiota in geographically well-separated, manganese oxide-rich sediments from Gullmar Fjord (Sweden), Skagerrak (Norway) and Ulleung Basin (Korea) were analyzed by 16S rRNA-stable isotope probing (SIP). Manganese reduction was the prevailing terminal electron-accepting process in anoxic incubations of surface sediments, and even the addition of acetate stimulated neither iron nor sulfate reduction. The three geographically distinct sediments harbored surprisingly similar communities of acetate-utilizing manganese-reducing bacteria: 16S rRNA of members of the genera Colwellia and Arcobacter and of novel genera within the Oceanospirillaceae and Alteromonadales were detected in heavy RNA-SIP fractions from these three sediments. Most probable number (MPN) analysis yielded up to 10(6) acetate-utilizing manganese-reducing cells cm(-3) in Gullmar Fjord sediment. A 16S rRNA gene clone library that was established from the highest MPN dilutions was dominated by sequences of Colwellia and Arcobacter species and members of the Oceanospirillaceae, supporting the obtained RNA-SIP results. In conclusion, these findings strongly suggest that (i) acetate-dependent manganese reduction in manganese oxide-rich sediments is catalyzed by members of taxa (Arcobacter, Colwellia and Oceanospirillaceae) previously not known to possess this physiological function, (ii) similar acetate-utilizing manganese reducers thrive in geographically distinct regions and (iii) the identified manganese reducers differ greatly from the extensively explored iron reducers in marine sediments. PMID:22572639

  7. Manganese oxide microswitch for electronic memory based on neural networks

    NASA Technical Reports Server (NTRS)

    Ramesham, R.; Daud, T.; Moopenn, A.; Thakoor, A. P.; Khanna, S. K.

    1989-01-01

    A solid-state, resistance tailorable, programmable-once, binary, nonvolatile memory switch based on manganese oxide thin films is reported. MnO(x) exhibits irreversible memory switching from conducting (on) to insulating (off) state, with the off and on resistance ratio of greater than 10,000. The switching mechanism is current-triggered chemical transformation of a conductive MnO(2-Delta) to an insulating Mn2O3 state. The energy required for switching is of the order of 4-20 nJ/sq micron. The low switching energy, stability of the on and off states, and tailorability of the on state resistance make these microswitches well suited as programmable binary synapses in electronic associative memories based on neural network models.

  8. Formation of methyl iodide on a natural manganese oxide.

    PubMed

    Allard, Sébastien; Gallard, Hervé; Fontaine, Claude; Croué, Jean-Philippe

    2010-08-01

    This paper demonstrates that manganese oxides can initiate the formation of methyl iodide, a volatile compound that participates to the input of iodine into the atmosphere. The formation of methyl iodide was investigated using a natural manganese oxide in batch experiments for different conditions and concentrations of iodide, natural organic matter (NOM) and manganese oxide. Methyl iodide was formed at concentrations oxidation of NOM on manganese dioxide in the presence of iodide. However, the implication of elemental iodine cannot be excluded at acidic pH. Manganese oxides can then participate with ferric oxides to the formation of methyl iodide in soils and sediments. The formation of methyl iodide is unlikely in technical systems such as drinking water treatment i.e. for ppt levels of iodide and low contact times with manganese oxides. PMID:20580399

  9. Photochemical water oxidation by crystalline polymorphs of manganese oxides: structural requirements for catalysis.

    PubMed

    Robinson, David M; Go, Yong Bok; Mui, Michelle; Gardner, Graeme; Zhang, Zhijuan; Mastrogiovanni, Daniel; Garfunkel, Eric; Li, Jing; Greenblatt, Martha; Dismukes, G Charles

    2013-03-01

    Manganese oxides occur naturally as minerals in at least 30 different crystal structures, providing a rigorous test system to explore the significance of atomic positions on the catalytic efficiency of water oxidation. In this study, we chose to systematically compare eight synthetic oxide structures containing Mn(III) and Mn(IV) only, with particular emphasis on the five known structural polymorphs of MnO2. We have adapted literature synthesis methods to obtain pure polymorphs and validated their homogeneity and crystallinity by powder X-ray diffraction and both transmission and scanning electron microscopies. Measurement of water oxidation rate by oxygen evolution in aqueous solution was conducted with dispersed nanoparticulate manganese oxides and a standard ruthenium dye photo-oxidant system. No Ru was absorbed on the catalyst surface as observed by XPS and EDX. The post reaction atomic structure was completely preserved with no amorphization, as observed by HRTEM. Catalytic activities, normalized to surface area (BET), decrease in the series Mn2O3 > Mn3O4 ≫ λ-MnO2, where the latter is derived from spinel LiMn2O4 following partial Li(+) removal. No catalytic activity is observed from LiMn2O4 and four of the MnO2 polymorphs, in contrast to some literature reports with polydispersed manganese oxides and electro-deposited films. Catalytic activity within the eight examined Mn oxides was found exclusively for (distorted) cubic phases, Mn2O3 (bixbyite), Mn3O4 (hausmannite), and λ-MnO2 (spinel), all containing Mn(III) possessing longer Mn-O bonds between edge-sharing MnO6 octahedra. Electronically degenerate Mn(III) has antibonding electronic configuration e(g)(1) which imparts lattice distortions due to the Jahn-Teller effect that are hypothesized to contribute to structural flexibility important for catalytic turnover in water oxidation at the surface. PMID:23391134

  10. Amperometric Biosensors Based on Carbon Paste Electrodes Modified with Nanostructured Mixed-valence Manganese Oxides and Glucose Oxidase

    SciTech Connect

    Cui, Xiaoli; Liu, Guodong; Lin, Yuehe

    2005-06-01

    Nanostructured multivalent manganese oxides octahedral molecular sieve (OMS), including cryptomelane-type manganese oxides and todorokite-type manganese oxides, were synthesized and evaluated for chemical sensing and biosensing at low operating potential. Both cryptomelane-type manganese oxides and todorokite-type manganese oxides are nanofibrous crystals with sub-nanometer open tunnels that provide a unique property for sensing applications. The electrochemical and electrocatalytic performance of OMS for the oxidation of H2O2 have been compared. Both cryptomelane-type manganese oxides and todorokite-type manganese oxides can be used to fabricate sensitive H2O2 sensors. Amperometric glucose biosensors are constructed by bulk modification of carbon paste electrodes (CPEs) with glucose oxidase as a biocomponent and nanostructured OMS as a mediator. A Nafion thin film was applied as an immobilization/encapsulation and protective layer. The biosensors were evaluated as an amperometric glucose detector at phosphate buffer solution with a pH 7.4 at an operating potential of 0.3 V (vs. Ag/AgCl). The biosensor is characterized by a well-reproducible amperometric response, linear signal-to-glucose concentration range up to 3.5 mM and 1.75 mM, and detection limits (S/N = 3) of 0.1 mM and 0.05 mM for todorokite-type manganese oxide and cryptomelane-type manganese oxide modified electrodes, respectively. The biosensors based on OMS exhibit considerable good reproducibility and stability, and the construction and renewal are simple and inexpensive.

  11. A manganese oxidation model for rivers

    SciTech Connect

    Hess, G.W. ); Kim, Byung R. ); Roberts, P.J.W. )

    1989-04-01

    The presence of manganese in natural waters (>0.05 mg/L) degrades water-supply quality. A model was devised to predict the variation of manganese concentrations in river water released from an impoundment with the distance downstream. The model is one-dimensional and was calibrated using dissolved oxygen, biochemical oxygen demand, pH, manganese, and hydraulic data collected in the Duck River, Tennessee. The results indicated that the model can predict manganese levels under various conditions. The model was then applied to the Chattahoochee River, Georgia. Discrepancies between observed and predicted may be due to inadequate pH data, precipitation of sediment particles, unsteady flow conditions in the Chattahoochee River, inaccurate rate expressions for the los pH conditions, or their combinations.

  12. Surfactant-mediated electrodeposition of a water-oxidizing manganese oxide.

    PubMed

    Osowiecki, Wojciech T; Sheehan, Stafford W; Young, Karin J; Durrell, Alec C; Mercado, Brandon Q; Brudvig, Gary W

    2015-10-14

    Splitting water into hydrogen and oxygen is one of the most promising ways of storing energy from intermittent, renewable sources in the future. Toward this goal, development of inexpensive, stable, and non-toxic catalysts for water oxidation is crucial. We report that the electrodeposition of manganese oxide in the presence of sodium dodecyl sulfate (SDS) produces a material that is highly active for electrocatalytic water oxidation at pH near 7 and remains stable for over 24 hours of sustained electrolysis. Clark electrode measurements demonstrate more than 95% Faradaic efficiency for oxygen evolution after an initial charging period. We found that catalytic performance was optimized in films prepared by electrodeposition using a precursor solution containing moderate concentration of substrates, namely 25 mM Mn(2+) and 25 mM SDS. Microstructure and elemental analyses revealed that the deposited material, a mixed-phase manganese oxide, is structurally similar to materials used for electrochemical capacitors and batteries, drawing a parallel between highly studied cathode materials for rechargeable batteries and heterogeneous catalysts for water oxidation. PMID:26350519

  13. Microstructure and properties of manganese dioxide films prepared by electrodeposition

    NASA Astrophysics Data System (ADS)

    Jacob, G. Moses; Zhitomirsky, I.

    2008-08-01

    Nanostructured manganese dioxide films were obtained by galvanostatic, pulse and reverse pulse electrodeposition from 0.01 to 0.1 M KMnO 4 solutions. The deposition yield was investigated by in situ monitoring the deposit mass using a quartz crystal microbalance (QCM). Obtained films were studied by electron microscopy, X-ray diffraction analysis, energy dispersive spectroscopy, thermogravimetric and differential thermal analysis. The QCM and electron microscopy data were utilized for the investigation of deposition kinetics and film formation mechanism. It was shown that the deposition rate and film microstructure could be changed by variation of deposition conditions. The method allowed the fabrication of dense or porous films. The thickness of dense films was limited to ˜0.1 μm due to the insulating properties of manganese dioxide and film cracking, attributed to drying shrinkage. Porous and crack-free 1-2 μm films were obtained using galvanostatic or reverse pulse deposition from 0.02 M KMnO 4 solutions. It was shown that film porosity is beneficial for the charge transfer during deposition and crack prevention in thick films. Moreover, porous nanostructured films showed good capacitive behavior for applications in electrochemical supercapacitors. The porous nanostructured films prepared in the reverse pulse regime showed higher specific capacitance (SC) compared to the SC of the galvanostatic films. The highest SC of 279 F/g in a voltage window of 1 V was obtained in 0.1 M Na 2SO 4 solutions at a scan rate of 2 mV/s.

  14. Synthesis of manganese oxide supported on mesoporous titanium oxide: Influence of the block copolymer

    NASA Astrophysics Data System (ADS)

    Schmit, F.; Bois, L.; Chiriac, R.; Toche, F.; Chassagneux, F.; Besson, M.; Descorme, C.; Khrouz, L.

    2015-01-01

    Manganese oxides supported on mesoporous titanium oxides were synthesized via a sol-gel route using block copolymer self-assembly. The oxides were characterized by X-ray diffraction, infrared spectroscopy, thermal analyses, nitrogen adsorption/desorption, electron microscopy and electronic paramagnetic resonance. A mesoporous anatase containing amorphous manganese oxide particles could be obtained with a 0.2 Mn:Ti molar ratio. At higher manganese loading (0.5 Mn:Ti molar ratio), segregation of crystalline manganese oxide occurred. The influence of block copolymer and manganese salt on the oxide structure was discussed. The evolution of the textural and structural characteristics of the materials upon hydrothermal treatment was also investigated.

  15. Energetic basis of catalytic activity of layered nanophase calcium manganese oxides for water oxidation

    PubMed Central

    Birkner, Nancy; Nayeri, Sara; Pashaei, Babak; Najafpour, Mohammad Mahdi; Casey, William H.; Navrotsky, Alexandra

    2013-01-01

    Previous measurements show that calcium manganese oxide nanoparticles are better water oxidation catalysts than binary manganese oxides (Mn3O4, Mn2O3, and MnO2). The probable reasons for such enhancement involve a combination of factors: The calcium manganese oxide materials have a layered structure with considerable thermodynamic stability and a high surface area, their low surface energy suggests relatively loose binding of H2O on the internal and external surfaces, and they possess mixed-valent manganese with internal oxidation enthalpy independent of the Mn3+/Mn4+ ratio and much smaller in magnitude than the Mn2O3-MnO2 couple. These factors enhance catalytic ability by providing easy access for solutes and water to active sites and facile electron transfer between manganese in different oxidation states. PMID:23667149

  16. Water defluoridation by aluminium oxide-manganese oxide composite material.

    PubMed

    Alemu, Sheta; Mulugeta, Eyobel; Zewge, Feleke; Chandravanshi, Bhagwan Singh

    2014-08-01

    In this study, aluminium oxide-manganese oxide (AOMO) composite material was synthesized, characterized, and tested for fluoride removal in batch experiments. AOMO was prepared from manganese(II) chloride and aluminium hydroxide. The surface area of AOMO was found to be 30.7m2/g and its specific density was determined as 2.78 g/cm3. Detailed investigation of the adsorbent by inductively coupled plasma-optical emission spectrometry, inductively coupled plasma-mass spectrometry, and ion chromatography (for sulphate only) showed that it is composed of Al, Mn, SO4, and Na as major components and Fe, Si, Ca, and Mg as minor components. Thermogravimetric analysis was used to study the thermal behaviour of AOMO. X-ray diffraction analysis showed that the adsorbent is poorly crystalline. The point of zero charge was determined as 9.54. Batch experiments (by varying the proportion of MnO, adsorbent dose, contact time, initial F concentration, and raw water pH) showed that fluoride removal efficiency ofAOMO varied significantly with percentage of MnO with an optimum value of about I11% of manganese oxide in the adsorbent. The optimum dose of the adsorbent was 4 g/L which corresponds to the equilibrium adsorption capacity of 4.8 mg F-/g. Both the removal efficiency and adsorption capacity showed an increasing trend with an increase in initial fluoride concentration of the water. The pH for optimum fluoride removal was found to be in the range between 5 and 7. The adsorption data were analysed using the Freundlich, Langmuir, and Dubinirn-Radushkevich models. The minimum adsorption capacity obtained from the non-linear Freundlich isotherm model was 4.94 mg F-/g and the maximum capacity from the Langmuir isotherm method was 19.2mg F-/g. The experimental data of fluoride adsorption on AOMO fitted well to the Freundlich isotherm model. Kinetic studies showed that the adsorption is well described by a non-linear pseudo-second-order reaction model with an average rate constant of 3

  17. Electrodeposition of layered manganese oxide nanocomposites intercalated with strong and weak polyelectrolytes.

    PubMed

    Nakayama, Masaharu; Tagashira, Hiroki

    2006-04-11

    Multilayered manganese oxide nanocomposites intercalated with strong (poly(diallyldimethylammonium) chloride, PDDA) and weak (poly(allylamine hydrochloride), PAH) polyelectrolytes can be produced on polycrystalline platinum electrode in a thin film form by a simple, one-step electrochemical route. The process involves a potentiostatic oxidation of aqueous Mn2+ ions at around +1.0 V (vs Ag/AgCl) in the presence of polyelectrolytes. Fully charged PDDA polycations are accommodated tightly in the interlayer space by electrostatic interaction with negative charges on the manganese oxide layers, leading to an interlayer distance of 0.97 nm. The layered film prepared with PAH has a larger polymer content (PAH/Mn molar ratio of 0.98) than that (PDDA/Mn molar ratio of 0.43) made with PDDA because of the smaller charging degree of PAH, exhibiting a larger interlayer distance (1.19 nm). The interlayer PAH contains neutral (-NH2) and positively charged (-NH3(+)) amine groups, and the -NH3(+) groups are associated with Cl- (to generate -NH3(+) Cl- ion pairs) as well as the negatively charged manganese oxide layers. Both polyelectrolytes once incorporated were not ion exchanged with small cations in solution. The layered structure of PDDA/MnO(x) was collapsed during the reduction process in a KCl electrolyte solution, accompanying an expansion of the interlayer as a result of incorporation of K+ ions for charge neutrality. On the contrary, the layered PAH/MnO(x) film showed a good electrochemical response due to the redox reaction of Mn3+/Mn4+ couple with no change in the structure. X-ray photoelectron spectroscopy revealed that, in this case, excess negative charges generated on the manganese oxide layers upon reduction can be balanced by the protons being released from the -NH3(+) Cl- sites in the interlayer PAH; the Cl- anions becoming unnecessary are inevitably excluded from the interlayer, and vice versa upon oxidation. PMID:16584268

  18. The sorption of silver by poorly crystallized manganese oxides

    USGS Publications Warehouse

    Anderson, B.J.; Jenne, E.A.; Chao, T.T.

    1973-01-01

    The sorption of silver by poorly crystallized manganese oxides was studied using synthesized samples of three members of the manganous manganite (birnessite) group, of different chemical composition and crystallinity, and a poorly organized ??-MnO2. All four oxides sorbed significant quantities of silver. The manganous manganites showed the greatest sorption (up to 0.5 moles silver/mole MnOx at pH 7) while the ??-MnO2 showed the least (0.3 moles silver/ mole MnOx at pH 7). Sorption of silver was adequately described by the Langmuir equation over a considerable concentration range. The relationship failed at low pH values and high equilibrium silver concentrations. The sorption capacity showed a direct relationship with pH. However, the rate of increase of sorption capacity decreased at the higher pH values. Silver sorption maxima. were not directly related to surface area but appeared to vary with the amount of occluded sodium and potassium present in the manganese oxide. The important processes involved in the uptake of silver by the four poorly crystallized manganese oxides ara considered to be surface exchange for manganese, potassium and sodium as well as exchange for structural manganese, potassium and sodium. ?? 1973.

  19. Synthesis of manganese oxide supported on mesoporous titanium oxide: Influence of the block copolymer

    SciTech Connect

    Schmit, F.; Bois, L.; Chiriac, R.; Toche, F.; Chassagneux, F.; Besson, M.; Descorme, C.; Khrouz, L.

    2015-01-15

    Manganese oxides supported on mesoporous titanium oxides were synthesized via a sol–gel route using block copolymer self-assembly. The oxides were characterized by X-ray diffraction, infrared spectroscopy, thermal analyses, nitrogen adsorption/desorption, electron microscopy and electronic paramagnetic resonance. A mesoporous anatase containing amorphous manganese oxide particles could be obtained with a 0.2 Mn:Ti molar ratio. At higher manganese loading (0.5 Mn:Ti molar ratio), segregation of crystalline manganese oxide occurred. The influence of block copolymer and manganese salt on the oxide structure was discussed. The evolution of the textural and structural characteristics of the materials upon hydrothermal treatment was also investigated. - Graphical abstract: One-pot amorphous MnO{sub 2} supported on mesoporous anataseTiO{sub 2}. - Highlights: • Mesoporous manganese titanium oxides were synthesized using block copolymer. • Block copolymers form complexes with Mn{sup 2+} from MnCl{sub 2}. • With block copolymer, manganese oxide can be dispersed around the titania crystallites. • With Mn(acac){sub 2}, manganese is dispersed inside titania. • MnOOH crystallizes outside mesoporous titania during hydrothermal treatment.

  20. Coordination between manganese and nitrogen within the ligands in the manganese complexes facilitates the reconstitution of the water-oxidizing complex in manganese-depleted photosystem II preparations.

    PubMed

    Li, Shuqin; Chen, Guiying; Han, Guangye; Ling, Lin; Huang, Deguang; Khorobrykh, A A; Zharmukhamedov, S K; Liu, Qiutian; Klimov, V V; Kuang, Tingyun

    2006-09-01

    The water-oxidizing complex (WOC) within photosystem II (PSII) can be reconstituted with synthetic manganese complexes by a process called photoactivation; however, the key factors affecting the efficiency of synthetic manganese complexes in reconstitution of electron transport and oxygen evolution activity in manganese-depleted PSII remain unclear. In the present study, four complexes with different manganese coordination environments were used to reconstitute the WOC, and an interesting relationship was found between the coordination environment of the manganese atom in the complexes and their efficiency in restoring electron transport and oxygen evolution. If Mn(II) is coordinated to nitrogen atoms within the ligand, it can restore significant rates of electron transport and oxygen evolution; however, if the manganese atom is coordinated only to oxygen atoms instead of nitrogen atoms, it has no capability to restore electron transport and oxygen evolution. So, our results demonstrate that the capability of manganese complexes to reconstitute the WOC is mainly determined by the coordination between nitrogen atoms from ligands and the manganese atom. It is suggested from our results that the ligation between the nitrogen atom and the manganese atom within the manganese complex facilitates the photoligation of the manganese atom to histidyl residues on the apo-protein in manganese-depleted PSII during photoactivation. PMID:16791637

  1. Suppressing Manganese Dissolution from Lithium Manganese Oxide Spinel Cathodes with Single-Layer Graphene

    SciTech Connect

    Jaber-Ansari, Laila; Puntambekar, Kanan P.; Kim, Soo; Aykol, Muratahan; Luo, Langli; Wu, Jinsong; Myers, Benjamin D.; Iddir, Hakim; Russell, John T.; Saldana, Spencer J.; Kumar, Rajan; Thackeray, Michael M.; Curtiss, Larry A.; Dravid, Vinayak P.; Wolverton, Christopher M.; Hersam, Mark C.

    2015-06-24

    Spinel-structured LiMn 2 O 4 (LMO) is a desirable cathode material for Li-ion batteries due to its low cost, abundance, and high power capability. However, LMO suffers from limited cycle life that is triggered by manganese dissolution into the electrolyte during electrochemical cycling. Here, it is shown that single-layer graphene coatings suppress manganese dissolution, thus enhancing the performance and lifetime of LMO cathodes. Relative to lithium cells with uncoated LMO cathodes, cells with graphene-coated LMO cathodes provide improved capacity retention with enhanced cycling stability. X-ray photoelectron spectroscopy reveals that graphene coatings inhibit manganese depletion from the LMO surface. Additionally, transmission electron microscopy demonstrates that a stable solid electrolyte interphase is formed on graphene, which screens the LMO from direct contact with the electrolyte. Density functional theory calculations provide two mechanisms for the role of graphene in the suppression of manganese dissolution. First, common defects in single-layer graphene are found to allow the transport of lithium while concurrently acting as barriers for manganese diffusion. Second, graphene can chemically interact with Mn 3+ at the LMO electrode surface, promoting an oxidation state change to Mn 4+ , which suppresses dissolution.

  2. Np and Pu Sorption to Manganese Oxide Minerals

    SciTech Connect

    Zhao, P; Johnson, M R; Roberts, S K; Zavarin, M

    2005-08-30

    Manganese oxide minerals are a significant component of the fracture lining mineralogy at Yucca Mountain (Carlos et al., 1993) and within the tuff-confining unit at Yucca Flat (Prothro, 1998), Pahute Mesa (Drellack et al., 1997), and other locations at the Nevada Test Site (NTS). Radionuclide sorption to manganese oxide minerals was not included in recent Lawrence Livermore National Laboratory (LLNL) hydrologic source term (HST) models which attempt to predict the migration behavior of radionuclides away from underground nuclear tests. However, experiments performed for the Yucca Mountain Program suggest that these minerals may control much of the retardation of certain radionuclides, particularly Np and Pu (Triay et al., 1991; Duff et al., 1999). As a result, recent HST model results may significantly overpredict radionuclide transport away from underground nuclear tests. The sorption model used in HST calculations performed at LLNL includes sorption to iron oxide, calcite, zeolite, smectite, and mica minerals (Zavarin and Bruton 2004a; 2004b). For the majority of radiologic source term (RST) radionuclides, we believe that this accounts for the dominant sorption processes controlling transport. However, for the case of Np, sorption is rather weak to all but the iron and manganese oxides (Figure 1). Thus, we can expect to significantly reduce predicted Np transport by accounting for Np sorption to manganese oxides. Similarly, Pu has been shown to be predominantly associated with manganese oxides in Yucca Mountain fractured tuffs (Duff et al., 1999). Recent results on colloid-facilitated Pu transport (Kersting and Reimus, 2003) also suggest that manganese oxide coatings on fracture surfaces may compete with colloids for Pu, thus reducing the effects of colloid-facilitated Pu transport (Figure 1b). The available data suggest that it is important to incorporate Np and Pu sorption to manganese oxides in reactive transport models. However, few data are available for

  3. Stabilized chromium oxide film

    DOEpatents

    Nyaiesh, A.R.; Garwin, E.L.

    1986-08-04

    Stabilized air-oxidized chromium films deposited on high-power klystron ceramic windows and sleeves having a thickness between 20 and 150A are useful in lowering secondary electron emission yield and in avoiding multipactoring and window failure due to overheating. The ceramic substrate for the film is chosen from alumina, sapphire or beryllium oxide.

  4. Stabilized chromium oxide film

    DOEpatents

    Garwin, Edward L.; Nyaiesh, Ali R.

    1988-01-01

    Stabilized air-oxidized chromium films deposited on high-power klystron ceramic windows and sleeves having a thickness between 20 and 150.ANG. are useful in lowering secondary electron emission yield and in avoiding multipactoring and window failure due to overheating. The ceramic substrate for the film is chosen from alumina, sapphire or beryllium oxide.

  5. 40 CFR 721.10529 - Cobalt iron manganese oxide, carboxylic acid-modified (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Cobalt iron manganese oxide... Significant New Uses for Specific Chemical Substances § 721.10529 Cobalt iron manganese oxide, carboxylic acid... substance identified generically as cobalt iron manganese oxide, carboxylic acid-modified (PMN P-12-35)...

  6. 40 CFR 721.10529 - Cobalt iron manganese oxide, carboxylic acid-modified (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Cobalt iron manganese oxide... Significant New Uses for Specific Chemical Substances § 721.10529 Cobalt iron manganese oxide, carboxylic acid... substance identified generically as cobalt iron manganese oxide, carboxylic acid-modified (PMN P-12-35)...

  7. 40 CFR 721.4587 - Lithium manganese oxide (LiMn204) (generic name).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Lithium manganese oxide (LiMn204... Specific Chemical Substances § 721.4587 Lithium manganese oxide (LiMn204) (generic name). (a) Chemical... as lithium manganese oxide (LiMn204) (P-96-175) is subject to reporting under this section for...

  8. 40 CFR 721.4587 - Lithium manganese oxide (LiMn204) (generic name).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Lithium manganese oxide (LiMn204... Specific Chemical Substances § 721.4587 Lithium manganese oxide (LiMn204) (generic name). (a) Chemical... as lithium manganese oxide (LiMn204) (P-96-175) is subject to reporting under this section for...

  9. 40 CFR 721.4587 - Lithium manganese oxide (LiMn204) (generic name).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Lithium manganese oxide (LiMn204... Specific Chemical Substances § 721.4587 Lithium manganese oxide (LiMn204) (generic name). (a) Chemical... as lithium manganese oxide (LiMn204) (P-96-175) is subject to reporting under this section for...

  10. 40 CFR 721.4587 - Lithium manganese oxide (LiMn204) (generic name).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Lithium manganese oxide (LiMn204... Specific Chemical Substances § 721.4587 Lithium manganese oxide (LiMn204) (generic name). (a) Chemical... as lithium manganese oxide (LiMn204) (P-96-175) is subject to reporting under this section for...

  11. 40 CFR 721.4587 - Lithium manganese oxide (LiMn204) (generic name).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Lithium manganese oxide (LiMn204... Specific Chemical Substances § 721.4587 Lithium manganese oxide (LiMn204) (generic name). (a) Chemical... as lithium manganese oxide (LiMn204) (P-96-175) is subject to reporting under this section for...

  12. 40 CFR 721.10010 - Barium manganese oxide (BaMnO3).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Barium manganese oxide (BaMnO3). 721... Substances § 721.10010 Barium manganese oxide (BaMnO3). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as barium manganese oxide (BaMnO3) (PMN...

  13. 40 CFR 721.10010 - Barium manganese oxide (BaMnO3).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Barium manganese oxide (BaMnO3). 721... Substances § 721.10010 Barium manganese oxide (BaMnO3). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as barium manganese oxide (BaMnO3) (PMN...

  14. 40 CFR 721.10010 - Barium manganese oxide (BaMnO3).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Barium manganese oxide (BaMnO3). 721... Substances § 721.10010 Barium manganese oxide (BaMnO3). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as barium manganese oxide (BaMnO3) (PMN...

  15. 40 CFR 721.10010 - Barium manganese oxide (BaMnO3).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Barium manganese oxide (BaMnO3). 721... Substances § 721.10010 Barium manganese oxide (BaMnO3). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as barium manganese oxide (BaMnO3) (PMN...

  16. 40 CFR 721.10010 - Barium manganese oxide (BaMnO3).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Barium manganese oxide (BaMnO3). 721... Substances § 721.10010 Barium manganese oxide (BaMnO3). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as barium manganese oxide (BaMnO3) (PMN...

  17. 40 CFR 721.10013 - Manganese yttrium oxide (Mn2YO5).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Manganese yttrium oxide (Mn2YO5). 721... Substances § 721.10013 Manganese yttrium oxide (Mn2YO5). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as manganese yttrium oxide (Mn2YO5) (PMN...

  18. 40 CFR 721.10009 - Manganese yttrium oxide (MnYO3).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Manganese yttrium oxide (MnYO3). 721... Substances § 721.10009 Manganese yttrium oxide (MnYO3). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as manganese yttrium oxide (MnYO3) (PMN...

  19. 40 CFR 721.10013 - Manganese yttrium oxide (Mn2YO5).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Manganese yttrium oxide (Mn2YO5). 721... Substances § 721.10013 Manganese yttrium oxide (Mn2YO5). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as manganese yttrium oxide (Mn2YO5) (PMN...

  20. 40 CFR 721.10013 - Manganese yttrium oxide (Mn2YO5).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Manganese yttrium oxide (Mn2YO5). 721... Substances § 721.10013 Manganese yttrium oxide (Mn2YO5). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as manganese yttrium oxide (Mn2YO5) (PMN...

  1. 40 CFR 721.10009 - Manganese yttrium oxide (MnYO3).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Manganese yttrium oxide (MnYO3). 721... Substances § 721.10009 Manganese yttrium oxide (MnYO3). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as manganese yttrium oxide (MnYO3) (PMN...

  2. 40 CFR 721.10009 - Manganese yttrium oxide (MnYO3).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Manganese yttrium oxide (MnYO3). 721... Substances § 721.10009 Manganese yttrium oxide (MnYO3). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as manganese yttrium oxide (MnYO3) (PMN...

  3. 40 CFR 721.10013 - Manganese yttrium oxide (Mn2YO5).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Manganese yttrium oxide (Mn2YO5). 721... Substances § 721.10013 Manganese yttrium oxide (Mn2YO5). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as manganese yttrium oxide (Mn2YO5) (PMN...

  4. 40 CFR 721.10009 - Manganese yttrium oxide (MnYO3).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Manganese yttrium oxide (MnYO3). 721... Substances § 721.10009 Manganese yttrium oxide (MnYO3). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as manganese yttrium oxide (MnYO3) (PMN...

  5. Manganese

    MedlinePlus

    Manganese is a mineral that is found in several foods including nuts, legumes, seeds, tea, whole grains, and leafy green vegetables. It is ... manganese by mouth along with other vitamins and minerals can promote growth in children who have low ...

  6. ChemCam Update ? Manganese Oxides on Mars

    ScienceCinema

    Lanza, Nina

    2016-07-14

    A recent discovery of manganese oxides in Martian rocks might tell us that the Red Planet was once more Earth-like than previously believed. So what exactly does that mean? Nina Lanza, Los Alamos scientist and lead author of the new paper about these findings in Geophysical Research Letters, breaks it down for us.

  7. Preparation and characterization of amorphous manganese sulfide thin films by SILAR method

    SciTech Connect

    Pathan, H.M.; Kale, S.S.; Lokhande, C.D.; Han, Sung-Hwan . E-mail: shhan@hanyang.ac.kr; Joo, Oh-Shim

    2007-08-07

    Manganese sulfide thin films were deposited by a simple and inexpensive successive ionic layer adsorption and reaction (SILAR) method using manganese acetate as a manganese and sodium sulfide as sulfide ion sources, respectively. Manganese sulfide films were characterized for their structural, surface morphological and optical properties by means of X-ray diffraction, scanning electron microscopy, energy dispersive X-ray analysis and optical absorption measurement techniques. The as-deposited film on glass substrate was amorphous. The optical band gap of the film was found to be thickness dependent. As thickness increases optical band gap was found to be increase. The water angle contact was found to be 34{sup o}, suggesting hydrophilic nature of manganese sulfide thin films. The presence of Mn and S in thin film was confirmed by energy dispersive X-ray analysis.

  8. Magnetotransport in Pulsed Laser Deposited Manganese Doped Lead Sulfide Films

    NASA Astrophysics Data System (ADS)

    Rimal, Gaurab; Sapkota, Keshab; Maksymov, Artur; Spinu, Leonard; Wang, Wenyong; Tang, Jinke

    Diluted magnetic semiconductors (DMS) have been proposed as promising candidates for spintronic applications. Most research in this field has been confined to III-V and II-VI semiconductor system. There are reports on IV-VI semiconductors, however reports on lead sulfide (PbS) based DMS is limited. We study the transport, magnetic and structural properties of manganese doped lead sulfide (Mn:PbS) films produced by pulsed laser deposition (PLD). The films are found to show hopping transport at low tempeature. Low temperature magnetoresistance (MR) studies show that the sign of MR can be changed by application of gate voltage. The magnetic properties of the films were also studied which showed ferromagnetic behavior at room temperature.

  9. 40 CFR 721.10008 - Manganese strontium oxide (MnSrO3).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Manganese strontium oxide (MnSrO3... Specific Chemical Substances § 721.10008 Manganese strontium oxide (MnSrO3). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as manganese strontium...

  10. 40 CFR 721.10008 - Manganese strontium oxide (MnSrO3).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Manganese strontium oxide (MnSrO3... Specific Chemical Substances § 721.10008 Manganese strontium oxide (MnSrO3). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as manganese strontium...

  11. 40 CFR 721.10008 - Manganese strontium oxide (MnSrO3).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Manganese strontium oxide (MnSrO3... Specific Chemical Substances § 721.10008 Manganese strontium oxide (MnSrO3). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as manganese strontium...

  12. 40 CFR 721.10008 - Manganese strontium oxide (MnSrO3).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Manganese strontium oxide (MnSrO3... Specific Chemical Substances § 721.10008 Manganese strontium oxide (MnSrO3). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as manganese strontium...

  13. 40 CFR 721.10008 - Manganese strontium oxide (MnSrO3).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Manganese strontium oxide (MnSrO3... Specific Chemical Substances § 721.10008 Manganese strontium oxide (MnSrO3). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as manganese strontium...

  14. Manganese oxidation state mediates toxicity in PC12 cells

    SciTech Connect

    Reaney, S.H. . E-mail: stevereaney@hotmail.com; Smith, D.R.

    2005-06-15

    The role of the manganese (Mn) oxidation state on cellular Mn uptake and toxicity is not well understood. Therefore, undifferentiated PC12 cells were exposed to 0-200 {mu}M Mn(II)-chloride or Mn(III)-pyrophosphate for 24 h, after which cellular manganese levels were measured along with measures of cell viability, function, and cytotoxicity (trypan blue exclusion, medium lactate dehydrogenase (LDH), 8-isoprostanes, cellular ATP, dopamine, serotonin, H-ferritin, transferrin receptor (TfR), Mn-superoxide dismutase (MnSOD), and copper-zinc superoxide dismutase (CuZnSOD) protein levels). Exposures to Mn(III) >10 {mu}M produced 2- to 5-fold higher cellular manganese levels than equimolar exposures to Mn(II). Cell viability and ATP levels both decreased at the highest Mn(II) and Mn(III) exposures (150-200 {mu}M), while Mn(III) exposures produced increases in LDH activity at lower exposures ({>=}50 {mu}M) than did Mn(II) (200 {mu}M only). Mn(II) reduced cellular dopamine levels more than Mn(III), especially at the highest exposures (50% reduced at 200 {mu}M Mn(II)). In contrast, Mn(III) produced a >70% reduction in cellular serotonin at all exposures compared to Mn(II). Different cellular responses to Mn(II) exposures compared to Mn(III) were also observed for H-ferritin, TfR, and MnSOD protein levels. Notably, these differential effects of Mn(II) versus Mn(III) exposures on cellular toxicity could not simply be accounted for by the different cellular levels of manganese. These results suggest that the oxidation state of manganese exposures plays an important role in mediating manganese cytotoxicity.

  15. Transformation of bisphenol A by manganese oxide-coated sand.

    PubMed

    Lin, Kunde; Peng, Yiwen; Huang, Xinwen; Ding, Jiafeng

    2013-03-01

    Oxidative transformation of organic contaminants by manganese oxides was commonly investigated with pure MnO(2) suspension, which deviates from the fact that natural manganese oxides are seldom present as a pure form in the natural environment. In this study, we prepared manganese oxide-coated sand (MOCS) and evaluated its oxidative capacity using bisphenol A (BPA) as the model compound. BPA was transformed by MOCS and the reaction followed an exponential decay model. The reaction was pH dependent and followed the order of pH 4.5>pH 5.5>pH 6.5>pH 7.5>pH 8.6>pH 9.6, indicating that acidic conditions facilitated BPA transformation while basic conditions disfavored the reaction. Coexisting metal ions exhibited inhibitory effects and followed the order of Fe(3+) > Zn(2+) > Cu(2+) > Ca(2+) > Mg(2+) > Na(+). Transformation of BPA by MOCS was much slower than that by pure MnO(2) suspension. However, similar transformation products were identified in both studies, suggesting the same reaction pathways. This work suggests that the reactivity of MnO(2) in the environment might be overestimated if extrapolating the result from the pure MnO(2) suspension because natural MnO(2) is mainly present as coating on the surface of soils and sediments. PMID:22752814

  16. Studies of Surface morphology and Atomic Force Microscope-induced Surface Modifications in Calcium Manganese Oxide (CaMnO) Thin Films

    NASA Astrophysics Data System (ADS)

    Johnson, Anthony; Hart, Cacie; Chaudhry, Adeel; Lawson, Bridget; Ferrone, Natalie; Neubauer, Samuel; Houston, David; Kolagani, Rajeswari; Schaefer, David

    CaMnOis a material of interest for applications as a catalyst for renewable energy applications. Our recent work on epitaxial thin films of this material has shown that films with a tensile lattice mismatch strain exhibit structural and electrical properties that indicate oxygen deficiency. We are studying the influence of strain and oxygen stoichiometry variations on surface morphology as revealed by atomic force microscopy. Our previous work in epitaxial thin films of the hole doped manganite nanoscale has demonstrated surface modifications induced by a voltage-biased AFM tip. Such surface modifications have been shown to be associated with changes in cation and oxygen stoichiometry. We will report results of similar studies on strained CaMnOthin films; relevant for understanding the surface mobility of oxygen vacancies. We acknowledge support from the Towson Office of University Undergraduate Research, Fisher Endowment Grant and Undergraduate Research Grant from the Fisher College of Science and Mathematics, and Seed Funding Grant from the School of Emerging technologies.

  17. Tensile Strain Effects on the Magneto-transport in Calcium Manganese Oxide Thin Films: Comparison with its Hole-doped Counterpart

    NASA Astrophysics Data System (ADS)

    Lawson, Bridget; Neubauer, Samuel; Chaudhry, Adeel; Hart, Cacie; Ferrone, Natalie; Houston, David; Yong, Grace; Kolagani, Rajeswari

    Magnetoresistance properties of the epitaxial thin films of doped rare earth manganites are known to be influenced by the effect of bi-axial strain induced by lattice mismatch with the substrate. In hole-doped manganites, the effect of both compressive and tensile strain is qualitatively consistent with the expected changes in unit cell symmetry from cubic to tetragonal, leading to Jahn-Teller strain fields that affect the energy levels of Mn3 + energy levels. Recent work in our laboratory on CaMnO3 thin films has pointed out that tetragonal distortions introduced by tensile lattice mismatch strain may also have the effect of modulating the oxygen content of the films in agreement with theoretical models that propose such coupling between strain and oxygen content. Our research focuses on comparing the magneto-transport properties of hole-doped manganite LaCaMnO3 thin films with that of its electron doped counter parts, in an effort to delineate the effects of oxygen stoichiometry changes on magneto-transport from the effects of Jahn-Teller type strain. Towson University Office of Undergraduate Research, Fisher Endowment Grant and Undergraduate Research Grant from the Fisher College of Science and Mathematics, Seed Funding Grant from the School of Emerging technologies and the NSF Grant ECCS 112856.

  18. Characterization of Synthetic and Natural Manganese Oxides as Martian Analogues

    NASA Technical Reports Server (NTRS)

    Fox, V. K.; Arvidson, R. E.; Jolliff, B. L.; Carpenter, P. K.; Catalano, J. G.; Hinkle, M. A. G.; Morris, R. V.

    2015-01-01

    Recent discoveries of highly concentrated manganese oxides in Gale Crater and on the rim of Endeavour Crater by the Mars Science Laboratory Curiosity and Mars Exploration Rover Opportunity, respectively, imply more highly oxidizing aqueous conditions than previously recognized. Manganese oxides are a significant environmental indicator about ancient aqueous conditions, provided the phases can be characterized reliably. Manganese oxides are typically fine-grained and poorly crystalline, making the mineral structures difficult to determine, and they generally have very low visible reflectance with few distinctive spectral features in the visible to near infrared, making them a challenge for interpretation from remote sensing data. Therefore, these recent discoveries motivate better characterization using methods available on Mars, particularly visible to near infrared (VNIR) spectroscopy, X-ray diffractometry (XRD), and compositional measurements. Both rovers have complementary instruments in this regard. Opportunity is equipped with its multispectral visible imager, Pancam, and an Alpha Particle X-ray Spectrometer (APXS), and Curiosity has the multispectral Mastcam, ChemCam (laser-induced breakdown spectroscopy and passive spectroscopy), and APXS for in situ characterization, and ChemMin (XRD) for collected samples.

  19. Distributions of Manganese, Iron, and Manganese-Oxidizing Bacteria In Lake Superior Sediments of Different Organic Carbon Content

    NASA Technical Reports Server (NTRS)

    Richardson, Laurie L.; Nealson, Kenneth H.

    1989-01-01

    Profiles of oxygen, soluble and particulate manganese and iron, organic carbon and nitrogen were examined in Lake Superior sediment cores, along with the distribution and abundance of heterotrophic and manganese oxidizing bacteria. Analyses were performed using cores collected with the submersible Johnson Sea Link II. Three cores, exhibiting a range of organic carbon content, were collected from the deepest basin in Lake Superior and the north and south ends of the Caribou trough, and brought to the surface for immediate analysis. Minielectrode profiles of oxygen concentration of the three cores were carried out using a commercially available minielectrode apparatus. Oxygen depletion to less than 1% occurred within 4 cm of the surface for two of the cores, but not until approximately 15 cm for the core from the south basin of the Caribou trough. The three cores exhibited very different profiles of soluble, as well as leachable, manganese and iron, suggesting different degrees of remobilization of these metals in the sediments. Vertical profiles of viable bacteria and Mn oxidizing bacteria, determined by plating and counting, showed that aerobic (and facultatively aerobic) heterotrophic bacteria were present at the highest concentrations near the surface and decreased steadily with depth, while Mn oxidizing bacteria were concentrations primarily at and above the oxic/anoxic interface. Soluble manganese in the pore waters, along with abundant organic carbon, appeared to enhance the presence of manganese oxidizing bacteria, even below the oxic/anoxic interface. Profiles of solid-phase leachable manganese suggested a microbial role in manganese reprecipitation in these sediments.

  20. Nano-sized manganese oxides as biomimetic catalysts for water oxidation in artificial photosynthesis: a review

    PubMed Central

    Najafpour, Mohammad Mahdi; Rahimi, Fahimeh; Aro, Eva-Mari; Lee, Choon-Hwan; Allakhverdiev, Suleyman I.

    2012-01-01

    There has been a tremendous surge in research on the synthesis of various metal compounds aimed at simulating the water-oxidizing complex (WOC) of photosystem II (PSII). This is crucial because the water oxidation half reaction is overwhelmingly rate-limiting and needs high over-voltage (approx. 1 V), which results in low conversion efficiencies when working at current densities required for hydrogen production via water splitting. Particular attention has been given to the manganese compounds not only because manganese has been used by nature to oxidize water but also because manganese is cheap and environmentally friendly. The manganese–calcium cluster in PSII has a dimension of about approximately 0.5 nm. Thus, nano-sized manganese compounds might be good structural and functional models for the cluster. As in the nanometre-size of the synthetic models, most of the active sites are at the surface, these compounds could be more efficient catalysts than micrometre (or bigger) particles. In this paper, we focus on nano-sized manganese oxides as functional and structural models of the WOC of PSII for hydrogen production via water splitting and review nano-sized manganese oxides used in water oxidation by some research groups. PMID:22809849

  1. Preliminary LIBS analysis of Yucca Mountain manganese oxide minerals

    SciTech Connect

    Blacic, J.; Pettit, D.; Cremers, D.

    1996-01-01

    The licensing and performance of a potential repository at Yucca Mountain will require the characterization of radionuclide sorptive capacity of the host rock, which in turn calls for hundreds of analyses based on extensive sampling or in situ measurements. A rapid method specifically for characterizing the manganese oxide minerals occurring heterogeneously throughout the Yucca Mountain block as fracture surface coatings is needed. Our unique solution is a laser-induced breakdown spectroscopy (LIBS) surface-analysis technique that is usable in the field to produce high-resolution atomic emission spectra. In tests with manganese oxide minerals and fracture surface coatings from a few Yucca Mountain core samples, we used four spectral bands to show that qualitative measurement of all constituent elements except K and Na (in the presence of Mn) is possible with LIBS. Detailed calibration of final hardware will make the system quantitative.

  2. Copper/Manganese Cocatalyzed Oxidative Coupling of Vinylarenes with Ketones.

    PubMed

    Lan, Xing-Wang; Wang, Nai-Xing; Zhang, Wei; Wen, Jia-Long; Bai, Cui-Bing; Xing, Yalan; Li, Yi-He

    2015-09-18

    A novel copper/manganese cocatalyzed direct oxidative coupling of terminal vinylarenes with ketones via C(sp(3))-H bond functionalization following C-C bond formation has been developed using tert-butyl hydroperoxide as the radical initiator. Various ketones underwent a free-radical addition of terminal vinylarenes to give the corresponding 1,4-dicarbonyl products with excellent regioselectivity and efficiency through one step. A possible reaction mechanism has been proposed. PMID:26348870

  3. Oxidation kinetics of pentachlorophenol by manganese dioxide.

    PubMed

    Zhao, Ling; Yu, Zhiqiang; Peng, Pingán; Huang, Weilin; Feng, Shunqing; Zhou, Haiyan

    2006-11-01

    This study examined the abiotic transformation kinetics of pentachlorophenol (PCP) by manganese dioxide (MnO2) at different solution chemistry and initial concentrations of PCP and MnO2. The measured PCP transformation rates were found to be on the order of 1.07 with respect to [PCP] and 0.91 and 0.87 with respect to [MnO2] and [H+], respectively. Dissolved Mn2+ and Ca2+ as background electrolytes considerably decreased the reaction rate because of their adsorption and hence blocking of active sites on MnO2 surfaces. The dechlorination number, 0.59 chloride ions per transformed PCP after a 1-h reaction, suggests that a fraction of the transformed PCP was not dechlorinated and may be coupled directly to dimeric products. Gas chromatography/ mass spectrometry and liquid chromatography/mass spectrometry/mass spectrometry techniques were used to identify two isomeric nonachlorohydroxybiphenylethers as major products and 2,3,5,6-tetrachloro-1,4-hydroquinone and tetrachlorocatechol as minor products. Product identification suggested that the reaction may include two parallel reactions to form either dimers or 2,3,5,6-tetrachloro-1,4-hydroquinone and tetrachlorocatechol via simultaneous dehydrochlorination and hydroxylation. PMID:17089714

  4. A redox-assisted supramolecular assembly of manganese oxide nanotube

    SciTech Connect

    Tao Li; Sun Chenggao; Fan Meilian; Huang Caijuan; Wu Hailong; Chao Zisheng . E-mail: zschao@yahoo.com; Zhai Hesheng . E-mail: hszhai@xmu.edu.cn

    2006-11-09

    In this paper, we report the hydrothermal synthesis of manganese oxide nanotube from an aqueous medium of pH 7, using KMnO{sub 4} and MnCl{sub 2} as inorganic precursors, polyoxyethylene (10) nonyl phenyl ether (TX-10) a surfactant and acetaldehyde an additive. The characterization of X-ray diffraction (XRD), transmission electron microscopy (TEM), selected area electron diffraction (SAED) and N{sub 2} adsorption at 77 K (BET) reveals that the synthesized manganese oxide nanotube has a mesopore size of ca. 3.65 nm and a wall thickness of ca. 12 nm, with the wall being composed of microporous crystals of monoclinic manganite. The X-ray photoelectron spectroscopy (XPS) result demonstrates a decrease of the binding energy of the Mn{sup 3+} in the manganese oxide nanotube, which may be related to both the nanotubular morphology and the crystalline pore wall. A mechanism of a redox-assisted supramolecular assembly, regulated by acetaldehyde, is postulated.

  5. Relations between magneto-optical properties and reactivity in cobalt-manganese ferrite thin films and powders

    NASA Astrophysics Data System (ADS)

    Bouet, Laurence; Tailhades, Philippe; Rousset, Abel

    1996-02-01

    Co-Mn spinel ferrites were prepared as submicron powders and thin films. Because of their finely divided state, these spinels could be oxidized at low temperatures to give novel cation-deficient ferrites. For these two material forms, the magneto-optical properties were found to be strongly dependent on the ferrite oxidation state. The highest coercivities and Faraday rotations were obtained when the ferrites were partially oxidized. These phenomena are attributed to the mechanical stress effect developed during the oxidation of the manganese ions. The properties of these ferrites could be of interest for magneto-optical recording applications. The first static recording tests were performed at 780 nm wavelength.

  6. Manganese ion-assisted assembly of superparamagnetic graphene oxide microbowls

    SciTech Connect

    Tian, Zhengshan; Xu, Chunxiang Li, Jitao; Zhu, Gangyi; Xu, Xiaoyong; Dai, Jun; Shi, Zengliang; Lin, Yi

    2014-03-24

    A facile manganese ion Mn(II)-assisted assembly has been designed to fabricate microbowls by using graphene oxide nanosheets as basic building blocks, which were exfoliated ultrasonically from the oxidized soot powders in deionized water. From the morphology evolution observations of transmission electron microscope and scanning electron microscope, a coordinating-tiling-collapsing manner is proposed to interpret the assembly mechanism based on attractive Van der Waals forces, π-π stacking, and capillary action. It is interesting to note that the as-prepared microbowls present a room temperature superparamagnetic behavior.

  7. Manganese oxide nanosheets and a 2D hybrid of graphene-manganese oxide nanosheets synthesized by liquid-phase exfoliation

    NASA Astrophysics Data System (ADS)

    Coelho, João; Mendoza-Sánchez, Beatriz; Pettersson, Henrik; Pokle, Anuj; McGuire, Eva K.; Long, Edmund; McKeon, Lorcan; Bell, Alan P.; Nicolosi, Valeria

    2015-06-01

    Manganese oxide nanosheets were synthesized using liquid-phase exfoliation that achieved suspensions in isopropanol (IPA) with concentrations of up to 0.45 mg ml-1. A study of solubility parameters showed that the exfoliation was optimum in N,N-dimethylformamide followed by IPA and diethylene glycol. IPA was the solvent of choice due to its environmentally friendly nature and ease of use for further processing. For the first time, a hybrid of graphene and manganese oxide nanosheets was synthesized using a single-step co-exfoliation process. The two-dimensional (2D) hybrid was synthesized in IPA suspensions with concentrations of up to 0.5 mg ml-1 and demonstrated stability against re-aggregation for up to six months. The co-exfoliation was found to be a energetically favorable process in which both solutes, graphene and manganese oxide nanosheets, exfoliate with an improved yield as compared to the single-solute exfoliation procedure. This work demonstrates the remarkable versatility of liquid-phase exfoliation with respect to the synthesis of hybrids with tailored properties, and it provides proof-of-concept ground work for further future investigation and exploitation of hybrids made of two or more 2D nanomaterials that have key complementary properties for various technological applications.

  8. Isotopic evidence for organic matter oxidation by manganese reduction in the formation of stratiform manganese carbonate ore

    USGS Publications Warehouse

    Okita, P.M.; Maynard, J.B.; Spiker, E. C.; Force, E.R.

    1988-01-01

    Unlike other marine-sedimentary manganese ore deposits, which are largely composed of manganese oxides, the primary ore at Molango (Hidalgo State, Mexico) is exclusively manganese carbonate (rhodochrosite, Mn-calcite, kutnahorite). Stable isotope studies of the carbonates from Molango provide critical new information relevant to the controversy over syngenetic and diagenetic models of stratiform manganese deposit formation. Negative ??13C values for carbonates from mineralized zones at Molango are strongly correlated with manganese content both on a whole rock scale and by mineral species. Whole rock ??13C data fall into three groups: high-grade ore = -16.4 to -11.5%.; manganese-rich, sub-ore-grade = -5.2 to 0%.; and unmineralized carbonates = 0 to +2.5%. (PDB). ??18O data show considerable overlap in values among the three groups: +4.8 to -2.8, -5.4 to -0.3%., and -7.4 to +6.2 (PDB), respectively. Isotopic data for individual co-existing minerals suggest a similar separation of ??13C values: ??13C values from calcite range from -1.1 to +0.7%. (PDB), whereas values from rhodochrosite are very negative, -12.9 to -5.5%., and values from kutnahorite or Mn-calcite are intermediate between calcite and rhodochrosite. 13C data are interpreted to indicate that calcite (i.e. unmineralized carbonate) formed from a normal marine carbon reservoir. However, 13C data for the manganese-bearing carbonates suggest a mixed seawater and organic source of carbon. The presence of only trace amounts of pyrite suggests sulfate reduction may have played a minor part in oxidizing organic matter. It is possible that manganese reduction was the predominant reaction that oxidized organic matter and that it released organic-derived CO2 to produce negative ??13C values and manganese carbonate mineralization. ?? 1988.

  9. Constraints on superoxide mediated formation of manganese oxides

    PubMed Central

    Learman, Deric R.; Voelker, Bettina M.; Madden, Andrew S.; Hansel, Colleen M.

    2013-01-01

    Manganese (Mn) oxides are among the most reactive sorbents and oxidants within the environment, where they play a central role in the cycling of nutrients, metals, and carbon. Recent discoveries have identified superoxide (O2−) both of biogenic and abiogenic origin as an effective oxidant of Mn(II) leading to the formation of Mn oxides. Here we examined the conditions under which abiotically produced superoxide led to oxidative precipitation of Mn and the solid-phases produced. Oxidized Mn, as both aqueous Mn(III) and Mn(III/IV) oxides, was only observed in the presence of active catalase, indicating that hydrogen peroxide (H2O2), a product of the reaction of O2− with Mn(II), inhibits the oxidation process presumably through the reduction of Mn(III). Citrate and pyrophosphate increased the yield of oxidized Mn but decreased the amount of Mn oxide produced via formation of Mn(III)-ligand complexes. While complexing ligands played a role in stabilizing Mn(III), they did not eliminate the inhibition of net Mn(III) formation by H2O2. The Mn oxides precipitated were highly disordered colloidal hexagonal birnessite, similar to those produced by biotically generated superoxide. Yet, in contrast to the large particulate Mn oxides formed by biogenic superoxide, abiotic Mn oxides did not ripen to larger, more crystalline phases. This suggests that the deposition of crystalline Mn oxides within the environment requires a biological, or at least organic, influence. This work provides the first direct evidence that, under conditions relevant to natural waters, oxidation of Mn(II) by superoxide can occur and lead to formation of Mn oxides. For organisms that oxidize Mn(II) by producing superoxide, these findings may also point to other microbially mediated processes, in particular enzymatic hydrogen peroxide degradation and/or production of organic ligand metabolites, that allow for Mn oxide formation. PMID:24027565

  10. Strontium and Actinides Removal from Savannah River Site Actual Waste Samples by Freshly Precipitated Manganese Oxide

    SciTech Connect

    Barnes, M.J.

    2003-10-30

    The authors investigated the performance of freshly precipitated manganese oxide and monosodium titanate (MST) for the removal of strontium (Sr) and actinides from actual high-level waste. Manganese oxide precipitation occurs upon addition of a reductant such as formate (HCO2-) or peroxide (H2O2) to a waste solution containing permanganate (MnO4-). Tests described in this document address the capability of manganese oxide treatment to remove Rs, Pu, and Np from actual high-level waste containing elevated concentrations of Pu. Additionally, tests investigate MST (using two unique batches) performance with the same waste for direct comparison to the manganese oxide performance.

  11. First principles calculations for lithiated manganese oxides.

    SciTech Connect

    Prasad, R.

    1998-12-23

    First principles calculations within the local-spin-density-functional theory (LSDFF) framework are presented of densities of electronic states for MnO, LiMnO{sub 2} in the monoclinic and orthorhombic structures, cubic LiMn{sub 2}O{sub 4} spinel and {lambda}-MnO{sub 2} (delithiated spinel), all in antiferromagnetic spin configurations. The changes in energy spectra as the Mn oxidation state varies between 2+ and 4+ are illustrated. Preliminary calculations for Co-doped LiMnO{sub 2} are presented, and the destabilization of a monoclinic relative to a rhombohedral structure is discussed.

  12. Iron and manganese oxide mineralization in the Pacific

    USGS Publications Warehouse

    Hein, J.R.; Koschinsky, A.; Halbach, P.; Manheim, F. T.; Bau, M.; Kang, J.-K.; Lubick, N.

    1997-01-01

    Iron, manganese, and iron-manganese deposits occur in nearly all geomorphologic and tectonic environments in the ocean basins and form by one or more of four processes: (1) hydrogenetic precipitation from cold ambient seawater, (2) precipitation from hydrothermal fluids, (3) precipitation from sediment pore waters that have been modified from bottom water compositions by diagenetic reactions in the sediment column and (4) replacement of rocks and sediment. Iron and manganese deposits occur in five forms: nodules, crusts, cements, mounds and sediment-hosted stratabound layers. Seafloor oxides show a wide range of compositions from nearly pure iron to nearly pure manganese end members. Fe/Mn ratios vary from about 24 000 (up to 58% elemental Fe) for hydrothermal seamount ironstones to about 0.001 (up to 52% Mn) for hydrothermal stratabound manganese oxides from active volcanic arcs. Hydrogenetic Fe-Mn crusts that occur on most seamounts in the ocean basins have a mean Fe/Mn ratio of 0.7 for open-ocean seamount crusts and 1.2 for continental margin seamount crusts. Fe-Mn nodules of potential economic interest from the Clarion-Clipperton Zone have a mean Fe/Mn ratio of 0.3, whereas the mean ratio for nodules from elsewhere in the Pacific is about 0.7. Crusts are enriched in Co, Ni and Pt and nodules in Cu and Ni, and both have significant concentrations of Pb, Zn, Ba, Mo, V and other elements. In contrast, hydrothermal deposits commonly contain only minor trace metal contents, although there are many exceptions, for example, with Ni contents up to 0.66%, Cr to 1.2%, and Zn to 1.4%. Chondrite-normalized REE patterns generally show a positive Ce anomaly and abundant ??REEs for hydrogenetic and mixed hydrogenetic-diagenetic deposits, whereas the Ce anomaly is negative for hydrothermal deposits and ??REE contents are low. However, the Ce anomaly in crusts may vary from strongly positive in East Pacific crusts to slightly negative in West Pacific crusts, which may reflect

  13. Manganese chlorins immobilized on silica as oxidation reaction catalysts.

    PubMed

    Castro, Kelly A D F; Pires, Sónia M G; Ribeiro, Marcos A; Simões, Mário M Q; Neves, M Graça P M S; Schreiner, Wido H; Wypych, Fernando; Cavaleiro, José A S; Nakagaki, Shirley

    2015-07-15

    Synthetic strategies that comply with the principles of green chemistry represent a challenge: they will enable chemists to conduct reactions that maximize the yield of products with commercial interest while minimizing by-products formation. The search for catalysts that promote the selective oxidation of organic compounds under mild and environmentally friendly conditions constitutes one of the most important quests of organic chemistry. In this context, metalloporphyrins and analogues are excellent catalysts for oxidative transformations under mild conditions. In fact, their reduced derivatives chlorins are also able to catalyze organic compounds oxidation effectively, although they have been still little explored. In this study, we synthesized two chlorins through porphyrin cycloaddition reactions with 1.3-dipoles and prepared the corresponding manganese chlorins (MnCHL) using adequate manganese(II) salts. These MnCHL were posteriorly immobilized on silica by following the sol-gel process and the resulting solids were characterized by powder X-ray diffraction (PXRD), UVVIS spectroscopy, FTIR, XPS, and EDS. The catalytic activity of the immobilized MnCHL was investigated in the oxidation of cyclooctene, cyclohexene and cyclohexane and the results were compared with the ones obtained under homogeneous conditions. PMID:25841060

  14. Biological manganese oxidation by Pseudomonas putida in trickling filters.

    PubMed

    McKee, Kyle P; Vance, Cherish C; Karthikeyan, Raghupathy

    2016-06-01

    Biological oxidation has been researched as a viable alternative for treating waters with high manganese (Mn) concentrations, typically found in mine drainage or in some geological formations. In this study, laboratory-scale trickling filters were constructed to compare the Mn removal efficiency between filters inoculated with the Mn oxidizing bacteria, Pseudomonas putida, and filters without inoculation. Manganese oxidation and removal was found to be significantly greater in trickling filters with Pseudomonas putida after startup times of only 48 h. Mn oxidation in Pseudomonas putida inoculated trickling filters was up to 75% greater than non-inoculated filters. One-dimensional advective-dispersive models were formulated to describe the transport of Mn in trickling filter porous media. Based on the experimental transport parameters obtained, the model predicted that a filter depth of only 16 cm is needed to reduce influent concentration of 10 mg L(-1) to 0.05 mg L(-1). PMID:26943637

  15. Oxidation of manganese(II) during chlorination: role of bromide.

    PubMed

    Allard, S; Fouche, L; Dick, J; Heitz, A; von Gunten, U

    2013-08-01

    The oxidation of dissolved manganese(II) (Mn(II)) during chlorination is a relatively slow process which may lead to residual Mn(II) in treated drinking waters. Chemical Mn(II) oxidation is autocatalytic and consists of a homogeneous and a heterogeneous process; the oxidation of Mn(II) is mainly driven by the latter process. This study demonstrates that Mn(II) oxidation during chlorination is enhanced in bromide-containing waters by the formation of reactive bromine species (e.g., HOBr, BrCl, Br2O) from the oxidation of bromide by chlorine. During oxidation of Mn(II) by chlorine in bromide-containing waters, bromide is recycled and acts as a catalyst. For a chlorine dose of 1 mg/L and a bromide level as low as 10 μg/L, the oxidation of Mn(II) by reactive bromine species becomes the main pathway. It was demonstrated that the kinetics of the reaction are dominated by the adsorbed Mn(OH)2 species for both chlorine and bromine at circumneutral pH. Reactive bromine species such as Br2O and BrCl significantly influence the rate of manganese oxidation and may even outweigh the reactivity of HOBr. Reaction orders in [HOBr]tot were found to be 1.33 (±0.15) at pH 7.8 and increased to 1.97 (±0.17) at pH 8.2 consistent with an important contribution of Br2O which is second order in [HOBr]tot. These findings highlight the need to take bromide, and the subsequent reactive bromine species formed upon chlorination, into account to assess Mn(II) removal during water treatment with chlorine. PMID:23859083

  16. Electrodeposited Manganese Oxides on Three-Dimensional Carbon Nanotube Substrate: Supercapacitive Behaviour in Aqueous and Organic Electrolytes

    SciTech Connect

    Nam,K.W.; Yang,X.

    2009-03-01

    Thin amorphous manganese oxide layers with a thickness of 3-5nm are electrodeposited on a carbon nanotube (CNT) film substrate that has a three-dimensional nanoporous structure (denoted asMnO2/CNT electrode). For the purpose of comparison, manganese oxide films are also electrodeposited on a flat Pt-coated Si wafer substrate (denoted as MnO2 film electrode). The pseudocapacitive properties of the MnO2 film and MnO2/CNT electrodes are examined in both aqueous electrolyte (1.0M KCl) and nonaqueousorganic electrolyte (1.0M LiClO4 in propylene carbonate). While both types of electrode showpseudocapacitive behaviour in the aqueous electrolyte, only the MnO2/CNT electrode does so in the organic electrolyte, due to its high oxide/electrolyte interfacial area and improved electron conduction through the CNT substrate. Compared with the MnO2 film electrode, the MnO2/CNT electrode shows a much higher specific capacitance and better high-rate capability, regardless of the electrolyte used.Use of the organic electrolyte results in a ∼6 times higher specific energy compared with that obtained with the aqueous electrolyte, while maintaining a similar specific power. The construction of a threedimensional nanoporous network structure consisting of a thin oxide layer on a CNT film substrate at the nm scale and the use of an organic electrolyte are promising approaches to improving the specific energyof supercapacitors.

  17. Manganese oxide composite electrodes for lithium batteries

    DOEpatents

    Thackeray, Michael M.; Johnson, Christopher S.; Li, Naichao

    2007-12-04

    An activated electrode for a non-aqueous electrochemical cell is disclosed with a precursor of a lithium metal oxide with the formula xLi.sub.2MnO.sub.3.(1-x)LiMn.sub.2-yM.sub.yO.sub.4 for 0

  18. Manganese oxide composite electrodes for lithium batteries

    DOEpatents

    Johnson, Christopher S.; Kang, Sun-Ho; Thackeray, Michael M.

    2009-12-22

    An activated electrode for a non-aqueous electrochemical cell is disclosed with a precursor thereof a lithium metal oxide with the formula xLi.sub.2MnO.sub.3.(1-x)LiMn.sub.2-yM.sub.yO.sub.4 for 0.5

  19. Solution synthesis and characterization of lithium manganese oxide cathode materials

    SciTech Connect

    Voigt, J.A.; Boyle, T.J.; Doughty, D.H.

    1995-07-01

    A nonaqueous coprecipitation process has been developed to prepare controlled stoichiometry lithium manganese oxalate precipitates. The process involved mixing a methanolic Li-Mn nitrate solution with a methanolic solution containing tetramethylammonium oxalate as the precipitating agent. The resulting oxalates were readily converted to a variety of phase pure lithium manganese oxides at moderate temperatures ({le}600{degrees}C), where the phase formed was determined by the initial Li/Mn ratio in the starting solution. Metal cation dopants have been incorporated into the oxalate precipitate by dissolving the appropriate metal nitrate in the Li-Mn precursor solution The various starting solutions, oxalate precipitates, and calcined oxides have been extensively characterized using a variety of techniques, including {sup 7}Li NMR, TGA/DTA, SEM, and XRD. Results indicate that a strong interaction occurs between Li and Mn in the nitrate solution which carries over into the oxalate phase during precipitation. The morphology and the crystallite size of the oxide powders were shown to be controlled by the morphology of the oxalate precursor and the oxalate calcination temperature, respectively. The results of initial cathode performance tests with respect to dopant type (Al, Ni, Co) and concentration for LiMn{sub 2}O{sub 4} are also reported.

  20. Long Cyclic Life in Manganese Oxide-Based Electrodes.

    PubMed

    Wang, Zhaoming; Qin, Qingqing; Xu, Wei; Yan, Jian; Wu, Yucheng

    2016-07-20

    Long cyclic life is very important to the practical application of the pseudocapacitors. A systematic study has been carried out to reveal what key factors and how they affecting the cycling behaviors of manganese oxides. The specific capacitance degradation of MnOx is usually attributed to the so-called "dissolution" issue. Our results indicate that "dissoluted MnOx" is in the form of the "flotsam" derived from the detached active materials instead of Mn(2+) in the solution, which causes color change of electrolyte and the loss of specific capacitance. During the cycling, the morphology of manganese oxides transformed to flower-like flakes regardless of the starting structures. After that, it tends to form nanowires especially at elevated temperatures. According to the relative low electrochemical utility of nanowires, specific capacitance might decrease at this stage. These results put forward new questions on charge storage mechanism. Besides, electrochemical oxidation of MnOx leads to an increase in specific capacitance. The cycling behavior of MnOx is mainly determined by these three factors. Excitingly, a very stable cycling performance with no capacitance degradation over 40 000 cycles has been achieved in MnO2 hierarchical sphere-based electrodes. This study provides insightful understanding of the fundamental cycling behavior of MnOx-based electrodes and useful instructions for developing highly stable supercapacitors. PMID:27347779

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

    PubMed

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

    2012-04-28

    CaMnO(3) and Ca(2)Mn(3)O(8) were synthesized and characterized by SEM, XRD, FTIR and BET. Both oxides showed oxygen evolution activity in the presence of oxone, cerium(IV) ammonium nitrate and H(2)O(2). Oxygen evolution from water during irradiation with visible light (λ > 400 nm) was also observed upon adding these manganese oxides to an aqueous solution containing tris(2,2'-bipyridyl) ruthenium(II), as photosensitizer, and chloro pentaammine cobalt(III) chloride, as electron acceptor, in an acetate buffer. The amounts of dissolved manganese and calcium from CaMnO(3) and Ca(2)Mn(3)O(8) in the oxygen evolving reactions were reported and compared with other (calcium) manganese oxides. Proposed mechanisms of oxygen evolution and proposed roles for the calcium ions are also considered. PMID:22382465

  2. Manganese

    MedlinePlus

    ... no RDAs for a nutrient, the Adequate Intake (AI) is used as a guide. The AI is the estimated amount of the nutrient that ... assumed to be adequate. The daily Adequate Intake (AI) levels for manganese are: infants birth to 6 ...

  3. Manganese

    Integrated Risk Information System (IRIS)

    Manganese ; CASRN 7439 - 96 - 5 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic Effect

  4. Manganese oxide micro-supercapacitors with ultra-high areal capacitance.

    PubMed

    Wang, Xu; Myers, Benjamin D; Yan, Jian; Shekhawat, Gajendra; Dravid, Vinayak; Lee, Pooi See

    2013-05-21

    A symmetric micro-supercapacitor is constructed by electrochemically depositing manganese oxide onto micro-patterned current collectors. High surface-to-volume ratio of manganese oxide and short diffusion distance between electrodes give an ultra-high areal capacitance of 56.3 mF cm(-2) at a current density of 27.2 μA cm(-2). PMID:23563785

  5. Manganese-Based Molecular Electrocatalysts for Oxidation of Hydrogen

    SciTech Connect

    Hulley, Elliott; Kumar, Neeraj; Raugei, Simone; Bullock, R. Morris

    2015-10-05

    Oxidation of H2 (1 atm) is catalyzed by the manganese electrocatalysts [(P2N2)MnI(CO)(bppm)]+ and [(PNP)MnI(CO)(bppm)]+ (P2N2= 1,5-dibenzyl-3,7-diphenyl-1,5-diaza-3,7-diphosphacyclooctane; PNP = (Ph2PCH2)2NMe); bppm = (PArF2)2CH2, and ArF = 3,5-(CF3)2C6H3). In fluorobenzene solvent using 2,6-lutidine as the exogeneous base, the turnover frequency for [(P2N2)MnI(CO)(bppm)]+ is 3.5 s-1 with an estimated overpotential of 590 mV. For [(PNP)MnI(CO)(bppm)], in fluorobenzene solvent using N-methylpyrrolidine as the exogeneous base, the turnover frequency is 1.4 s-1 with an estimated overpotential of 700 mV. Density functional theory calculations suggest that the slow step in the catalytic cycle is proton transfer from the oxidized 17-electron manganese hydride, e.g., [(P2N2)MnIIH(CO)(bppm)]+ to the pendant amine. The computed activation barrier for intramolecular proton transfer from the metal to the pendant amine is 20.4 kcal/mol in [(P2N2)MnIIH(CO)(bppm)]+ and 21.3 kcal/mol in [(PNP)MnI(CO)(bppm)]. The high barrier appears to result from both the unfavorability of metal-to-nitrogen proton transfer (thermodynamically uphill by 6.6 pKa units, 9 kcal/mol), as well as the relatively long manganese-nitrogen separation in the MnIIH complexes.

  6. Fully Converting Graphite into Graphene Oxide Hydrogels by Preoxidation with Impure Manganese Dioxide.

    PubMed

    Sun, Jiaojiao; Yang, Ningxin; Sun, Zhe; Zeng, Mengqi; Fu, Lei; Hu, Chengguo; Hu, Shengshui

    2015-09-30

    Potassium permanganate (KMnO4) has been proved to be an efficient oxidant for converting graphite into graphite oxide, but its slow diffusion in the interlayer of graphite seriously restricts the production of graphene oxide (GO). Here, we demonstrate that the preoxidation of graphite by impure manganese dioxide (MnO2) in a mixture of concentrated sulfuric acid (H2SO4) and phosphorus pentoxide (P2O5) can efficiently improve the synthesis of GO when KMnO4 is employed as the oxidant. The prepared honey-like GO hydrogels possess a high yield of single-layer sheets, large sizes (average lateral size up to 20 μm), wide ranges of stable dispersion concentrations (from dilute solutions, viscous hydrogels, to dry films), and good conductivity after reduction (~2.9 × 10(4) S/m). The mechanism for the improved synthesis of GO by impure MnO2 was explored. The enhanced exfoliation and oxidation of graphite by oxidative Mn ions (mainly Mn(3+)), which are synergistically produced by the reaction of impure MnO2 with H2SO4 and P2O5, are found to be responsible for the improved synthesis of such GO hydrogels. Particularly, preoxidized graphite (POG) can be partially dispersed in water with sonication, which allows the facile construction of flexible and highly conductive graphene nanosheet film electrodes with excellent electrochemical sensing properties. PMID:26352992

  7. Chromite oxidation by manganese oxides in subseafloor basalts and the presence of putative fossilized microorganisms

    PubMed Central

    2011-01-01

    Chromite is a mineral with low solubility and is thus resistant to dissolution. The exception is when manganese oxides are available, since they are the only known naturally occurring oxidants for chromite. In the presence of Mn(IV) oxides, Cr(III) will oxidise to Cr(VI), which is more soluble than Cr(III), and thus easier to be removed. Here we report of chromite phenocrysts that are replaced by rhodochrosite (Mn(II) carbonate) in subseafloor basalts from the Koko Seamount, Pacific Ocean, that were drilled and collected during the Ocean Drilling Program (ODP) Leg 197. The mineral succession chromite-rhodochrosite-saponite in the phenocrysts is interpreted as the result of chromite oxidation by manganese oxides. Putative fossilized microorganisms are abundant in the rhodochrosite and we suggest that the oxidation of chromite has been mediated by microbial activity. It has previously been shown in soils and in laboratory experiments that chromium oxidation is indirectly mediated by microbial formation of manganese oxides. Here we suggest a similar process in subseafloor basalts. PMID:21639896

  8. Chromite oxidation by manganese oxides in subseafloor basalts and the presence of putative fossilized microorganisms.

    PubMed

    Ivarsson, Magnus; Broman, Curt; Holm, Nils G

    2011-01-01

    Chromite is a mineral with low solubility and is thus resistant to dissolution. The exception is when manganese oxides are available, since they are the only known naturally occurring oxidants for chromite. In the presence of Mn(IV) oxides, Cr(III) will oxidise to Cr(VI), which is more soluble than Cr(III), and thus easier to be removed. Here we report of chromite phenocrysts that are replaced by rhodochrosite (Mn(II) carbonate) in subseafloor basalts from the Koko Seamount, Pacific Ocean, that were drilled and collected during the Ocean Drilling Program (ODP) Leg 197. The mineral succession chromite-rhodochrosite-saponite in the phenocrysts is interpreted as the result of chromite oxidation by manganese oxides. Putative fossilized microorganisms are abundant in the rhodochrosite and we suggest that the oxidation of chromite has been mediated by microbial activity. It has previously been shown in soils and in laboratory experiments that chromium oxidation is indirectly mediated by microbial formation of manganese oxides. Here we suggest a similar process in subseafloor basalts. PMID:21639896

  9. Exceptionally Active and Stable Spinel Nickel Manganese Oxide Electrocatalysts for Urea Oxidation Reaction.

    PubMed

    Periyasamy, Sivakumar; Subramanian, Palaniappan; Levi, Elena; Aurbach, Doron; Gedanken, Aharon; Schechter, Alex

    2016-05-18

    Spinel nickel manganese oxides, widely used materials in the lithium ion battery high voltage cathode, were studied in urea oxidation catalysis. NiMn2O4, Ni1.5Mn1.5O4, and MnNi2O4 were synthesized by a simple template-free hydrothermal route followed by a thermal treatment in air at 800 °C. Rietveld analysis performed on nonstoichiometric nickel manganese oxide-Ni1.5Mn1.5O4 revealed the presence of three mixed phases: two spinel phases with different lattice parameters and NiO unlike the other two spinels NiMn2O4 and MnNi2O4. The electroactivity of nickel manganese oxide materials toward the oxidation of urea in alkaline solution is evaluated using cyclic voltammetric measurements. Ni1.5Mn1.5O4 exhibits excellent redox characteristics and lower charge transfer resistances in comparison with other compositions of nickel manganese oxides and nickel oxide prepared under similar conditions.The Ni1.5Mn1.5O4modified electrode oxidizes urea at 0.29 V versus Ag/AgCl with a corresponding current density of 6.9 mA cm(-2). At a low catalyst loading of 50 μg cm(-2), the urea oxidation current density of Ni1.5Mn1.5O4 in alkaline solution is 7 times higher than that of nickel oxide and 4 times higher than that of NiMn2O4 and MnNi2O4, respectively. PMID:27123873

  10. Manganese oxide minerals: Crystal structures and economic and environmental significance

    PubMed Central

    Post, Jeffrey E.

    1999-01-01

    Manganese oxide minerals have been used for thousands of years—by the ancients for pigments and to clarify glass, and today as ores of Mn metal, catalysts, and battery material. More than 30 Mn oxide minerals occur in a wide variety of geological settings. They are major components of Mn nodules that pave huge areas of the ocean floor and bottoms of many fresh-water lakes. Mn oxide minerals are ubiquitous in soils and sediments and participate in a variety of chemical reactions that affect groundwater and bulk soil composition. Their typical occurrence as fine-grained mixtures makes it difficult to study their atomic structures and crystal chemistries. In recent years, however, investigations using transmission electron microscopy and powder x-ray and neutron diffraction methods have provided important new insights into the structures and properties of these materials. The crystal structures for todorokite and birnessite, two of the more common Mn oxide minerals in terrestrial deposits and ocean nodules, were determined by using powder x-ray diffraction data and the Rietveld refinement method. Because of the large tunnels in todorokite and related structures there is considerable interest in the use of these materials and synthetic analogues as catalysts and cation exchange agents. Birnessite-group minerals have layer structures and readily undergo oxidation reduction and cation-exchange reactions and play a major role in controlling groundwater chemistry. PMID:10097056

  11. Direct growth of flower-like manganese oxide on reduced graphene oxide towards efficient oxygen reduction reaction.

    PubMed

    Zhang, Jintao; Guo, Chunxian; Zhang, Lianying; Li, Chang Ming

    2013-07-18

    Three-dimensional manganese oxide is directly grown on reduced graphene oxide (RGO) sheets, exhibiting comparable catalytic activity, higher selectivity and better stability towards oxygen reduction reaction than those of the commercial Pt/XC-72 catalyst. PMID:23745182

  12. Comparative evaluation of oxidative stress status and manganese availability in plants growing on manganese mine.

    PubMed

    Boojar, Massod Mashhadi Akbar; Goodarzi, Faranak

    2008-11-01

    This study pioneered an approach that determined the effects of excess manganese (Mn) on three species; Datura stramonium, Alhagi camelthorn and Chenopodium ambrosioides. We investigated their levels of Mn, antioxidative enzymes and oxidative damage biomarkers in plants (zone 1) in and outside (zone 2) the Mn mine. The results showed that total and available Mn were at toxic levels for plants growing on zone 1. The Mn levels in each plant species were higher in leaves, stems and roots. Mn was only accumulated significantly in leaf vacuoles of A. camelthorn. Antioxidative enzyme activities of C. ambrosioides and/or D. stramonium in zone 1 were higher in leaves, stems and then in their roots. Malondialdehyde (MDA) and dityrosine levels were insignificantly higher in tissues of the studied plants in zone 1 with respect to zone 2. The roots of studied plants showed significantly higher levels of these biomarkers in comparison with their leaves in zone 1. Accordingly, antioxidative enzymatic response to Mn-stress in D. stramonium and C. ambrosioides and possibly accumulation of Mn in leaf vacuoles of A. camelthorn, protected them from oxidative damages and involved in their tolerance in Mn mine. PMID:18068229

  13. Preparation and Characterization of Nanostructured Manganese Oxide for Supercapacitors.

    PubMed

    Jang, Jaeyong; Kim, Taewoo; Choi, Young Il; Park, Inyeong; Lim, Dongwook; Shim, Sang Eun; Baeck, Sung-Hyeon

    2016-05-01

    Nanostructured manganese oxides were synthesized by a sol-gel method using manganese acetate (MnAc2) and citric acid (C6H8O7,) as precursors, and characterized by Brunauer-Emmett-Teller (BET) analysis, Barrett-Joyner-Halenda (BJH), X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM) techniques. The nano-rod structure of MnO2 developed gradually when the calcination temperature varied from 380 to 580 degrees C. As the pH increased, the pore size increased, while the specific surface area decreased. The effects of the pH and calcination temperature on the electrochemical properties of the nano-MnO2 electrode, including the supercapacitive behavior, were investigated by cyclic voltammetry (CV) tests. The tests were performed between 0 and 0.8 V versus Ag/AgCl in 1 M Na2SO4 electrolyte at various scan rates (10-200 mVs(-1)). The specific capacitance of the SP-380 sample, prepared at pH 6, was equal to 269.3 Fg(-1). After 300 cycles, approximately a 3.4% increase of the specific capacitance was measured, confirming the excellent cyclability. PMID:27483899

  14. Manganese Oxide Nanoarray-Based Monolithic Catalysts: Tunable Morphology and High Efficiency for CO Oxidation.

    PubMed

    Chen, Sheng-Yu; Song, Wenqiao; Lin, Hui-Jan; Wang, Sibo; Biswas, Sourav; Mollahosseini, Mehdi; Kuo, Chung-Hao; Gao, Pu-Xian; Suib, Steven L

    2016-03-30

    A generic one-pot hydrothermal synthesis route has been successfully designed and utilized to in situ grow uniform manganese oxide nanorods and nanowires onto the cordierite honeycomb monolithic substrates, forming a series of nanoarray-based monolithic catalysts. During the synthesis process, three types of potassium salt oxidants have been used with different reduction potentials, i.e., K2Cr2O7, KClO3, and K2S2O8, denoted as HM-DCM, HM-PCR, and HM-PSF, respectively. The different reduction potentials of the manganese source (Mn(2+)) and oxidants induced the formation of manganese oxide nanoarrays with different morphology, surface area, and reactivity of carbon monoxide (CO) oxidation. K2Cr2O7 and KClO3 can induce sharp and long nanowires with slow growth rates due to their low reduction potentials. In comparison, the nanoarrays of HM-PSF presented shorter nanorods but displayed an efficient 90% CO oxidation conversion at 200 °C (T90) without noble-metal loading. Reducibility tests for the three monolithic catalysts by hydrogen temperature-programmed reduction revealed an activation energy order of HM-PSF > HM-DCM > HM-PCR for CO oxidation. The characterizations of oxygen temperature-programmed desorption and X-ray photoelectron spectroscopy indicated the abundant surface-adsorbed oxygen and lattice oxygen contributing to the superior reactivity of HM-PSF. The straightforward synthetic process showed a scalable, low-cost, and template-free method to fabricate manganese oxide nanoarray monolithic catalysts for exhaust treatment. PMID:26954301

  15. Thermodynamics of Manganese Oxides at Bulk and Nanoscale: Phase Formation, Transformation, Oxidation-Reduction, and Hydration

    NASA Astrophysics Data System (ADS)

    Birkner, Nancy R.

    Natural manganese oxides are generally formed in surficial environments that are near ambient temperature and water-rich, and may be exposed to wet-dry cycles and a variety of adsorbate species that influence dramatically their level of hydration. Manganese oxide minerals are often poorly crystalline, nanophase, and hydrous. In the near-surface environment they are involved in processes that are important to life, such as water column oxygen cycling, biomineralization, and transport of minerals/nutrients through soils and water. These processes, often involving transformations among manganese oxide polymorphs, are governed by a complex interplay between thermodynamics and kinetics. Manganese oxides are also used in technology as catalysts, and for other applications. The major goal of this dissertation is to examine the energetics of bulk and nanophase manganese oxide phases as a function of particle size, composition, and surface hydration. Careful synthesis and characterization of manganese oxide phases with different surface areas provided samples for the study of enthalpies of formation by high temperature oxide melt solution calorimetry and of the energetics of water adsorption on their surfaces. These data provide a quantitative picture of phase stability and how it changes at the nanoscale. The surface energy of the hydrous surface of Mn3O4 is 0.96 +/- 0.08 J/m2, of Mn2O3 is 1.29 +/- 0.10 J/m2, and of MnO2 is 1.64 +/- 0.10 J/m2. The surface energy of the anhydrous surface of Mn3O4 is 1.62 +/- 0.08 J/m 2, of Mn2O3 is 1.77 +/- 0.10 J/m 2, and of MnO2 is 2.05 +/- 0.10 J/m2. Supporting preliminary findings (Navrotsky et al., 2010), the spinel phase (Mn3O4) has a lower surface energy (more stabilizing) than bixbyite, while the latter has a smaller surface energy than pyrolusite. These differences significantly change the positions in oxygen fugacity---temperature space of the redox couples Mn3O4-Mn2O 3 and Mn2O3-MnO2 favoring the lower surface enthalpy phase (the

  16. Manganese(III) binding to a pyoverdine siderophore produced by a manganese(II)-oxidizing bacterium

    NASA Astrophysics Data System (ADS)

    Parker, Dorothy L.; Sposito, Garrison; Tebo, Bradley M.

    2004-12-01

    The possible roles of siderophores (high affinity chelators of iron(III)) in the biogeochemistry of manganese remain unknown. Here we investigate the interaction of Mn(III) with a pyoverdine-type siderophore (PVD MnB1) produced by the model Mn(II)-oxidizing bacterium Pseudomonas putida strain MnB1. PVD MnB1 confirmed typical pyoverdine behavior with respect to: (a) its absorption spectrum at 350-600 nm, both in the absence and presence of Fe(III), (b) the quenching of its fluorescence by Fe(III), (c) the formation of a 1:1 complex with Fe(III), and (d) the thermodynamic stability constant of its Fe(III) complex. The Mn(III) complex of PVD MnB1 had a 1:1 Mn:pvd molar ratio, showed fluorescence quenching, and exhibited a light absorption spectrum (A max = 408-410 nm) different from that of either PVD MnB1-Fe(III) or uncomplexed PVD MnB1. Mn(III) competed strongly with Fe(III) for binding by PVD MnB1 in culture filtrates (pH 8, 4°C). Equilibration with citrate, a metal-binding ligand, did not detectably release Mn from its PVD MnB1 complex at a citrate/PVD MnB1 molar ratio of 830 (pH 8, 4°C), whereas pyrophosphate under the same conditions removed 55% of the Mn from its PVD MnB1 complex. Most of the PVD MnB1-complexed Mn was released by reaction with ascorbate, a reducing agent, or with EDTA, a ligand that is also oxidized by Mn(III). Data on the competition for binding to PVD MnB1 by Fe(III) vs. Mn(III) were used to determine a thermodynamic stability constant (nominally at 4°C) for the neutral species MnHPVD MnB1 (log K = 47.5 ± 0.5, infinite dilution reference state). This value was larger than that determined for FeHPVD MnB1 (log K = 44.6 ± 0.5). This result has important implications for the metabolism, solubility, speciation, and redox cycling of manganese, as well as for the biologic uptake of iron.

  17. Monte Carlo study of double exchange interaction in manganese oxide

    SciTech Connect

    Naa, Christian Fredy; Suprijadi, Viridi, Sparisoma Djamal, Mitra; Fasquelle, Didier

    2015-09-30

    In this paper we study the magnetoresistance properties attributed by double exchange (DE) interaction in manganese oxide by Monte Carlo simulation. We construct a model based on mixed-valence Mn{sup 3+} and Mn{sup 4+} on the general system of Re{sub 2/3}Ae{sub 1/3}MnO{sub 3} in two dimensional system. The conduction mechanism is based on probability of e{sub g} electrons hopping from Mn{sup 3+} to Mn{sup 4+}. The resistivity dependence on temperature and the external magnetic field are presented and the validity with related experimental results are discussed. We use the resistivity power law to fit our data on metallic region and basic activated behavior on insulator region. On metallic region, we found our result agree well with the quantum theory of DE interaction. From general arguments, we found our simulation agree qualitatively with experimental results.

  18. Sol-gel synthesis and characterization of mesoporous manganese oxide

    SciTech Connect

    Hong Xinlin; Zhang Gaoyong; Zhu Yinyan; Yang Hengquan

    2003-10-30

    Mesoporous manganese oxide (MPMO) from reduction of KMnO{sub 4} with maleic acid, was obtained and characterized in detail. The characterization of the material was confirmed by high-resolution transmission electron microscopy (HRTEM), X-ray powder diffractometry (XRD) and N{sub 2} sorptometry. The results showed that MPMO is a pseudo-crystalline material with complex network pore structure, of which BET specific surface area is 297 m{sup 2}/g and pore size distribution is approximately in the range of 0.7-6.0 nm. The MPMO material turns to cryptomelane when the calcinating temperature rises to 400 deg. C. The optimum sol-gel reaction conditions are KMnO{sub 4}/C{sub 4}H{sub 4}O{sub 4} molar ratio=3, pH=7 and gelation time>6 h.

  19. Water exchange in manganese-based water-oxidizing catalysts in photosynthetic systems: from the water-oxidizing complex in photosystem II to nano-sized manganese oxides.

    PubMed

    Najafpour, Mohammad Mahdi; Isaloo, Mohsen Abbasi; Eaton-Rye, Julian J; Tomo, Tatsuya; Nishihara, Hiroshi; Satoh, Kimiyuki; Carpentier, Robert; Shen, Jian-Ren; Allakhverdiev, Suleyman I

    2014-09-01

    The water-oxidizing complex (WOC), also known as the oxygen-evolving complex (OEC), of photosystem II in oxygenic photosynthetic organisms efficiently catalyzes water oxidation. It is, therefore, responsible for the presence of oxygen in the Earth's atmosphere. The WOC is a manganese-calcium (Mn₄CaO₅(H₂O)₄) cluster housed in a protein complex. In this review, we focus on water exchange chemistry of metal hydrates and discuss the mechanisms and factors affecting this chemical process. Further, water exchange rates for both the biological cofactor and synthetic manganese water splitting are discussed. The importance of fully unveiling the water exchange mechanism to understand the chemistry of water oxidation is also emphasized here. This article is part of a special issue entitled: photosynthesis research for sustainability: keys to produce clean energy. PMID:24685431

  20. Towards a mechanistic understanding of carbon stabilization in manganese oxides

    PubMed Central

    Johnson, Karen; Purvis, Graham; Lopez-Capel, Elisa; Peacock, Caroline; Gray, Neil; Wagner, Thomas; März, Christian; Bowen, Leon; Ojeda, Jesus; Finlay, Nina; Robertson, Steve; Worrall, Fred; Greenwell, Chris

    2015-01-01

    Minerals stabilize organic carbon (OC) in sediments, thereby directly affecting global climate at multiple scales, but how they do it is far from understood. Here we show that manganese oxide (Mn oxide) in a water treatment works filter bed traps dissolved OC as coatings build up in layers around clean sand grains at 3%w/wC. Using spectroscopic and thermogravimetric methods, we identify two main OC fractions. One is thermally refractory (>550 °C) and the other is thermally more labile (<550 °C). We postulate that the thermal stability of the trapped OC is due to carboxylate groups within it bonding to Mn oxide surfaces coupled with physical entrapment within the layers. We identify a significant difference in the nature of the surface-bound OC and bulk OC . We speculate that polymerization reactions may be occurring at depth within the layers. We also propose that these processes must be considered in future studies of OC in natural systems. PMID:26194625

  1. Towards a mechanistic understanding of carbon stabilization in manganese oxides.

    PubMed

    Johnson, Karen; Purvis, Graham; Lopez-Capel, Elisa; Peacock, Caroline; Gray, Neil; Wagner, Thomas; März, Christian; Bowen, Leon; Ojeda, Jesus; Finlay, Nina; Robertson, Steve; Worrall, Fred; Greenwell, Chris

    2015-01-01

    Minerals stabilize organic carbon (OC) in sediments, thereby directly affecting global climate at multiple scales, but how they do it is far from understood. Here we show that manganese oxide (Mn oxide) in a water treatment works filter bed traps dissolved OC as coatings build up in layers around clean sand grains at 3%w/wC. Using spectroscopic and thermogravimetric methods, we identify two main OC fractions. One is thermally refractory (>550 °C) and the other is thermally more labile (<550 °C). We postulate that the thermal stability of the trapped OC is due to carboxylate groups within it bonding to Mn oxide surfaces coupled with physical entrapment within the layers. We identify a significant difference in the nature of the surface-bound OC and bulk OC . We speculate that polymerization reactions may be occurring at depth within the layers. We also propose that these processes must be considered in future studies of OC in natural systems. PMID:26194625

  2. Sulfur Dioxide Capture by Heterogeneous Oxidation on Hydroxylated Manganese Dioxide.

    PubMed

    Wu, Haodong; Cai, Weimin; Long, Mingce; Wang, Hairui; Wang, Zhiping; Chen, Chen; Hu, Xiaofang; Yu, Xiaojuan

    2016-06-01

    Here we demonstrate that sulfur dioxide (SO2) is efficiently captured via heterogeneous oxidation into sulfate on the surface of hydroxylated manganese dioxide (MnO2). Lab-scale activity tests in a fluidized bed reactor showed that the removal efficiency for a simulated flue gas containing 5000 mg·Nm(-3) SO2 could reach nearly 100% with a GHSV (gas hourly space velocity) of 10000 h(-1). The mechanism was investigated using a combination of experimental characterizations and theoretical calculations. It was found that formation of surface bound sulfate proceeds via association of SO2 with terminal hydroxyls. Both H2O and O2 are essential for the generation of reactive terminal hydroxyls, and the indirect role of O2 in heterogeneous SO2 oxidation at low temperature was also revealed. We propose that the high reactivity of terminal hydroxyls is attributed to the proper surface configuration of MnO2 to adsorb water with degenerate energies for associative and dissociative states, and maintain rapid proton dynamics. Viability analyses suggest that the desulfurization method that is based on such a direct oxidation reaction at the gas/solid interface represents a promising approach for SO2 capture. PMID:27123922

  3. Insights into the solar light driven thermocatalytic oxidation of VOCs over tunnel structured manganese oxides.

    PubMed

    Zheng, Yali; Wang, Wenzhong; Jiang, Dong; Zhang, Ling; Li, Xiaoman; Wang, Zhong

    2016-07-21

    Different tunnel structured manganese oxides (1*1, 2*2, and 3*3) have been synthesized via a facile hydrothermal strategy. The three catalysts exhibit high photothermal performance, resulting in a considerable increase of temperature above the light-off temperature for VOC oxidation. On this point, aerobic oxidation reactions of propane and propylene under simulated sunlight and infrared light irradiation were selected as probe reactions to explore their light driven thermocatalytic activity. Furthermore, the light-off curves of the manganese oxides for propane and propylene were carefully investigated, which clearly explained the possibility of combining both the efficient photothermal effect and excellent thermocatalytic activity of the manganese oxides. Results show that the catalytic effects follow the order of 1*1 < 3*3 < 2*2. 2*2 exhibited the best catalytic properties due to better low-temperature reducibility, suitable tunnel structure and the presence of more Mn(4+). This work suggests new applications for traditional catalysts with intense photoabsorption and provides insights into the overall utilization of solar energy. PMID:27333408

  4. Metal oxide films on metal

    DOEpatents

    Wu, Xin D.; Tiwari, Prabhat

    1995-01-01

    A structure including a thin film of a conductive alkaline earth metal oxide selected from the group consisting of strontium ruthenium trioxide, calcium ruthenium trioxide, barium ruthenium trioxide, lanthanum-strontium cobalt oxide or mixed alkaline earth ruthenium trioxides thereof upon a thin film of a noble metal such as platinum is provided.

  5. Understanding Organic Film Behavior on Alloy and Metal Oxides

    PubMed Central

    Raman, Aparna; Quiñones, Rosalynn; Barriger, Lisa; Eastman, Rachel; Parsi, Arash

    2010-01-01

    Native oxide surfaces of stainless steel 316L and Nitinol alloys and their constituent metal oxides namely, nickel, chromium, molybdenum, manganese, iron and titanium were modified with long chain organic acids to better understand organic film formation. The adhesion and stability of films of octadecylphosphonic acid, octadecylhydroxamic acid, octadecylcarboxylic acid and octadecylsulfonic acid on these substrates was examined in this study. The films formed on these surfaces were analyzed by diffuse reflectance infrared Fourier transform spectroscopy, contact angle goniometry, atomic force microscopy and matrix assisted laser desorption ionization mass spectrometry. The effect of the acidity of the organic moiety and substrate composition on the film characteristics and stability is discussed. Interestingly, on the alloy surfaces, the presence of less reactive metal sites does not inhibit film formation. PMID:20039608

  6. Understanding organic film behavior on alloy and metal oxides.

    PubMed

    Raman, Aparna; Quiñones, Rosalynn; Barriger, Lisa; Eastman, Rachel; Parsi, Arash; Gawalt, Ellen S

    2010-02-01

    Native oxide surfaces of stainless steel 316L and Nitinol alloys and their constituent metal oxides, namely nickel, chromium, molybdenum, manganese, iron, and titanium, were modified with long chain organic acids to better understand organic film formation. The adhesion and stability of films of octadecylphosphonic acid, octadecylhydroxamic acid, octadecylcarboxylic acid, and octadecylsulfonic acid on these substrates were examined in this study. The films formed on these surfaces were analyzed by diffuse reflectance infrared Fourier transform spectroscopy, contact angle goniometry, atomic force microscopy, and matrix-assisted laser desorption ionization mass spectrometry. The effect of the acidity of the organic moiety and substrate composition on the film characteristics and stability is discussed. Interestingly, on the alloy surfaces, the presence of less reactive metal sites does not inhibit film formation. PMID:20039608

  7. Does manganese protect cultured human skin fibroblasts against oxidative injury by UVA, dithranol and hydrogen peroxide?

    PubMed

    Parat, M O; Richard, M J; Leccia, M T; Amblard, P; Favier, A; Beani, J C

    1995-10-01

    Reactive oxygen species (ROS) are involved in the mechanism of photoaging and carcinogenesis. Skin is endowed with antioxidant enzymes including superoxide dismutases (SOD): cytosolic copper zinc SOD and mitochondrial manganese SOD. The aim of our study was to estimate the protective effect of manganese against oxidative injury on cultured human skin fibroblasts. Dithranol, hydrogen peroxide and UV-A radiation (375 nm) were employed as oxidative stressors. The supply of manganese chloride produced an increase in cellular content of this element up to 24 fold without concomitant elevation of MnSOD activity. Nevertheless, manganese protects cells against two of the three ROS generating systems assessed, namely hydrogen peroxyde and UV-A. This protective effect depends on the concentration of manganese in the medium, 0.1 mM and 0.2 mM protect against UVA cytotoxicity, only 0.2 mM protects against H2O2 cytotoxicity. PMID:7493040

  8. Electrochemical Deposition of Nanostructured Manganese Oxide on Carbon Cloth for Flexible High-Performance Supercapacitor Electrodes.

    PubMed

    Huang, Zilong; Zhao, Xin; Ren, Jianli; Zhang, Junxian; Li, Yingzhi; Zhang, Qinghua

    2016-06-01

    Well-ordered manganese oxide (MnO2) arrays were directly grown on the treated carbon cloth (CC) though a simple electrochemical deposition method. The structures and the thickness of MnO2 film were controlled by tuning the deposition time. The morphologies and structures of MnO2 deposited on CC were examined by scanning electron microscopy, Raman and X-ray photoelectron spectroscopy. With appropriate reaction time, the MnO2/CC composite demonstrates a high specific capacitance of 291 mF/cm2 and a superior cycling stability at a current density of 0.2 mA/cm2. The specific capacitance shows a little improvement at the first 200 cycles and remains unchanged after continuous 2000 charge/discharge cycles. The MnO2 nanosheet arrays with high degree of ordering, combined with the flexible carbon cloth substrate can coffer great promise for supercapacitor applications. PMID:27427613

  9. Fabrication of MnO 2-pillared layered manganese oxide through an exfoliation/reassembling and oxidation process

    NASA Astrophysics Data System (ADS)

    Yuan, Jiaqi; Liu, Zong-Huai; Qiao, Shanfeng; Ma, Xiangrong; Xu, Naicai

    MnO 2-pillared layered manganese oxide has been first fabricated by a delamination/reassembling process followed by oxidation reaction and then by heat treatment. The structural evolution of MnO 2-pillared layered manganese oxide has been characterized by XRD, SEM, DSC-GTA, IR and N 2 adsorption-desorption. MnO 2-pillared layered manganese oxide shows a relative high thermal stability and mesoporous characteristic. The layered structure with a basal spacing of 0.66 nm could be maintained up to 400 °C. The electrochemical properties of the synthesized MnO 2-pillared layered manganese oxide have been studied using cyclic voltammetry in a mild aqueous electrolyte. Sample MnO 2-BirMO (300 °C) shows good capacitive behavior and cycling stability, and the specific capacitance value is 206 F g -1.

  10. Sodium perxenate permits rapid oxidation of manganese for easy spectrophotometric determination

    NASA Technical Reports Server (NTRS)

    Bane, R. W.

    1967-01-01

    Sodium perxenate oxidizes manganese to permanganate almost instantaneously in dilute acid solution and without a catalyst. A solution is prepared by dissolving 200 mg of sodium perxenate in distilled water and diluting to 100 ml.

  11. Rapidly reversible redox transformation in nanophase manganese oxides at room temperature triggered by changes in hydration

    PubMed Central

    Birkner, Nancy; Navrotsky, Alexandra

    2014-01-01

    Chemisorption of water onto anhydrous nanophase manganese oxide surfaces promotes rapidly reversible redox phase changes as confirmed by calorimetry, X-ray diffraction, and titration for manganese average oxidation state. Surface reduction of bixbyite (Mn2O3) to hausmannite (Mn3O4) occurs in nanoparticles under conditions where no such reactions are seen or expected on grounds of bulk thermodynamics in coarse-grained materials. Additionally, transformation does not occur on nanosurfaces passivated by at least 2% coverage of what is likely an amorphous manganese oxide layer. The transformation is due to thermodynamic control arising from differences in surface energies of the two phases (Mn2O3 and Mn3O4) under wet and dry conditions. Such reversible and rapid transformation near room temperature may affect the behavior of manganese oxides in technological applications and in geologic and environmental settings. PMID:24733903

  12. Visible-Light-Driven Water Oxidation by a Molecular Manganese Vanadium Oxide Cluster.

    PubMed

    Schwarz, Benjamin; Forster, Johannes; Goetz, McKenna K; Yücel, Duygu; Berger, Claudia; Jacob, Timo; Streb, Carsten

    2016-05-17

    Photosynthetic water oxidation in plants occurs at an inorganic calcium manganese oxo cluster, which is known as the oxygen evolving complex (OEC), in photosystem II. Herein, we report a synthetic OEC model based on a molecular manganese vanadium oxide cluster, [Mn4 V4 O17 (OAc)3 ](3-) . The compound is based on a [Mn4 O4 ](6+) cubane core, which catalyzes the homogeneous, visible-light-driven oxidation of water to molecular oxygen and is stabilized by a tripodal [V4 O13 ](6-) polyoxovanadate and three acetate ligands. When combined with the photosensitizer [Ru(bpy)3 ](2+) and the oxidant persulfate, visible-light-driven water oxidation with turnover numbers of approximately 1150 and turnover frequencies of about 1.75 s(-1) is observed. Electrochemical, mass-spectrometric, and spectroscopic studies provide insight into the cluster stability and reactivity. This compound could serve as a model for the molecular structure and reactivity of the OEC and for heterogeneous metal oxide water-oxidation catalysts. PMID:27062440

  13. Extracellular zinc competitively inhibits manganese uptake and compromises oxidative stress management in Streptococcus pneumoniae.

    PubMed

    Eijkelkamp, Bart A; Morey, Jacqueline R; Ween, Miranda P; Ong, Cheryl-lynn Y; McEwan, Alastair G; Paton, James C; McDevitt, Christopher A

    2014-01-01

    Streptococcus pneumoniae requires manganese for colonization of the human host, but the underlying molecular basis for this requirement has not been elucidated. Recently, it was shown that zinc could compromise manganese uptake and that zinc levels increased during infection by S. pneumoniae in all the niches that it colonized. Here we show, by quantitative means, that extracellular zinc acts in a dose dependent manner to competitively inhibit manganese uptake by S. pneumoniae, with an EC50 of 30.2 µM for zinc in cation-defined media. By exploiting the ability to directly manipulate S. pneumoniae accumulation of manganese, we analyzed the connection between manganese and superoxide dismutase (SodA), a primary source of protection for S. pneumoniae against oxidative stress. We show that manganese starvation led to a decrease in sodA transcription indicating that expression of sodA was regulated through an unknown manganese responsive pathway. Intriguingly, examination of recombinant SodA revealed that the enzyme was potentially a cambialistic superoxide dismutase with an iron/manganese cofactor. SodA was also shown to provide the majority of protection against oxidative stress as a S. pneumoniae ΔsodA mutant strain was found to be hypersensitive to oxidative stress, despite having wild-type manganese levels, indicating that the metal ion alone was not sufficiently protective. Collectively, these results provide a quantitative assessment of the competitive effect of zinc upon manganese uptake and provide a molecular basis for how extracellular zinc exerts a 'toxic' effect on bacterial pathogens, such as S. pneumoniae. PMID:24558498

  14. Extracellular Zinc Competitively Inhibits Manganese Uptake and Compromises Oxidative Stress Management in Streptococcus pneumoniae

    PubMed Central

    Eijkelkamp, Bart A.; Morey, Jacqueline R.; Ween, Miranda P.; Ong, Cheryl-lynn Y.; McEwan, Alastair G.; Paton, James C.; McDevitt, Christopher A.

    2014-01-01

    Streptococcus pneumoniae requires manganese for colonization of the human host, but the underlying molecular basis for this requirement has not been elucidated. Recently, it was shown that zinc could compromise manganese uptake and that zinc levels increased during infection by S. pneumoniae in all the niches that it colonized. Here we show, by quantitative means, that extracellular zinc acts in a dose dependent manner to competitively inhibit manganese uptake by S. pneumoniae, with an EC50 of 30.2 µM for zinc in cation-defined media. By exploiting the ability to directly manipulate S. pneumoniae accumulation of manganese, we analyzed the connection between manganese and superoxide dismutase (SodA), a primary source of protection for S. pneumoniae against oxidative stress. We show that manganese starvation led to a decrease in sodA transcription indicating that expression of sodA was regulated through an unknown manganese responsive pathway. Intriguingly, examination of recombinant SodA revealed that the enzyme was potentially a cambialistic superoxide dismutase with an iron/manganese cofactor. SodA was also shown to provide the majority of protection against oxidative stress as a S. pneumoniae ΔsodA mutant strain was found to be hypersensitive to oxidative stress, despite having wild-type manganese levels, indicating that the metal ion alone was not sufficiently protective. Collectively, these results provide a quantitative assessment of the competitive effect of zinc upon manganese uptake and provide a molecular basis for how extracellular zinc exerts a ‘toxic’ effect on bacterial pathogens, such as S. pneumoniae. PMID:24558498

  15. Oxidative damage and neurodegeneration in manganese-induced neurotoxicity

    SciTech Connect

    Milatovic, Dejan; Yu, Yingchun

    2009-10-15

    Exposure to excessive manganese (Mn) levels results in neurotoxicity to the extrapyramidal system and the development of Parkinson's disease (PD)-like movement disorder, referred to as manganism. Although the mechanisms by which Mn induces neuronal damage are not well defined, its neurotoxicity appears to be regulated by a number of factors, including oxidative injury, mitochondrial dysfunction and neuroinflammation. To investigate the mechanisms underlying Mn neurotoxicity, we studied the effects of Mn on reactive oxygen species (ROS) formation, changes in high-energy phosphates (HEP), neuroinflammation mediators and associated neuronal dysfunctions both in vitro and in vivo. Primary cortical neuronal cultures showed concentration-dependent alterations in biomarkers of oxidative damage, F{sub 2}-isoprostanes (F{sub 2}-IsoPs) and mitochondrial dysfunction (ATP), as early as 2 h following Mn exposure. Treatment of neurons with 500 {mu}M Mn also resulted in time-dependent increases in the levels of the inflammatory biomarker, prostaglandin E{sub 2} (PGE{sub 2}). In vivo analyses corroborated these findings, establishing that either a single or three (100 mg/kg, s.c.) Mn injections (days 1, 4 and 7) induced significant increases in F{sub 2}-IsoPs and PGE{sub 2} in adult mouse brain 24 h following the last injection. Quantitative morphometric analyses of Golgi-impregnated striatal sections from mice exposed to single or three Mn injections revealed progressive spine degeneration and dendritic damage of medium spiny neurons (MSNs). These findings suggest that oxidative stress, mitochondrial dysfunction and neuroinflammation are underlying mechanisms in Mn-induced neurodegeneration.

  16. Surface characteristics and in vitro biocompatibility of a manganese-containing titanium oxide surface

    NASA Astrophysics Data System (ADS)

    Park, Jin-Woo; Kim, Youn-Jeong; Jang, Je-Hee

    2011-11-01

    This study investigated the surface characteristics and in vitro biocompatibility of a titanium (Ti) oxide layer incorporating the manganese ions (Mn) obtained by hydrothermal treatment with the expectation of utilizing potent integrin-ligand binding enhancement effect of Mn for future applications as an endosseous implant surface. The surface characteristics were evaluated by scanning electron microscopy, thin-film X-ray diffractometry, X-ray photoelectron spectroscopy, optical profilometry and inductively coupled plasma-atomic emission spectroscopy (ICP-AES). The in vitro biocompatibility of the Mn-containing Ti oxide surface was evaluated in comparison with untreated bare Ti using a mouse calvaria-derived osteoblastic cell line (MC3T3-E1). The hydrothermal treatment produced a nanostructured Mn-incorporated Ti oxide layer approximately 0.6 μm thick. ICP-AES analysis demonstrated that the Mn ions were released from the hydrothermally treated surface into the solution. Mn incorporation notably decreased cellular attachment, spreading, proliferation, alkaline phosphatase activity, and osteoblast phenotype gene expression compared with the bare Ti surface (p < 0.05). The results indicate that the Mn-incorporation into the surface Ti oxide layer has no evident beneficial effects on osteoblastic cell function, but instead, actually impaired cell behavior.

  17. Visible and near-infrared spectra of manganese oxides: Detecting high manganese phases in Curiosity Mastcam multispectral images

    NASA Astrophysics Data System (ADS)

    Hardgrove, C. J.; Lanza, N.; Bell, J. F., III; Wiens, R. C.; Johnson, J. R.; Morris, R. V.

    2014-12-01

    The Mars Science Laboratory Curiosity rover's Chemcam instrument has identified manganese in relatively high abundance on several rock surfaces. The manganese abundances are several orders of magnitude greater than has been previously identified on Mars, indicating the presence of a manganese-rich phase. Although the specific phase has yet to be identified, these results suggest that the martian surface may have been much more highly oxidizing than has previously been recognized. The presence of a manganese-rich phase could provide an additional indicator of habitable aqueous environments. Given the importance of manganese for understanding past habitability, and the high abundances identified with Chemcam, we investigate the utility of using Mastcam multispectral imaging surveys to identify areas for subsequent detailed analysis with Chemcam. Vempati et al. showed that Mn3+ affect the reflectance spectra of Mn-bearing minerals. Specifically, relatively weak features due to electronic transitions and crystal field effects are observed in Mn-enriched hematites and geothites at 454, 554, 596 and 700 nm. The Mastcam-34 medium angle camera has filter band-passes at 550, 675 and 750nm, and we will explore the utility of using these bands (or combinations thereof) to determine if there is a contribution of Mn-bearing phases on spectra, specifically those that have been identified as having elevated Mn with Chemcam. The most common Mn-bearing mineral phase in terrestrial varnishes, Birnessite, has charge-transfer features that are similar to Fe-oxides but are centered at slightly longer wavelength band positions. Longer wavelength features are also common for other Mn-oxides, and this could be used to distinguish these phases from other Fe-oxide components. In this study we will present visible to near-infrared (0.4 - 3 µm) reflectance spectra on a suite of Mn-oxide laboratory standards. The set of standards includes Mn-oxide abundances that vary from less than 1 up to

  18. Photosynthetic water oxidation: insights from manganese model chemistry.

    PubMed

    Young, Karin J; Brennan, Bradley J; Tagore, Ranitendranath; Brudvig, Gary W

    2015-03-17

    Catalysts for light-driven water oxidation are a critical component for development of solar fuels technology. The multielectron redox chemistry required for this process has been successfully deployed on a global scale in natural photosynthesis by green plants and cyanobacteria using photosystem II (PSII). PSII employs a conserved, cuboidal Mn4CaOX cluster called the O2-evolving complex (OEC) that offers inspiration for artificial O2-evolution catalysts. In this Account, we describe our work on manganese model chemistry relevant to PSII, particularly the functional model [Mn(III/IV)2(terpy)2(μ-O)2(OH2)2](NO3)3 complex (terpy = 2,2';6',2″-terpyridine), a mixed-valent di-μ-oxo Mn dimer with two terminal aqua ligands. In the presence of oxo-donor oxidants such as HSO5(-), this complex evolves O2 by two pathways, one of which incorporates solvent water in an O-O bond-forming reaction. Deactivation pathways of this catalyst include comproportionation to form an inactive Mn(IV)Mn(IV) dimer and also degradation to MnO2, a consequence of ligand loss when the oxidation state of the complex is reduced to labile Mn(II) upon release of O2. The catalyst's versatility has been shown by its continued catalytic activity after direct binding to the semiconductor titanium dioxide. In addition, after binding to the surface of TiO2 via a chromophoric linker, the catalyst can be oxidized by a photoinduced electron-transfer mechanism, mimicking the natural PSII process. Model oxomanganese complexes have also aided in interpreting biophysical and computational studies on PSII. In particular, the μ-oxo exchange rates of the Mn-terpy dimer have been instrumental in establishing that the time scale for μ-oxo exchange of high-valent oxomanganese complexes with terminal water ligands is slower than O2 evolution in the natural photosynthetic system. Furthermore, computational studies on the Mn-terpy dimer and the OEC point to similar Mn(IV)-oxyl intermediates in the O-O bond

  19. Mercury removal from waste gases by manganese oxide acceptors

    SciTech Connect

    Cavallaro, S.; Bertuccio, N.; Antonucci, P.; Giordano, N.

    1982-02-01

    Removal of mercury vapor from a waste gas has been investigated at atmospheric pressure and at ambient temperature using a series of manganese-based reagents supported on an inert medium. The effect of catalyst composition on activity and the influence of relative humidity of the air stream have been studied. Whereas ..gamma..-Al/sub 2/O/sub 3/ has a very low mercury sorption capacity, sorption occurs copiously on impregnated silver- and copper-doped MnO/sub 2/ acceptors but the much higher activity is reduced by the presence of water vapour in the carrier gas. The morphological and microstructural characterization of the (MnO/sub 2/, AgNO/sub 3/) ..gamma..-Al/sub 2/O/sub 3/ reagents has shown selective deposition of AgNO/sub 3/ particles on ..beta..-MnO/sub 2/ crystallites which are dispersed on the ..gamma..-Al/sub 2/O/sub 3/ matrix. As the adsorption is associated with a sequence of specific colour changes a chemical oxidation mechanism is proposed. Acceptor deactivation is discussed. 9 figures, 3 tables.

  20. Effects of FeS on Chromium Oxidation Mediated by Manganese Oxidizers

    SciTech Connect

    Wu, Youxian; Deng, Baolin

    2004-03-31

    Reductive immobilization of Cr(VI) has been widely explored as a cost-effective approach for Cr-contaminated site remediation. The long-term stability of the immobilized Cr(III), however, is a concern. Cr(III) is known to be oxidized by Mn oxides chemically and Mn-oxides could be produced through microbially mediated Mn(II) oxidation. This study examined the effect of FeS on Cr(III) oxidation mediated by Pseudomonas putida. The results showed that commercial granular FeS did not affect Cr(III) oxidation in the culture of P. putida with Mn(II), but freshly precipitated FeS slurry inhibited Cr(III) oxidation. A 10 mg/l of FeS did not inhibit the microbial growth, but delayed the production of Mn oxides, thus postponing potential Cr(III) oxidation. In the presence of excessive FeS slurry, both Cr(VI) and Mn oxides were reduced rapidly. The reduced Cr(III) could not be re-oxidized as long as freshly formed FeS was present, even in the presence of the manganese oxidizers.

  1. Study of a QCM Dimethyl Methylphosphonate Sensor Based on a ZnO-Modified Nanowire-Structured Manganese Dioxide Film

    PubMed Central

    Pei, Zhifu; Ma, Xingfa; Ding, Pengfei; Zhang, Wuming; Luo, Zhiyuan; Li, Guang

    2010-01-01

    Sensitive, selective and fast detection of chemical warfare agents is necessary for anti-terrorism purposes. In our search for functional materials sensitive to dimethyl methylphosphonate (DMMP), a simulant of sarin and other toxic organophosphorus compounds, we found that zinc oxide (ZnO) modification potentially enhances the absorption of DMMP on a manganese dioxide (MnO2) surface. The adsorption behavior of DMMP was evaluated through the detection of tiny organophosphonate compounds with quartz crystal microbalance (QCM) sensors coated with ZnO-modified MnO2 nanofibers and pure MnO2 nanofibers. Experimental results indicated that the QCM sensor coated with ZnO-modified nanostructured MnO2 film exhibited much higher sensitivity and better selectivity in comparison with the one coated with pure MnO2 nanofiber film. Therefore, the DMMP sensor developed with this composite nanostructured material should possess excellent selectivity and reasonable sensitivity towards the tiny gaseous DMMP species. PMID:22163653

  2. Study of a QCM dimethyl methylphosphonate sensor based on a ZnO-modified nanowire-structured manganese dioxide film.

    PubMed

    Pei, Zhifu; Ma, Xingfa; Ding, Pengfei; Zhang, Wuming; Luo, Zhiyuan; Li, Guang

    2010-01-01

    Sensitive, selective and fast detection of chemical warfare agents is necessary for anti-terrorism purposes. In our search for functional materials sensitive to dimethyl methylphosphonate (DMMP), a simulant of sarin and other toxic organophosphorus compounds, we found that zinc oxide (ZnO) modification potentially enhances the absorption of DMMP on a manganese dioxide (MnO(2)) surface. The adsorption behavior of DMMP was evaluated through the detection of tiny organophosphonate compounds with quartz crystal microbalance (QCM) sensors coated with ZnO-modified MnO(2) nanofibers and pure MnO(2) nanofibers. Experimental results indicated that the QCM sensor coated with ZnO-modified nanostructured MnO(2) film exhibited much higher sensitivity and better selectivity in comparison with the one coated with pure MnO(2) nanofiber film. Therefore, the DMMP sensor developed with this composite nanostructured material should possess excellent selectivity and reasonable sensitivity towards the tiny gaseous DMMP species. PMID:22163653

  3. Room-Temperature Oxidation of Formaldehyde by Layered Manganese Oxide: Effect of Water.

    PubMed

    Wang, Jinlong; Zhang, Pengyi; Li, Jinge; Jiang, Chuanjia; Yunus, Rizwangul; Kim, Jeonghyun

    2015-10-20

    Layered manganese oxide, i.e., birnessite was prepared via the reaction of potassium permanganate with ammonium oxalate. The water content in the birnessite was adjusted by drying/calcining the samples at various temperatures (30 °C, 100 °C, 200 °C, 300 °C, and 500 °C). Thermogravimetry-mass spectroscopy showed three types of water released from birnessite, which can be ascribed to physically adsorbed H2O, interlayer H2O and hydroxyl, respectively. The activity of birnessite for formaldehyde oxidation was positively associated with its water content, i.e., the higher the water content, the better activity it has. In-situ DRIFTS and step scanning XRD analysis indicate that adsorbed formaldehyde, which is promoted by bonded water via hydrogen bonding, is transformed into formate and carbonate with the consumption of hydroxyl and bonded water. Both bonded water and water in air can compensate the consumed hydroxyl groups to sustain the mineralization of formaldehyde at room temperature. In addition, water in air stimulates the desorption of carbonate via water competitive adsorption, and accordingly the birnessite recovers its activity. This investigation elucidated the role of water in oxidizing formaldehyde by layered manganese oxides at room temperature, which may be helpful for the development of more efficient materials. PMID:26426569

  4. Effect of oxide formation mechanisms on lead adsorption by biogenic manganese (hydr)oxides, iron (hydr)oxides, and their mixtures.

    PubMed

    Nelson, Yarrow M; Lion, Leonard W; Shuler, Michael L; Ghiorse, William C

    2002-02-01

    The effects of iron and manganese (hydr)oxide formation processes on the trace metal adsorption properties of these metal (hydr)oxides and their mixtures was investigated by measuring lead adsorption by iron and manganese (hydr)oxides prepared by a variety of methods. Amorphous iron (hydr)oxide formed by fast precipitation at pH 7.5 exhibited greater Pb adsorption (gamma(max) = 50 mmol of Pb/mol of Fe at pH 6.0) than iron (hydr)oxide formed by slow, diffusion-controlled oxidation of Fe(II) at pH 4.5-7.0 or goethite. Biogenic manganese(III/IV) (hydr)oxide prepared by enzymatic oxidation of Mn(II) by the bacterium Leptothrix discophora SS-1 adsorbed five times more Pb (per mole of Mn) than an abiotic manganese (hydr)oxide prepared by oxidation of Mn(II) with permanganate, and 500-5000 times more Pb than pyrolusite oxides (betaMnO2). X-ray crystallography indicated that biogenic manganese (hydr)oxide and iron (hydr)oxide were predominantly amorphous or poorly crystalline and their X-ray diffraction patterns were not significantly affected by the presence of the other (hydr)oxide during formation. When iron and manganese (hydr)oxides were mixed after formation, or for Mn biologically oxidized with iron(III) (hydr)oxide present, observed Pb adsorption was similar to that expected for the mixture based on Langmuir parameters for the individual (hydr)oxides. These results indicate that interactions in iron/manganese (hydr)oxide mixtures related to the formation process and sequence of formation such as site masking, alterations in specific surface area, or changes in crystalline structure either did not occur or had a negligible effect on Pb adsorption by the mixtures. PMID:11871557

  5. Manganese-oxidizing bacteria mediate the degradation of 17α-ethinylestradiol.

    PubMed

    Sabirova, Julia S; Cloetens, L F F; Vanhaecke, L; Forrez, I; Verstraete, Willy; Boon, N

    2008-11-01

    Manganese (II) and manganese-oxidizing bacteria were used as an efficient biological system for the degradation of the xenoestrogen 17α-ethinylestradiol (EE2) at trace concentrations. Mn(2+)-derived higher oxidation states of Mn (Mn(3+), Mn(4+)) by Mn(2+)-oxidizing bacteria mediate the oxidative cleavage of the polycyclic target compound EE2. The presence of manganese (II) was found to be essential for the degradation of EE2 by Leptothrix discophora, Pseudomonas putida MB1, P. putida MB6 and P. putida MB29. Mn(2+)-dependent degradation of EE2 was found to be a slow process, which requires multi-fold excess of Mn(2+) and occurs in the late stationary phase of growth, implying a chemical process taking place. EE2-derived degradation products were shown to no longer exhibit undesirable estrogenic activity. PMID:21261871

  6. Catalytic role of Manganese oxides in prebiotic Nucleobases synthesis from Formamide

    NASA Astrophysics Data System (ADS)

    Bhushan, Brij

    2012-07-01

    The evolution of living cell from chemicals is more complicated reaction which could be studied in multistep. A study of prebiotic synthesis of naturally occurring purine and pyrimidine derivatives from formamide under catalytic condition with different oxides of manganese reveals a significant role. Manganese oxides are highly efficient in the conversion of formamide into different nucleobases. Neat formamide is converted to the purine, 9-(hydroxyacetyl) purine, cytosine, 4(3H)-pyrimidinone, thymine and adenine in good yield. Metal oxides have provided their surfaces and catalyzed the reactions from simple molecules to more complex bio-organic molecules. Our results show that probably prebiotic reactions might have occured on the sea floor where the existence of manganese oxide is second to iron transition metal minerals.

  7. Microbial oxidation and reduction of manganese: consequences in groundwater and applications.

    PubMed

    Gounot, A M

    1994-08-01

    In the natural environment, manganese is found as reduced soluble or adsorbed Mn(II) and insoluble Mn(III) and Mn(IV) oxides. Mn oxidation has been reported in various microorganisms. Several possible pathways, indirect or direct, have been proposed. A wider variety of Mn-reducing microorganisms, from highly aerobic to strictly anaerobic, has been described. The mechanisms of Mn reduction can be either an indirect process resulting from interactions with organic or inorganic compounds, or a direct enzymatic (electron-transfer) reaction. The role of microorganisms in Mn cycle is now well demonstrated by various methods in superficial natural environments, and research has been initiated on subsurface sediments. Observations in vivo (Rhône valley) and under in vitro suggested that bacterial activities are the main processes that promote manganese evolution and migration in shallow aquifers. After the building of hydroelectric dams, the stream of the Rhône was modified, giving rise to mud deposition on the bank. In the mud, bacteria are stimulated by the high organic content and consume oxygen. The redox potential drops. The manganese oxides previously formed under aerobic conditions are reduced and soluble manganese (Mn(II)) migrates into the aquifer. If the subsurface sediments are coarse-grained, the aquifer is well aerated, allowing the re-oxidation of Mn(II) by the oligotrophic attached bacteria in aquifer sediments. If the aquifer is confined, aeration is not sufficient for Mn-reoxidation. Mn(II) remains in a reduced state and migrates to the wells. Furthermore, the presence of organic matter in subsurface sediments results in the reduction of previously formed Mn oxides. Pseudo-amorphous manganese oxides, which were probably recently formed by bacteria, are more readily reduced than old crystalline manganese oxides. Although the concentrations of soluble manganese found in groundwaters are not toxic, it still is a problem since its oxidation results in

  8. Electrocatalytic oxidation of dopamine based on non-covalent functionalization of manganese tetraphenylporphyrin/reduced graphene oxide nanocomposite.

    PubMed

    Sakthinathan, Subramanian; Lee, Hsin Fang; Chen, Shen-Ming; Tamizhdurai, P

    2016-04-15

    In the present work, a reduced graphene oxide (RGO) supported manganese tetraphenylporphyrin (Mn-TPP) nanocomposite was electrochemically synthesized and used for the highly selective and sensitive detection of dopamine (DA). The nuclear magnetic resonance, scanning electron microscopy and elemental analysis were confirmed the successful formation of RGO/Mn-TPP nanocomposite. The prepared RGO/Mn-TPP nanocomposite modified electrode exhibited an enhanced electrochemical response to DA with less oxidation potential and enhanced response current. The electrochemical studies revealed that the oxidation of the DA at the composite electrode is a surface controlled process. The cyclic voltammetry, differential pulse voltammetry and amperometry methods were enable to detect DA. The working linear range of the electrode was observed from 0.3 to 188.8 μM, limit of detection was 8 nM and the sensitivity was 2.606 μA μM(-1) cm(-2). Here, the positively charged DA and negatively charged porphyrin modified RGO can accelerate the electrocatalysis of DA via electrostatic attraction, while the negatively charged ascorbic acid (AA) repulsed by the negatively charged electrode surface which supported for good selectivity. The good recovery results obtained for the determination of DA present in DA injection samples and human pathological sample further revealed the good practicality of RGO/Mn-TPP nanocomposite film modified electrode. PMID:26835582

  9. In-situ X-Ray Absorption Spectroscopy (XAS) Investigation of a Bifunctional Manganese Oxide Catalyst with High Activity for Electrochemical Water Oxidation and Oxygen Reduction

    PubMed Central

    Benck, Jesse D.; Gul, Sheraz; Webb, Samuel M.; Yachandra, Vittal K.; Yano, Junko; Jaramillo, Thomas F.

    2013-01-01

    In-situ x-ray absorption spectroscopy (XAS) is a powerful technique that can be applied to electrochemical systems, with the ability to elucidate the chemical nature of electrocatalysts under reaction conditions. In this study, we perform in-situ XAS measurements on a bifunctional manganese oxide (MnOx) catalyst with high electrochemical activity for the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER). Using x-ray absorption near edge structure (XANES) and extended x-ray absorption fine structure (EXAFS), we find that exposure to an ORR-relevant potential of 0.7 V vs. RHE produces a disordered Mn3II,III,IIIO4 phase with negligible contributions from other phases. After the potential is increased to a highly anodic value of 1.8 V vs. RHE, relevant to the OER, we observe an oxidation of approximately 80% of the catalytic thin film to form a mixed MnIII,IV oxide, while the remaining 20% of the film consists of a less oxidized phase, likely corresponding to unchanged Mn3II,III,IIIO4. XAS and electrochemical characterization of two thin film catalysts with different MnOx thicknesses reveals no significant influence of thickness on the measured oxidation states, at either ORR or OER potentials, but demonstrates that the OER activity scales with film thickness. This result suggests that the films have porous structure, which does not restrict electrocatalysis to the top geometric layer of the film. As the portion of the catalyst film that is most likely to be oxidized at the high potentials necessary for the OER is that which is closest to the electrolyte interface, we hypothesize that the MnIII,IV oxide, rather than Mn3II,III,IIIO4, is the phase pertinent to the observed OER activity. PMID:23758050

  10. Manganese Compounds as Water-Oxidizing Catalysts: From the Natural Water-Oxidizing Complex to Nanosized Manganese Oxide Structures.

    PubMed

    Najafpour, Mohammad Mahdi; Renger, Gernot; Hołyńska, Małgorzata; Moghaddam, Atefeh Nemati; Aro, Eva-Mari; Carpentier, Robert; Nishihara, Hiroshi; Eaton-Rye, Julian J; Shen, Jian-Ren; Allakhverdiev, Suleyman I

    2016-03-01

    All cyanobacteria, algae, and plants use a similar water-oxidizing catalyst for water oxidation. This catalyst is housed in Photosystem II, a membrane-protein complex that functions as a light-driven water oxidase in oxygenic photosynthesis. Water oxidation is also an important reaction in artificial photosynthesis because it has the potential to provide cheap electrons from water for hydrogen production or for the reduction of carbon dioxide on an industrial scale. The water-oxidizing complex of Photosystem II is a Mn-Ca cluster that oxidizes water with a low overpotential and high turnover frequency number of up to 25-90 molecules of O2 released per second. In this Review, we discuss the atomic structure of the Mn-Ca cluster of the Photosystem II water-oxidizing complex from the viewpoint that the underlying mechanism can be informative when designing artificial water-oxidizing catalysts. This is followed by consideration of functional Mn-based model complexes for water oxidation and the issue of Mn complexes decomposing to Mn oxide. We then provide a detailed assessment of the chemistry of Mn oxides by considering how their bulk and nanoscale properties contribute to their effectiveness as water-oxidizing catalysts. PMID:26812090

  11. Studies of layered and pillared manganese oxide materials

    NASA Astrophysics Data System (ADS)

    Ma, Ying

    Synthetic Birnessite, an octahedral layered manganese oxide material called OL-1 was synthesized with Na+, K+, Na +/Mg2+, K+/Mg2+, Na +/K+ ions as interlayer cations by redox reactions between permanganate and alcohols in a strong basic media. Chromia pillared OL-1s were prepared under reflux conditions using trinuclear chromium hydroxyl acetate as a pillaring agent followed by calcination in a N2 atmosphere at 200°C. Vanadium oxide pillared OL-1s were obtained by intercalating neutral vanadyl acetylacetonate (VOacac) or vanadium acetylacetonate (Vacac) into the interlayer of OL-1 and subsequently calcining in air at 300°C. The synthesis procedures were monitored using X-ray diffraction studies. The resultant materials were characterized by XRD, X-ray absorption, X-ray photoelectron spectra, FTIR, UV-VIS, inductively coupled plasma, transmission electron spectroscopy, scanning electron microscopy with energy dispersive X-ray analysis, potentiometric titration, thermal analyses, TPD measurements, BET surface area and pore size distribution measurements. OL-1 materials prepared using this alcohol route showed enhanced thermal stabilities and increased Mg accommodation compared to OL-1s prepared with other methods. Based on the analysis methods developed here, Na-OL-1 exhibited recoverable and reversible structural and surface O2 oxygen species while K-OL-1 showed higher stability. Na-OL-1 had predominantly Bronsted acid sites resulting from OH groups bonded to Mn on Na-OL-1 surfaces, while the Na/Mg-OL-1 had mainly Lewis acid sites. Large porosity was obtained in chromia pillared OL-1 materials with a narrow pore size distribution centered around 18 A. Although these materials remained "amorphous" as determined by XRD after calcination, TEM morphology studies suggest that the materials were still layered. EXAFS studies indicated the formation of Cr-O-Mn bonds in the resultant materials via comer-shared linkages of CrO6 and MnO6 octahedra. Good crystallinity in

  12. Determination of uranyl incorporation into biogenic manganese oxides using X-ray absorption spectroscopy and scattering

    USGS Publications Warehouse

    Webb, S.M.; Fuller, C.C.; Tebo, B.M.; Bargar, J.R.

    2006-01-01

    Biogenic manganese oxides are common and an important source of reactive mineral surfaces in the environment that may be potentially enhanced in bioremediation cases to improve natural attenuation. Experiments were performed in which the uranyl ion, UO22+ (U(VI)), at various concentrations was present during manganese oxide biogenesis. At all concentrations, there was strong uptake of U onto the oxides. Synchrotron-based extended X-ray absorption fine structure (EXAFS) spectroscopy and X-ray diffraction (XRD) studies were carried out to determine the molecular-scale mechanism by which uranyl is incorporated into the oxide and how this incorporation affects the resulting manganese oxide structure and mineralogy. The EXAFS experiments show that at low concentrations (2 mol % U, >4 ??M U(VI) in solution), the presence of U(VI) affects the stability and structure of the Mn oxide to form poorly ordered Mn oxide tunnel structures, similar to todorokite. EXAFS modeling shows that uranyl is present in these oxides predominantly in the tunnels of the Mn oxide structure in a tridentate complex. Observations by XRD corroborate these results. Structural incorporation may lead to more stable U(VI) sequestration that may be suitable for remediation uses. These observations, combined with the very high uptake capacity of the Mn oxides, imply that Mn-oxidizing bacteria may significantly influence dissolved U(VI) concentrations in impacted waters via sorption and incorporation into Mn oxide biominerals. ?? 2006 American Chemical Society.

  13. Ethanedithiol-treated manganese oxide nanoparticles for rapidly responsive and transparent supercapacitors

    NASA Astrophysics Data System (ADS)

    Ryu, Ilhwan; Kim, Green; Park, Dasom; Yim, Sanggyu

    2015-11-01

    Metal oxide nanoparticles (NPs) provide a large surface area and short diffusion pathways for ions in supercapacitor electrode materials. However, binders and conductive additives used for tight connections with current collectors and improved conductivity hamper these benefits. In this work, we successfully fix manganese oxide (Mn3O4) NPs onto ITO current collectors by a simple 1,2-ethanedithiol (EDT) treatment without using any binders or conductive additives. As compared to the electrode fabricated using binder-mixed Mn3O4 NPs, the EDT-treated electrode shows significantly improved specific capacitance of 403 F g-1 at a scan rate of 10 mV s-1. The EDT-treatment is more effective at higher scan rates. The specific capacitances, 278 F g-1 at 100 mV s-1 and 202 F g-1 at 200 mV s-1, are larger than those reported so far at scan rates ≥100 mV s-1. The deconvolution of capacitive elements indicates that these improved capacitive properties are attributed to large insertion elements of the binder-free NP electrodes. Furthermore, this additive-free electrode is highly transparent and can be easily fabricated by simple spray-coating on various substrates including polymer films, implying that this new method is promising for the fabrication of large-area, transparent and flexible electrodes for next-generation supercapacitors.

  14. Effect of additives on electrochemical performance of lithium nickel cobalt manganese oxide at high temperature

    NASA Astrophysics Data System (ADS)

    Kang, Kyoung Seok; Choi, Suneui; Song, JunHo; Woo, Sang-Gil; Jo, Yong Nam; Choi, Jungkyu; Yim, Taeeun; Yu, Ji-Sang; Kim, Young-Jun

    2014-05-01

    Lithium-nickel-cobalt-manganese oxide, Li[NixCoyMnz]O2 (NCM) is a low-cost cathode material with a high capacity and a moderately high rate capability, however, it still suffers from poor electrochemical performance. In this study, several types of additives are attempted to enhance the surface stability of high-Ni-content (Ni ≥ 60%) cathodes and the most effective additive turns out to be PS. The cycle performance in the presence of 2% PS is much improved at a high temperature of 60 °C: (1) 98.9% of its initial capacity is preserved, (2) the increase in thickness is only 17.9%, preventing undesired swellings, and (3) gases are not generated in large amounts with the internal pressure being 56.4 kPa. The FT-IR spectroscopy results suggest that the surface of the cathode in the presence of 2% PS is covered with a film of alkyl sulfone components (RSOSR and RSO2SR), which is possibly formed by the electrochemical oxidation of PS. The current results confirm that the electrochemical performance of Ni-rich cathodes can be improved via the appropriate use of additives. They also indicate that among the tested additive candidates in this study, PS is highly desirable for enhancing the electrochemical performance of Ni-rich cathodes.

  15. Sol-gel synthesis and adsorption properties of mesoporous manganese oxide

    NASA Astrophysics Data System (ADS)

    Ivanets, A. I.; Kuznetsova, T. F.; Prozorovich, V. G.

    2015-03-01

    Sol-gel synthesis of mesoporous xerogels of manganese oxide with different phase compositions has been performed. The manganese oxide sols were obtained by redox reactions of potassium permanganate with hydrogen peroxide or manganese(II) chloride in aqueous solutions. The isotherms of the low-temperature adsorption-desorption of nitrogen with manganese oxide xerogels treated at 80, 200, 400, and 600°C were measured. The samples were studied by electron microscopy and thermal and XRD analysis. The phase transformation and the changes in the adsorption and capillary-condensation properties of manganese oxide were shown to depend on the sol synthesis conditions and the temperature of the thermal treatment of the gel. The X-ray amorphous samples heated at 80°C were shown to have low values of the specific surface; at higher temperatures, the xerogel crystallized into mixed phases with various compositions and its surface area increased at 200-400°C and decreased at 600°C.

  16. Catalytic ozonation of sulfosalicylic acid over manganese oxide supported on mesoporous ceria.

    PubMed

    Xing, Shengtao; Lu, Xiaoyang; Liu, Jia; Zhu, Lin; Ma, Zichuan; Wu, Yinsu

    2016-02-01

    Manganese oxide supported on mesoporous ceria was prepared and used as catalyst for catalytic ozonation of sulfosalicylic acid (SA). Characterization results indicated that the manganese oxide was mostly incorporated into the pores of ceria. The synthesized catalyst exhibited high activity and stability for the mineralization of SA in aqueous solution by ozone, and more than 95% of total organic carbon was removed in 30 min under various conditions. Mechanism studies indicated that SA was mainly degraded by ozone molecules, and hydroxyl radical reaction played an important role for the degradation of its ozonation products (small molecular organic acids). The manganese oxide in the pores of CeO2 improved the adsorption of small molecular organic acids and the generation of hydroxyl radicals from ozone decomposition, resulting in high TOC removal efficiency. PMID:26344143

  17. Sorption of lead ions on diatomite and manganese oxides modified diatomite.

    PubMed

    Al-Degs, Y; Khraisheh, M A; Tutunji, M F

    2001-10-01

    Naturally occurring diatomaceous earth (diatomite) has been tested as a potential sorbent for Pb(II) ions. The intrinsic exchange properties were further improved by modification with manganese oxides. Modified adsorbent (referred to as Mn-diatomite) showed a higher tendency for adsorbing lead ions from solution at pH 4. The high performance exhibited by Mn-diatomite was attributed to increased surface area and higher negative surface charge after modification. Scanning electron microscope pictures revealed a birnessite structure of manganese oxides, which was featured by a plate-like-crystal structure. Diatomite filtration quality was improved after modification by manganese oxides. Good filtration qualities combined with high exchange capacity emphasised the potential use of Mn-diatomite in filtration systems. PMID:11561635

  18. Electrochemically formed 3D hierarchical thin films of cobalt-manganese (Co-Mn) hexacyanoferrate hybrids for electrochemical applications

    NASA Astrophysics Data System (ADS)

    Alam Venugopal, Narendra Kumar; Joseph, James

    2016-02-01

    Here we report the feasibility of forming 3D nanostructured hexacyanoferates of Cobalt and Manganese (Co-MnHCF) on GC surface by a facile electrochemical method. This 3D architecture on glassy carbon electrode characterised systematically by voltammetry and other physical characterisation techniques like Field emission scanning electron microscopy (FESEM), X-ray diffraction (XRD) and Fourier transform Infrared spectroscopy (FTIR) etc,. Electrochemical Quartz crystal microbalance (EQCM) studies helped out to calculate the total mass change during Co-MnHCF formation. Electrochemical studies reveal that the formal redox potentials of both Co and MnHCF films remained close to that of newly formed Co-MnHCF hybrid films. These 3D modified films were successfully applied for two different electrochemical applications i) For pseudocapacitor studies in KNO3 medium ii) Investigated the electrocatalytic behaviour of redox film towards water oxidation reaction in alkaline medium. Electrochemical performances of newly formed Co-MnHCF are compared with their individual transition metal (Co, Mn) hexacyanoferrates. The resulting material shows a specific capacitance of 350 F g-1 through its fast reversible redox reaction of electrochemically formed Co-MnHCF modified film. Interestingly we showed the overpotential of 450 mV (from its thermodynamic voltage 1.2 V) to attain its optimum current density of 10 mA cm-2 for O2 evolution in alkaline medium.

  19. Synthesis and Characterization of a Layered Manganese Oxide: Materials Chemistry for the Inorganic or Instrumental Methods Lab

    ERIC Educational Resources Information Center

    Ching, Stanton; Neupane, Ram P.; Gray, Timothy P.

    2006-01-01

    A three-week laboratory project involving synthesis and characterization of a layered manganese oxide provides an excellent vehicle for teaching important concepts of inorganic chemistry and instrumental methods related to non-molecular systems. Na-birnessite is an easily prepared manganese oxide with a 7 A interlayer spacing and Na[superscript +]…

  20. Microcolumn studies of dye adsorption onto manganese oxides modified diatomite.

    PubMed

    Al-Ghouti, M A; Khraisheh, M A M; Ahmad, M N; Allen, S J

    2007-07-19

    The method described here cannot fully replace the analysis of large columns by small test columns (microcolumns). The procedure, however, is suitable for speeding up the determination of adsorption parameters of dye onto the adsorbent and for speeding up the initial screening of a large adsorbent collection that can be tedious if a several adsorbents and adsorption conditions must be tested. The performance of methylene blue (MB), a basic dye, Cibacron reactive black (RB) and Cibacron reactive yellow (RY) was predicted in this way and the influence of initial dye concentration and other adsorption conditions on the adsorption behaviour were demonstrated. On the basis of the experimental results, it can be concluded that the adsorption of RY onto manganese oxides modified diatomite (MOMD) exhibited a characteristic "S" shape and can be simulated effectively by the Thomas model. It is shown that the adsorption capacity increased as the initial dye concentration increased. The increase in the dye uptake capacity with the increase of the adsorbent mass in the column was due to the increase in the surface area of adsorbent, which provided more binding sites for the adsorption. It is shown that the use of high flow rates reduced the time that RY in the solution is in contact with the MOMD, thus allowing less time for adsorption to occur, leading to an early breakthrough of RY. A rapid decrease in the column adsorption capacity with an increase in particle size with an average 56% reduction in capacity resulting from an increase in the particle size from 106-250 microm to 250-500 microm. The experimental data correlated well with calculated data using the Thomas equation and the bed depth-service time (BDST) equation. Therefore, it might be concluded that the Thomas equation and the BDST equations can produce accurate predication for variation of dye concentration, mass of the adsorbent, flow rate and particle size. In general, the values of adsorption isotherm capacity

  1. The oxidation of iron-chromium-manganese alloys at 900C

    SciTech Connect

    Marasco, A.L.; Young, D.J. )

    1991-08-01

    The oxidation of nine ternary iron-chromium-manganese alloys was studied at 900C in an oxygen partial pressure of 26.7 kPa. The manganese concentration was set at 2, 6, and 10 wt.%, and chromium at 5, 12, and 20 wt.%. The scales formed on the low-chromium alloys consisted of (Mn,Fe){sub 2}O{sub 3}, {alpha}-Fe{sub 2}O{sub 3}, and Fe{sub 3}O{sub 4}. These alloys all exhibited internal oxidation and scale detachment upon cooling. The scales formed on the higher-chromium alloys were complicated by nodule formation. Initially, these scales had an outer layer of MnCr{sub 2}O{sub 4} with Cr{sub 2}O{sub 3} underneath, adjacent to the alloy. With the passage of time, however, nodules formed, and the overall reaction rate increased. This tendency was more marked at higher manganese contents. Although these alloys contained a high chromium content, the product chromia scale usually contained manganese. It was concluded that the presence of manganese in iron-chromium alloys had an adverse effect on the oxidation resistance over a wide range of chromium levels.

  2. Oxidation and dechlorination of chlorophenols in dilute aqueous suspensions of manganese oxides: Reaction products

    SciTech Connect

    Ukrainczyk, L.; McBride, M.B. . Dept.of Soil, Crop, and Atmospheric Sciences)

    1993-11-01

    Some monomeric and dimeric oxidation products of para- and/or ortho-chlorinated phenols in dilute (1 mmol/L phenol), acidified, aqueous suspensions of manganese oxide (Na-buserite) were identified by MS, Fourier-transform IR spectroscopy and UV/visible spectroscopy. The para-chlorinated phenols (4-chlorophenol, 2,4-dichlorophenol, 2,4,6-trichlorophenol, 4-chloro-2-methylphenol) gave corresponding p-benzoquionones (benzoquinone, 2-chlorobenzoquinone, 2,6-dichlorobenzoquinone, 2-methylbenzoquinone) as the detectable water-soluble oxidation products. Dimeric products were present in the extracts obtained by washing the oxide with methylene chloride. Michael addition of phenolate to quinone seems to be the predominant mode of coupling. Chlorinated phenols without chlorine in the para-position (2-chlorophenol, 2,6-dichlorophenol) were more difficult to oxidize and afforded diphenoquinones as the only detectable water-soluble products. For all studied phenols, with the exception of 2,4,6-trichlorophenol, the amount of water-soluble products accounts only for a small fraction of oxidized phenol. The quinone and diphenoquinone products readily couple with phenols into humus like materials.

  3. Processes of nickel and cobalt uptake by a manganese oxide forming sediment in Pinal Creek, Globe mining district, Arizona

    USGS Publications Warehouse

    Kay, J.T.; Conklin, M.H.; Fuller, C.C.; O'Day, P. A.

    2001-01-01

    A series of column experiments was conducted using manganese oxide coated sediments collected from the hyporheic zone in Pinal Creek (AZ), a metal-contaminated stream, to study the uptake and retention of Mn, Ni, and Co. Experimental variables included the absence (abiotic) and presence (biotic) of active Mn-oxidizing bacteria, the absence and presence of dissolved Mn, and sediment manganese oxide content. Uptake of Mn under biotic conditions was between 8 and 39% higher than under abiotic conditions. Continuous uptake of Mn due to biotic oxidation was evident from extraction of column sediments. Manganese uptake is hypothesized to initially occur as adsorption, which led to subsequent surface and/or microbial oxidation. Complete breakthrough of Ni within 100 pore volumes indicated no process of continuous uptake and was modeled as an equilibrium adsorption process. Nickel uptake in the presence of dissolved Mn was 67-100% reversible. Sediment extractions suggest that Ni uptake occurred through weak and strong adsorption. Continuous uptake of cobalt increased with sediment manganese oxide content, and Co uptake was up to 75% greater under biotic than abiotic conditions. Cobalt uptake was controlled by both existing and newly formed manganese oxides. Only a small amount of Co uptake was reversible (10-25%). XANES spectral analysis indicated that most Co(II) was oxidized to Co(III) and probably incorporated structurally into manganese oxides. Although manganese oxides were the primary phase controlling uptake and retention of Mn, Ni, and Co, the mechanisms varied among the metals.

  4. The scavenging of silver by manganese and iron oxides in stream sediments collected from two drainage areas of Colorado

    USGS Publications Warehouse

    Chao, T.T.; Anderson, B.J.

    1974-01-01

    Stream sediments of two well-weathered and aerated drainage areas of Colorado containing anomalous amounts of silver were allowed to react by shaking with nitric acid of different concentrations (1-10M). Silver, manganese, and iron simultaneously dissolved were determined by atomic absorption. The relationship between silver dissolution and the dissolution of manganese and/or iron was evaluated by linear and multiple regression analyses. The highly significant correlation coefficient (r = 0.913) between silver and manganese dissolution suggests that manganese oxides are the major control on the scavenging of silver in these stream sediments, whereas iron oxides only play a secondary role in this regard. ?? 1974.

  5. Reactivity of biogenic manganese oxide for metal sequestration and photochemistry: Computational solid state physics study

    SciTech Connect

    Kwon, K.D.; Sposito, G.

    2010-02-01

    Many microbes, including both bacteria and fungi, produce manganese (Mn) oxides by oxidizing soluble Mn(II) to form insoluble Mn(IV) oxide minerals, a kinetically much faster process than abiotic oxidation. These biogenic Mn oxides drive the Mn cycle, coupling it with diverse biogeochemical cycles and determining the bioavailability of environmental contaminants, mainly through strong adsorption and redox reactions. This mini review introduces recent findings based on quantum mechanical density functional theory that reveal the detailed mechanisms of toxic metal adsorption at Mn oxide surfaces and the remarkable role of Mn vacancies in the photochemistry of these minerals.

  6. Adsorption of iron cyanide complexes onto clay minerals, manganese oxide, and soil.

    PubMed

    Kang, Dong-Hee; Schwab, A Paul; Johnston, C T; Banks, M Katherine

    2010-09-01

    The adsorption characteristics of an iron cyanide complex, soluble Prussian blue KFe(III)[Fe(II)(CN)(6)], were evaluated for representative soil minerals and soil at pH 3.7, 6.4 and 9.7. Three specimen clay minerals (kaolinite, montmorillonite, and illite), two synthesized manganese oxides (birnessite and cryptomelane), and a Drummer soil from Indiana were used as the adsorbents. Surface protonation of variable charge sites increased with decreasing pH yielding positively charged sites on crystal edges and enhancing the attractive force between minerals and iron cyanide complexes. Anion adsorption on clays often is correlated to the metal content of the adsorbent, and a positive relationship was observed between iron or aluminum content and Prussian blue adsorption. Illite had high extractable iron and adsorbed more ferro-ferricyande anion, while kaolinite and montmorillonite had lower extractable iron and adsorbed less. However, less pH effect was observed on the adsorption of iron cyanide to manganese oxides. This may due to the manganese oxide mediated oxidation of ferrocyanide [Fe(II)(CN)(6)(4-)], to ferricyanide [Fe(III)(CN)(6)(3-)], which has a low affinity for manganese oxides. PMID:20665323

  7. Preparation of anionic clay-birnessite manganese oxide composites by interlayer oxidation of oxalate ions by permanganate

    NASA Astrophysics Data System (ADS)

    Arulraj, James; Rajamathi, Michael

    2013-02-01

    Oxalate intercalated anionic clay-like nickel zinc hydroxysalt was obtained starting from nickel zinc hydroxyacetate, Ni3Zn2(OH)8(OAc)2·2H2O, by anion exchange. The intercalated oxalate species was reacted with potassium permanganate in such a way that the layered manganese oxide formed was within the interlayer region of the anionic clay resulting in a layered composite in which the negative charges on the birnessite type manganese oxide layers compensate the positive charges on the anionic clay layers. Birnessite to anionic clay ratio could be varied by varying the reaction time or the amount of potassium permanganate used.

  8. The kinetics of iodide oxidation by the manganese oxide mineral birnessite

    USGS Publications Warehouse

    Fox, P.M.; Davis, J.A.; Luther, G. W., III

    2009-01-01

    The kinetics of iodide (I-) and molecular iodine (I2) oxidation by the manganese oxide mineral birnessite (??-MnO2) was investigated over the pH range 4.5-6.25. I- oxidation to iodate (IO3-) proceeded as a two-step reaction through an I2 intermediate. The rate of the reaction varied with both pH and birnessite concentration, with faster oxidation occurring at lower pH and higher birnessite concentration. The disappearance of I- from solution was first order with respect to I- concentration, pH, and birnessite concentration, such that -d[I-]/dt = k[I-][H+][MnO2], where k, the third order rate constant, is equal to 1.08 ?? 0.06 ?? 107 M-2 h-1. The data are consistent with the formation of an inner sphere I- surface complex as the first step of the reaction, and the adsorption of I- exhibited significant pH dependence. Both I2, and to a lesser extent, IO3- sorbed to birnessite. The results indicate that iodine transport in mildly acidic groundwater systems may not be conservative. Because of the higher adsorption of the oxidized I species I2 and IO3-, as well as the biophilic nature of I2, redox transformations of iodine must be taken into account when predicting I transport in aquifers and watersheds.

  9. Manganese Homeostasis in Group A Streptococcus Is Critical for Resistance to Oxidative Stress and Virulence

    PubMed Central

    Turner, Andrew G.; Ong, Cheryl-lynn Y.; Gillen, Christine M.; Davies, Mark R.; West, Nicholas P.; McEwan, Alastair G.

    2015-01-01

    ABSTRACT Streptococcus pyogenes (group A Streptococcus [GAS]) is an obligate human pathogen responsible for a spectrum of human disease states. Metallobiology of human pathogens is revealing the fundamental role of metals in both nutritional immunity leading to pathogen starvation and metal poisoning of pathogens by innate immune cells. Spy0980 (MntE) is a paralog of the GAS zinc efflux pump CzcD. Through use of an isogenic mntE deletion mutant in the GAS serotype M1T1 strain 5448, we have elucidated that MntE is a manganese-specific efflux pump required for GAS virulence. The 5448ΔmntE mutant had significantly lower survival following infection of human neutrophils than did the 5448 wild type and the complemented mutant (5448ΔmntE::mntE). Manganese homeostasis may provide protection against oxidative stress, explaining the observed ex vivo reduction in virulence. In the presence of manganese and hydrogen peroxide, 5448ΔmntE mutant exhibits significantly lower survival than wild-type 5448 and the complemented mutant. We hypothesize that MntE, by maintaining homeostatic control of cytoplasmic manganese, ensures that the peroxide response repressor PerR is optimally poised to respond to hydrogen peroxide stress. Creation of a 5448ΔmntE-ΔperR double mutant rescued the oxidative stress resistance of the double mutant to wild-type levels in the presence of manganese and hydrogen peroxide. This work elucidates the mechanism for manganese toxicity within GAS and the crucial role of manganese homeostasis in maintaining GAS virulence. PMID:25805729

  10. Organ weight changes in mice after long-term inhalation exposure to manganese oxides nanoparticles

    NASA Astrophysics Data System (ADS)

    Zeman, T.; Buchtová, M.; Dočekal, B.; Míšek, I.; Navrátil, J.; Mikuška, P.; Šerý, O.; Večeřa, Z.

    2015-05-01

    Recently, it has been proven that manganese from inhaled particles of manganese compounds can accumulate in the internal organs of laboratory animals. Nevertheless, there were only a few researches dealing with changes in body morphology induced by inhalation of these particles, even though results of some studies indicate existence of such changes. The aim of our research was to assess the effect of inhaled manganese oxides nanoparticles on weight of internal organs. For this purpose a long-term inhalation experiment on laboratory mice was performed, during which the mice were exposed to MnO.Mn2O3 nanoparticles in concentration 2 × 106 particles/cm3 for 17 weeks, 24 hours a day, 7 days a week. Manganese oxides nanoparticles were synthesized continuously via aerosol route in a hot wall tube flow reactor using thermal decomposition of metal organic precursor manganese(II)acetylacetonate in the flow tube reactor at temperature 750 °C in the presence of 30 vol% of oxygen. It was proven that inhaled nanoparticles can influence the weight of internal organs of mice. Moreover, it was discovered that the resulting change in weight of selected organs is disproportional. The mice from the experimental group had statistically significantly lighter kidneys, liver and spleen and heavier pancreas compared to the mice from the control group.

  11. Electrochromism in nickel oxide films

    SciTech Connect

    Wruck, D.A.

    1991-01-01

    Optical absorption in a thin-film nickel oxide electrode depends on the state of charge of the electrode; the effect has been called electrochromism, and it may have practical applications in low-speed light modulation devices. In this dissertation, the physical and chemical processes which lead to the change in optical properties are investigated. Preparation of NiO film electrodes by reactive sputtering of a Ni target in an Ar + O[sub 2] gas mixture is described, and the electrochromic response is correlated to film growth conditions. Structural, electronic, and electrochemical properties of the NiO films are characterized by x-ray diffraction, infrared absorption, x-ray photoemission, optical absorption, electrical conductivity, and electrochemical measurements. It is proposed that the electrochromism results from the adsorption and desorption of protons at the oxygen-rich surface of a granular and porous NiO film. The surface electronic levels are then modified by the presence or absence of the O-H bonds, and the effect on the film electronic properties is discussed. A general discussion is also given of the current-limiting processes at the NiO film electrodes.

  12. Spinel coatings for solid oxide fuel cell interconnects and crystal structure of copper manganese oxide

    NASA Astrophysics Data System (ADS)

    Wei, Ping

    Long-term stability and chromium (Cr) contamination are two major concerns for application of chromium-bearing metallic materials as interconnects of solid oxide fuel cells (SOFCs) at intermediate temperature (˜800°C). Copper-manganese (Cu-Mn) and cobalt-manganese (Co-Mn) spinel can be promising coating materials for the metallic interconnects as they show high electrical conductivities. The first objective of this research is to develop an economical and convenient method through which the spinel coatings can be applied to the metallic substrates. The investigations on the crystal structure of Cu xMn3-xO4 spinel, e.g., structure symmetry and cation distributions, have always been controversial, which hinders the total understanding of the detailed structure of the material. In order to resolve the inconsistency, in-situ neutron and X-ray diffraction were employed to determine the structure of the spinel. A novel method was developed to obtain high quality manganese coating without any additives (sulphur or selenium compounds). Cu-Mn and Co-Mn spinel coatings were applied to metallic coupons by electrodeposition and subsequent annealing. The method is convenient and easy to control. The performance testing showed that the area specific resistances (ASRs) of the coated samples (0.003 O·cm 2) are much lower than that of the uncoated UNS 430 (0.189 O·cm 2) after oxidation at 750°C for 1500 hours. Moreover, both spinel coatings can effectively suppress the outward diffusion of Cr, which resulted in reduction of Cr contamination significantly. The oxidation studies of Cu-Mn coating revealed the transformation mechanisms of Cu-Mn coating to the spinel. In-situ neutron and X-ray diffraction analysis clarified the crystal symmetry of CuxMn3-xO4 spinel and CuMnO2 at high temperatures. Rietveld refinement revealed the cation distribution of Cu and Mn ions on tetrahedral and octrahedral sites of CuxMn 3-xO4 spinel, which was compared to values in the literatures.

  13. Process for fabrication of metal oxide films

    SciTech Connect

    Tracy, C.E.; Benson, D.; Svensson, S.

    1990-07-17

    This invention is comprised of a method of fabricating metal oxide films from a plurality of reactants by inducing a reaction by plasma deposition among the reactants. The plasma reaction is effective for consolidating the reactants and producing thin films of metal oxides, e.g. electro-optically active transition metal oxides, at a high deposition rate. The presence of hydrogen during the plasma reaction enhances the deposition rate of the metal oxide. Various types of metal oxide films can be produced.

  14. SERUM CHEMISTRIES OF COTURNIX JAPONICA GIVEN DIETARY MANGANESE OXIDE (MN3O4)

    EPA Science Inventory

    Plasma creatinine and inorganic phosphorus were increased in manganese oxide (Mn3O4)-treated adult male Coturnix quail, but BUN, BUN/creatinine ratio, uric acid, and total calcium were decreased. 2. Serum enzymes (alkaline phosphatase glutamic oxaloacetic transaminase, glutamic p...

  15. Influence of sequential lithium insertions on the physical properties of spinel manganese oxide

    NASA Astrophysics Data System (ADS)

    Ning, Liancai; Wu, Jinping; Zhou, Chenggang; Yao, Shujuan; Pi, Zhenbang; Cheng, Hansong

    We present first principles studies based on density functional theory (DFT) to investigate the lithium intercalation process in spinel manganese oxide compound. The lattice volume change, energetics, and insertion voltage were systematically examined upon sequential lithium insertions into the lattice. The charge transfer mechanism upon lithium intercalation was studied by analyzing the calculated spectra of density of states.

  16. Hybrid ternary rice paper-manganese oxide-carbon nanotube nanocomposites for flexible supercapacitors.

    PubMed

    Jiang, Wenchao; Zhang, Kaixi; Wei, Li; Yu, Dingshan; Wei, Jun; Chen, Yuan

    2013-11-21

    Modern portable electronic devices create a strong demand for flexible energy storage devices. Paper based nanocomposites are attractive as sustainable materials for such applications. Here, we directly explored the hydroxyl chemistry of cellulose fibers to synthesize hybrid ternary nanocomposites, comprised of rice paper, single-walled carbon nanotubes (SWCNTs) and manganese oxide nanoparticles. The functional groups on cellulose fibers can react with adsorbed permanganate ions, resulting in uniform deposition of manganese oxide nanoparticles. SWCNTs coated on top of manganese oxide nanoparticles form a highly conductive network connecting individual manganese oxide particles. By using the hybrid ternary composites as electrodes, the assembled two-electrode supercapacitors demonstrated high capacitance (260.2 F g(-1)), energy (9.0 W h kg(-1)), power (59.7 kW kg(-1)), and cycle stability (12% drop after 3000 cycles). In addition, the nanocomposites show good strength and excellent mechanical flexibility, and their capacitance shows negligible changes after bending more than 100 times. These findings suggest that opportunities exist to further explore the rich chemistry of cellulose fibers for innovative energy applications. PMID:24077360

  17. Diclofenac and 2-anilinophenylacetate degradation by combined activity of biogenic manganese oxides and silver.

    PubMed

    Meerburg, Francis; Hennebel, Tom; Vanhaecke, Lynn; Verstraete, Willy; Boon, Nico

    2012-05-01

    The occurrence of a range of recalcitrant organic micropollutants in our aquatic environment has led to the development of various tertiary wastewater treatment methods. In this study, biogenic manganese oxides (Bio-MnOx), biogenic silver nanoparticles (Bio-Ag(0)) and ionic silver were used for the oxidative removal of the frequently encountered drug diclofenac and its dechlorinated form, 2-anilinophenylacetate (APA). Diclofenac was rapidly degraded during ongoing manganese oxidation by Pseudomonas putida MnB6. Furthermore, whereas preoxidized Bio-MnOx, Bio-Ag(0) and Ag(+) separately did not show any removal capacity for diclofenac, an enhanced removal occurred when Bio-MnOx and silver species were combined. Similar results were obtained for APA. Finally, a slow removal of diclofenac but more rapid APA degradation was observed when silver was added to manganese-free P. putida biomass. Combining these results, three mechanisms of diclofenac and APA removal could be distinguished: (i) a co-metabolic removal during active Mn(2+) oxidation by P. putida; (ii) a synergistic interaction between preoxidized Bio-MnOx and silver species; and (iii) a (bio)chemical process by biomass enriched with silver catalysts. This paper demonstrates the use of P. putida for water treatment purposes and is the first report of the application of silver combined with biogenic manganese for the removal of organic water contaminants. PMID:22221449

  18. Nanostructural evolution from nanosheets to one-dimensional nanoparticles for manganese oxide

    SciTech Connect

    Pan, Hongmei; Kong, Xingang; Wen, Puhong; Kitayama, Tomonori; Feng, Qi

    2012-09-15

    Highlights: ► Nanosheets were transformed to other one-dimensional nanoparticles. ► Nanofibers, nanotubes, nanoribbons, and nanobelts were obtained. ► Nanoparticle morphology can be controlled with organic amines. ► Organic amines act as morphology directing agent. -- Abstract: This paper introduces a novel hydrothermal soft chemical synthesis process for manganese oxide nanostructured particles using two-dimensional manganese oxide nanosheets as precursor. In this process, a birnessite-type manganese oxide with a layered structure was exfoliated into its elementary layer nanosheets, and then the nanosheets were hydrothermally treated to transform the two-dimensional morphology of the nanosheets to one-dimensional nanoparticles. The manganese oxide nanofibers, nanotubes, nanobelts, nanoribbons, and fabric-ribbon-like particles constructed from nanofibers or nanobelts were obtained using this hydrothermal soft chemical process. The nanostructural evolution from the two-dimensional nanosheets to the one-dimensional nanoparticles was characterized by XRD, SEM, TEM, and TG-DTA analysis. The morphology and nanostructure of the products are strongly dependent on the molecular dimension of organic amine cations added in the reaction system. The organic amine cations act as a morphology directing agent in the nanostructural evolution process.

  19. Manganese oxide micro-supercapacitors with ultra-high areal capacitance

    NASA Astrophysics Data System (ADS)

    Wang, Xu; Myers, Benjamin D.; Yan, Jian; Shekhawat, Gajendra; Dravid, Vinayak; Lee, Pooi See

    2013-05-01

    A symmetric micro-supercapacitor is constructed by electrochemically depositing manganese oxide onto micro-patterned current collectors. High surface-to-volume ratio of manganese oxide and short diffusion distance between electrodes give an ultra-high areal capacitance of 56.3 mF cm-2 at a current density of 27.2 μA cm-2.A symmetric micro-supercapacitor is constructed by electrochemically depositing manganese oxide onto micro-patterned current collectors. High surface-to-volume ratio of manganese oxide and short diffusion distance between electrodes give an ultra-high areal capacitance of 56.3 mF cm-2 at a current density of 27.2 μA cm-2. Electronic supplementary information (ESI) available: Experimental procedures; optical images of micro-supercapacitors; areal capacitances of samples M-0.3C, M-0.6C and M-0.9C; illustration of interdigital finger electrodes; Nyquist plot of Co(OH)2 deposited on micro-electrodes. See DOI: 10.1039/c3nr00210a

  20. Facile synthesis of birnessite-type manganese oxide nanoparticles as supercapacitor electrode materials.

    PubMed

    Liu, Lihu; Luo, Yao; Tan, Wenfeng; Zhang, Yashan; Liu, Fan; Qiu, Guohong

    2016-11-15

    Manganese oxides are environmentally benign supercapacitor electrode materials and, in particular, birnessite-type structure shows very promising electrochemical performance. In this work, nanostructured birnessite was facilely prepared by adding dropwise NH2OH·HCl to KMnO4 solution under ambient temperature and pressure. In order to fully exploit the potential of birnessite-type manganese oxide electrode materials, the effects of specific surface area, pore size, content of K(+), and manganese average oxidation state (Mn AOS) on their electrochemical performance were studied. The results showed that with the increase of NH2OH·HCl, the Mn AOS decreased and the corresponding pore sizes and specific surface area of birnessite increased. The synthesized nanostructured birnessite showed the highest specific capacitance of 245Fg(-1) at a current density of 0.1Ag(-1) within a potential range of 0-0.9V, and excellent cycle stability with a capacitance retention rate of 92% after 3000 cycles at a current density of 1.0Ag(-1). The present work implies that specific capacitance is mainly affected by specific surface area and pore volume, and provides a new method for the facile preparation of birnessite-type manganese oxide with excellent capacitive performance. PMID:27501042

  1. Synthesis of nanostructured manganese oxides based materials and application for supercapacitor

    NASA Astrophysics Data System (ADS)

    Dung Dang, Trung; Le, Thi Thu Hang; Bich Thuy Hoang, Thi; Mai, Thanh Tung

    2015-01-01

    Manganese oxides are important materials with a variety of applications in different fields such as chemical sensing devices, magnetic devices, field-emission devices, catalysis, ion-sieves, rechargeable batteries, hydrogen storage media and microelectronics. To open up new applications of manganese oxides, novel morphologies or nanostructures are required to be developed. Via sol—gel and anodic electrodeposition methods, M (Co, Fe) doped manganese oxides were prepared. On the other hand, nanostructured (nanoparticles, nanorods and hollow nanotubes) manganese oxides were synthesized via a process including a chemical reaction with carbon nanotubes (CNTs) templates followed by heat treatment. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), cyclic voltammetry (CV) and impedance spectroscopy (EIS) were used for characterization of the prepared materials. The influence of chemical reaction conditions, heat treatment and template present on the morphology, structure, chemical and electrochemical properties of the prepared materials were investigated. Chronopotentiometry (CP) and CV results show high specific capacitance of 186.2 to 298.4 F g-1 and the charge/discharge stability of the prepared materials and the ideal pseudocapacitive behaviors were observed. These results give an opening and promising application of these materials in advanced energy storage applications.

  2. IMPACT OF WATER CHEMISTRY ON MANGANESE REMOVAL DURING OXIDATION/FILTRATION TREATMENT

    EPA Science Inventory

    This is a poster showing the purpose and setup of our pilot plant experiments with manganese filtration. The focus is on the differences, effectiveness, and problems with using chlorine and potassium permanganate in oxidation/filtration. The poster will show the results and findi...

  3. Synthesis and characterisation of manganese oxides from potassium permanganate and citric acid mixtures

    NASA Astrophysics Data System (ADS)

    Burhanuddin, Syazwani; Yarmo, Ambar; Yamin, Bohari M.

    2013-11-01

    Reaction of KMnO4 and citric acid at different stoichiometric ratio found to give black precipitate after calcined at 500 %C. The black precipitate are classified as two type of manganese oxides mineral namely as bixbyite and hollandite. IR and XRD data were in agreement with the literature report.

  4. The effect of lanthanum(III) and cerium(III) ions between layers of manganese oxide on water oxidation.

    PubMed

    Najafpour, Mohammad Mahdi; Isaloo, Mohsen Abbasi; Hołyńska, Małgorzata; Shen, Jian-Ren; Allakhverdiev, Suleyman I; Allakhverdiev, Suleyman

    2015-12-01

    Manganese oxide structure with lanthanum(III) or cerium(III) ions between the layers was synthesized by a simple method. The ratio of Mn to Ce or La in samples was 0.00, 0.04, 0.08, 0.16, 0.32, 0.5, 0.82, or 1.62. The compounds were characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction studies, and atomic absorption spectroscopy. The compounds show efficient catalytic activity of water oxidation in the presence of cerium(IV) ammonium nitrate with a turnover frequency of 1.6 mmol O2/mol Mn.s. In contrast to the water-oxidizing complex in Photosystem II, calcium(II) has no specific role to enhance the water-oxidizing activity of the layered manganese oxides and other cations can be replaced without any significant decrease in water-oxidizing activities of these layered Mn oxides. Based on this and previously reported results from oxygen evolution in the presence of H 2 (18) O, we discuss the mechanism and the important factors influencing the water-oxidizing activities of the manganese oxides. PMID:25701552

  5. Endowing manganese oxide with fast adsorption ability through controlling the manganese carbonate precursor assembled in ionic liquid.

    PubMed

    Ge, X; Gu, C D; Wang, X L; Tu, J P

    2015-01-15

    Manganese oxides with desired structure are controllably obtained through annealing MnCO3 precursors with required structures. The structures of MnCO3 precursors are determined by a "mesocrystal formation" process in an ionic liquid system of a choline chloride/urea (CU) mixture. Without addition of surfactants, only CU solvent and manganese chloride are needed in the reaction system, in which the CU acts as reaction medium as well as control agent for particle growth. A shape transformation of MnCO3 particles from well-defined rhombohedral mesocrystals to ellipsoidal polycrystal ensembles, and to nanoparticulate aggregates is observed when heating the reaction system for 4 h at 120, 150, and 180 °C, respectively. With a longer aging time at 120 °C, etching and disassembly of MnCO3 mesocrystals happened. The correlation between the microstructure and the underlying formation mechanism is highlighted. Porous and nanowire-like MnO(x) nanostructures are obtained through a facile thermal conversion process from the diverse MnCO3 precursors, which are demonstrated as effective and efficient adsorbents to remove organic waste (e.g. Congo red) from water. Significantly, the nanowire-like MnO(x) nanostructures obtained by annealing the MnCO3 mesocrystals at 300 °C for 4 h can remove about 95% Congo red in waste water at room temperature in only one minute, which is superior to the reported hierarchical hollow nanostructured MnO2. PMID:25454437

  6. Cobalt(II) Oxidation by the Marine Manganese(II)-Oxidizing Bacillus sp. Strain SG-1

    PubMed Central

    Lee, Yoon; Tebo, Bradley M.

    1994-01-01

    The geochemical cycling of cobalt (Co) has often been considered to be controlled by the scavenging and oxidation of Co(II) on the surface of manganese [Mn(III,IV)] oxides or manganates. Because Mn(II) oxidation in the environment is often catalyzed by bacteria, we have investigated the ability of Mn(II)-oxidizing bacteria to bind and oxidize Co(II) in the absence of Mn(II) to determine whether some Mn(II)-oxidizing bacteria also oxidize Co(II) independently of Mn oxidation. We used the marine Bacillus sp. strain SG-1, which produces mature spores that oxidize Mn(II), apparently due to a protein in their spore coats (R.A. Rosson and K. H. Nealson, J. Bacteriol. 151:1027-1034, 1982; J. P. M. de Vrind et al., Appl. Environ. Microbiol. 52:1096-1100, 1986). A method to measure Co(II) oxidation using radioactive 57Co as a tracer and treatments with nonradioactive (cold) Co(II) and ascorbate to discriminate bound Co from oxidized Co was developed. SG-1 spores were found to oxidize Co(II) over a wide range of pH, temperature, and Co(II) concentration. Leucoberbelin blue, a reagent that reacts with Mn(III,IV) oxides forming a blue color, was found to also react with Co(III) oxides and was used to verify the presence of oxidized Co in the absence of added Mn(II). Co(II) oxidation occurred optimally around pH 8 and between 55 and 65°C. SG-1 spores oxidized Co(II) at all Co(II) concentrations tested from the trace levels found in seawater to 100 mM. Co(II) oxidation was found to follow Michaelis-Menten kinetics. An Eadie-Hofstee plot of the data suggests that SG-1 spores have two oxidation systems, a high-affinity-low-rate system (Km, 3.3 × 10-8 M; Vmax, 1.7 × 10-15 M · spore-1 · h-1) and a low-affinity-high-rate system (Km, 5.2 × 10-6 M; Vmax, 8.9 × 10-15 M · spore-1 · h-1). SG-1 spores did not oxidize Co(II) in the absence of oxygen, also indicating that oxidation was not due to abiological Co(II) oxidation on the surface of preformed Mn(III,IV) oxides. These

  7. Determining the Oxidation States of Manganese in NT2 Cells and Cultured Astrocytes

    SciTech Connect

    Gunter,K.; Aschner, M.; Miller, L.; Eliseev, R.; Salter, J.; Andersen, K.; Gunter, T.

    2006-01-01

    Excessive brain manganese (Mn) can produce a syndrome called 'manganism', which correlates with loss of striatal dopamine and cell death in the striatum and globus pallidus. The prevalent hypothesis for the cause of this syndrome has been oxidation of cell components by the strong oxidizing agent, Mn{sup 3+}, either formed by oxidation of intracellular Mn{sup 2+} or transported into the cell as Mn{sup 3+}. We have recently used X-ray absorption near edge structure spectroscopy (XANES) to determine the oxidation states of manganese complexes in brain and liver mitochondria and in nerve growth factor (NGF)-induced and non-induced PC12 cells. No evidence was found for stabilization or accumulation of Mn{sup 3+} complexes because of oxidation of Mn{sup 2+} by reactive oxygen species in these tissues. Here we extend these studies of manganese oxidation state to cells of brain origin, human neuroteratocarcinoma (NT2) cells and primary cultures of rat astrocytes. Again we find no evidence for stabilization or accumulation of any Mn{sup 3+} complex derived from oxidation of Mn{sup 2+} under a range of conditions.

  8. Oxidation of manganese and iron by Leptothrix discophora: Use of N,N,N prime ,N prime -tetramethyl-p-phenylenediamine as an indicator of metal oxidation

    SciTech Connect

    de Vrind-de Jong, E.W.; Corstjens, P.L.A.M.; Kempers, E.S.; Westbroek, P.; de Vrind, J.P.M. )

    1990-11-01

    A new method for the quantification and characterization of manganese-oxidizing activity by spent culture medium of Leptothrix discophora SS-1 was developed. It is based on the formation of the dye Wurster blue from N,N,N{prime},N{prime}-tetramethyl-p-phenylenediamine by oxidized manganese generated in the spent medium. The kinetic parameters thus obtained agreed well with data obtained with other methods. It was also possible to demonstrate iron oxidation by spent culture medium. The kinetics of the process and inhibition by enzyme poisons suggest that iron oxidation is enzymatically catalyzed. Probably two different factors are involved in manganese and iron oxidation.

  9. Oxidation of Manganese and Iron by Leptothrix discophora: Use of N,N,N',N'-Tetramethyl-p-Phenylenediamine as an Indicator of Metal Oxidation.

    PubMed

    de Vrind-de Jong, E W; Corstjens, P L; Kempers, E S; Westbroek, P; de Vrind, J P

    1990-11-01

    A new method for the quantification and characterization of manganese-oxidizing activity by spent culture medium of Leptothrix discophora SS-1 was developed. It is based on the formation of the dye Wurster blue from N,N,N',N'-Tetramethyl-p-phenylenediamine by oxidized manganese generated in the spent medium. The kinetic parameters thus obtained agreed well with data obtained with other methods. It was also possible to demonstrate iron oxidation by spent culture medium. The kinetics of the process and inhibition by enzyme poisons suggest that iron oxidation is enzymatically catalyzed. Probably two different factors are involved in manganese and iron oxidation. PMID:16348351

  10. Study and optimisation of manganese oxide-based electrodes for electrochemical supercapacitors

    NASA Astrophysics Data System (ADS)

    Staiti, P.; Lufrano, F.

    A manganese oxide material was synthesised by an easy precipitation method based on reduction of potassium permanganate(VII) with a manganese(II) salt. The material was treated at different temperatures to study the effect of thermal treatment on capacitive property. The best capacitive performance was obtained with the material treated at 200 °C. This material was used to prepare electrodes with different amounts of polymer binder, carbon black and graphite fibres to individuate the optimal composition that gave the best electrochemical performances. It was found that graphite fibres improve the electrochemical performance of electrodes. The highest specific capacitance (267 F g -1 MnO x) was obtained with an electrode containing 70% of MnO x, 15% of carbon black, 10% of graphite fibres and 5% of PVDF. This electrode, with CB/GF ratio of 1.5, showed a higher utilization of manganese oxide. The results reported in the present paper further confirmed that manganese oxide is a very interesting material for supercapacitor application.

  11. Oxidation of manganese(II) with ferrate: Stoichiometry, kinetics, products and impact of organic carbon.

    PubMed

    Goodwill, Joseph E; Mai, Xuyen; Jiang, Yanjun; Reckhow, David A; Tobiason, John E

    2016-09-01

    Manganese is a contaminant of concern for many drinking water utilities, and future regulation may be pending. An analysis of soluble manganese (Mn(II)) oxidation by ferrate (Fe(VI)) was executed at the bench-scale, in a laboratory matrix, both with and without the presence of natural organic matter (NOM) and at two different pH values, 6.2 and 7.5. In the matrix without NOM, the oxidation of Mn(II) by Fe(VI) followed a stoichiometry of 2 mol Fe(VI) to 3 mol Mn(II). The presence of NOM did not significantly affect the stoichiometry of the oxidation reaction, indicating relative selectivity of Fe(VI) for Mn(II). The size distribution of resulting particles included significant amounts of nanoparticles. Resulting manganese oxide particles were confirmed to be MnO2 via X-ray photoelectron spectroscopy. The rate of the Mn(II) oxidation reaction was fast relative to typical time scales in drinking water treatment, with an estimated second order rate constant of approximately 1 × 10(4) M(-1) s(-1) at pH 9.2 and > 9 × 10(4) M(-1) s(-1) at pH 6.2. In general, ferrate is a potential option for Mn(II) oxidation in water treatment. PMID:27341149

  12. Population Structure of Manganese-Oxidizing Bacteria in Stratified Soils and Properties of Manganese Oxide Aggregates under Manganese–Complex Medium Enrichment

    PubMed Central

    Zhang, Zhongming; Chen, Hong; Liu, Jin; Ali, Muhammad; Liu, Fan; Li, Lin

    2013-01-01

    Manganese-oxidizing bacteria in the aquatic environment have been comprehensively investigated. However, little information is available about the distribution and biogeochemical significance of these bacteria in terrestrial soil environments. In this study, stratified soils were initially examined to investigate the community structure and diversity of manganese-oxidizing bacteria. Total 344 culturable bacterial isolates from all substrata exhibited Mn(II)-oxidizing activities at the range of 1 µM to 240 µM of the equivalent MnO2. The high Mn(II)-oxidizing isolates (>50 mM MnO2) were identified as the species of phyla Actinobacteria, Firmicutes and Proteobacteria. Seven novel Mn(II)-oxidizing bacterial genera (species), namely, Escherichia, Agromyces, Cellulomonas, Cupriavidus, Microbacterium, Ralstonia, and Variovorax, were revealed via comparative phylogenetic analysis. Moreover, an increase in the diversity of soil bacterial community was observed after the combined enrichment of Mn(II) and carbon-rich complex. The phylogenetic classification of the enriched bacteria represented by predominant denaturing gradient gel electrophoresis bands, was apparently similar to culturable Mn(II)-oxidizing bacteria. The experiments were further undertaken to investigate the properties of the Mn oxide aggregates formed by the bacterial isolates with high Mn(II)-oxidizing activity. Results showed that these bacteria were closely encrusted with their Mn oxides and formed regular microspherical aggregates under prolonged Mn(II) and carbon-rich medium enrichment for three weeks. The biotic oxidation of Mn(II) to Mn(III/IV) by these isolates was confirmed by kinetic examinations. X-ray diffraction assays showed the characteristic peaks of several Mn oxides and rhodochrosite from these aggregates. Leucoberbelin blue tests also verified the Mn(II)-oxidizing activity of these aggregates. These results demonstrated that Mn oxides were formed at certain amounts under the enrichment

  13. Significantly improved cyclability of lithium manganese oxide under elevated temperature by an easily oxidized electrolyte additive

    NASA Astrophysics Data System (ADS)

    Zhu, Yunmin; Rong, Haibo; Mai, Shaowei; Luo, Xueyi; Li, Xiaoping; Li, Weishan

    2015-12-01

    Spinel lithium manganese oxide, LiMn2O4, is a promising cathode for lithium ion battery in large-scale applications, because it possesses many advantages compared with currently used layered lithium cobalt oxide (LiCoO2) and olivine phosphate (LiFePO4), including naturally abundant resource, environmental friendliness and high and long work potential plateau. Its poor cyclability under high temperature, however, limits its application. In this work, we report a significant cyclability improvement of LiMn2O4 under elevated temperature by using dimethyl phenylphonite (DMPP) as an electrolyte additive. Charge/discharge tests demonstrate that the application of 0.5 wt.% DMPP yields a capacity retention improvement from 16% to 82% for LiMn2O4 after 200 cycles under 55 °C at 1 C (1C = 148 mAh g-1) between 3 and 4.5 V. Electrochemical and physical characterizations indicate that DMPP is electrochemically oxidized at the potential lower than that for lithium extraction, forming a protective cathode interphase on LiMn2O4, which suppresses the electrolyte decomposition and prevents LiMn2O4 from crystal destruction.

  14. Influence of film thickness and air exposure on the transport gap of manganese phthalocyanine

    SciTech Connect

    Haidu, F.; Fechner, A.; Salvan, G.; Gordan, O. D.; Fronk, M.; Zahn, D. R. T.; Lehmann, D.; Mahns, B.; Knupfer, M.

    2013-06-15

    The interface formation between manganese phthalocyanine (MnPc) and cobalt was investigated combining ultraviolet photoelectron spectroscopy and inverse photoelectron spectroscopy. The transport band gap of the MnPc increases with the film thickness up to a value of (1.2 {+-} 0.3) eV while the optical band gap as determined from spectroscopic ellipsometry amounts to 0.5 eV. The gap values are smaller compared to other phthalocyanines due to metallic Mn 3d states close to the Fermi level. The transport band gap was found to open upon air exposure as a result of the disappearance of the occupied 3d electronic states.

  15. Thin-film zinc/manganese dioxide electrodes based on microporous polymer foils

    NASA Astrophysics Data System (ADS)

    Barbic, P. A.; Binder, L.; Voss, S.; Hofer, F.; Grogger, W.

    Thin-film electrodes allow manufacturing of flat batteries of variable design which can be used for the development of smaller electric appliances. Substituting the metal carrier by conductive plastics leads to a considerable reduction of battery weight. Usually the electroactive materials are deposited onto the surface of the carrier. A significant improvement of the originally poor adherence between polymer foil and electroactive layers can be achieved by mechanical (surface roughening) or chemical (etching) pretreatment. Another way to form extremely thin electrodes having a thickness in the range of some ten micrometers is reported here. First, a metallic layer is deposited onto one surface of a 25 μm thin porous polypropylene foil. Subsequently, the electroactive materials are electrolytically deposited into the pores of the metallized foil providing the required conductive connection through the plastic matrix by themselves. In this case the flexibility of the polymer has a positive influence on the problem of volume change of manganese dioxide during charging and discharging, respectively, because the plastic provides flexible `mechanical struts' which act as a `binder' and therefore prevent increasing internal resistance due to contact problems. Assembling a zinc filled polymer and a manganese dioxide filled one in such a way that both metallic back-layers are in contact, a thin bipolar zinc/manganese dioxide electrode can be obtained.

  16. Decreased methane formation from the hydrogenation of carbon monoxide using zeolite/cobalt-manganese oxide composite catalysts.

    PubMed

    Johns, M; Landon, P; Alderson, T; Hutchings, G J

    2001-12-01

    A composite catalyst comprising a physical mixture of a zeolite and a cobalt/manganese oxide Fischer-Tropsch catalyst decreases the formation of methane in the hydrogenation of carbon monoxide without significantly affecting conversion. PMID:12240011

  17. Diclofenac and 2‐anilinophenylacetate degradation by combined activity of biogenic manganese oxides and silver

    PubMed Central

    Meerburg, Francis; Hennebel, Tom; Vanhaecke, Lynn; Verstraete, Willy; Boon, Nico

    2012-01-01

    Summary The occurrence of a range of recalcitrant organic micropollutants in our aquatic environment has led to the development of various tertiary wastewater treatment methods. In this study, biogenic manganese oxides (Bio‐MnOx), biogenic silver nanoparticles (Bio‐Ag0) and ionic silver were used for the oxidative removal of the frequently encountered drug diclofenac and its dechlorinated form, 2‐anilinophenylacetate (APA). Diclofenac was rapidly degraded during ongoing manganese oxidation by Pseudomonas putida MnB6. Furthermore, whereas preoxidized Bio‐MnOx, Bio‐Ag0 and Ag+ separately did not show any removal capacity for diclofenac, an enhanced removal occurred when Bio‐MnOx and silver species were combined. Similar results were obtained for APA. Finally, a slow removal of diclofenac but more rapid APA degradation was observed when silver was added to manganese‐free P. putida biomass. Combining these results, three mechanisms of diclofenac and APA removal could be distinguished: (i) a co‐metabolic removal during active Mn2+ oxidation by P. putida; (ii) a synergistic interaction between preoxidized Bio‐MnOx and silver species; and (iii) a (bio)chemical process by biomass enriched with silver catalysts. This paper demonstrates the use of P. putida for water treatment purposes and is the first report of the application of silver combined with biogenic manganese for the removal of organic water contaminants. PMID:22221449

  18. Effects of a manganese oxide-modified biochar composite on adsorption of arsenic in red soil.

    PubMed

    Yu, Zhihong; Zhou, Li; Huang, Yifan; Song, Zhengguo; Qiu, Weiwen

    2015-11-01

    The arsenic adsorption capacity of a manganese oxide-modified biochar composite (MBC), prepared by pyrolysis of a mixture of potassium permanganate and biochar, was investigated in red soil. Adsorption experiments using batch procedures were used to estimate the arsenic adsorption capacities of the absorbent materials. Adsorption and desorption isotherms, Fourier-transform infrared spectroscopy (FTIR), and X-ray photoelectron spectroscopy (XPS) were used to characterise the prepared adsorbent materials, and a plausible mechanism for arsenic removal by MBC was proposed. Arsenic in red soil-MBC mixtures exhibited lower mobility than that in soils amended with pristine biochar. The improved removal performance of soil-MBC mixtures was attributed to a lower H/C ratio, higher O/C ratio, higher surface hydrophilicity, and higher surface sorption capacity, even though the impregnation of manganese oxide decreased the specific surface area of the biochar. Arsenic retention increased as the biochar content increased, mainly owing to an increase in soil pH. Several oxygenated functional groups, especially O-H, CO, Mn-O, and Si-O, participated in the adsorption process, and manganese oxides played a significant role in the oxidation of arsenic. This study highlights the potential of MBC as an absorbent to immobilise arsenic for use in contaminated land remediation in the red soils region. PMID:26320008

  19. Interactions between manganese oxides and multiple-ringed aromatic compounds

    SciTech Connect

    Whelan, G. ); Sims, R.C. . Dept. of Civil and Environmental Engineering)

    1992-08-01

    Objective is to determine whether Mn reductive dissolution can oxidize multiple-ringed aromatics, such as PAHs, in an oxic environment Research indicated that certain PAHs (eg, dihydrodiols and diones that form free-radical intermediates) are susceptible to oxidation and polymerization. Over 14 days, 83, 76, 54, 70, and 20% of the Mn was reduced by 2,3-, 1,3-, and 1,4-naphthalenediol, quinizarin, and 1,4-naphthoquinone, respectively. 100, 100, and 65% of the first three PAHs were oxidized, respectively. Aromatics with diol functional groups were more easily oxidized than those with only dione groups. Relatively insoluble compounds like quinizarin can be oxidized; insoluble ''humic-like'' material precipitated, indicating a polymerization-humification process. Results suggest that electron transfer/organic release from the oxide surface is the rate-limiting step.

  20. Interactions between manganese oxides and multiple-ringed aromatic compounds

    SciTech Connect

    Whelan, G.; Sims, R.C.

    1992-08-01

    Objective is to determine whether Mn reductive dissolution can oxidize multiple-ringed aromatics, such as PAHs, in an oxic environment? Research indicated that certain PAHs (eg, dihydrodiols and diones that form free-radical intermediates) are susceptible to oxidation and polymerization. Over 14 days, 83, 76, 54, 70, and 20% of the Mn was reduced by 2,3-, 1,3-, and 1,4-naphthalenediol, quinizarin, and 1,4-naphthoquinone, respectively. 100, 100, and 65% of the first three PAHs were oxidized, respectively. Aromatics with diol functional groups were more easily oxidized than those with only dione groups. Relatively insoluble compounds like quinizarin can be oxidized; insoluble ``humic-like`` material precipitated, indicating a polymerization-humification process. Results suggest that electron transfer/organic release from the oxide surface is the rate-limiting step.

  1. Regulating proton-coupled electron transfer for efficient water splitting by manganese oxides at neutral pH

    PubMed Central

    Yamaguchi, Akira; Inuzuka, Riko; Takashima, Toshihiro; Hayashi, Toru; Hashimoto, Kazuhito; Nakamura, Ryuhei

    2014-01-01

    Manganese oxides have been extensively investigated as model systems for the oxygen-evolving complex of photosystem II. However, most bioinspired catalysts are inefficient at neutral pH and functional similarity to the oxygen-evolving complex has been rarely achieved with manganese. Here we report the regulation of proton-coupled electron transfer involved in water oxidation by manganese oxides. Pyridine and its derivatives, which have pKa values intermediate to the water ligand bound to manganese(II) and manganese(III), are used as proton-coupled electron transfer induction reagents. The induction of concerted proton-coupled electron transfer is demonstrated by the detection of deuterium kinetic isotope effects and compliance of the reactions with the libido rule. Although proton-coupled electron transfer regulation is essential for the facial redox change of manganese in photosystem II, most manganese oxides impair these regulatory mechanisms. Thus, the present findings may provide a new design rationale for functional analogues of the oxygen-evolving complex for efficient water splitting at neutral pH. PMID:24977746

  2. Coordination compounds of manganese(II) with polyamines - catalysts of the oxidation of organic dyes by hydrogen peroxide

    SciTech Connect

    Batyr, D.G.; Isak, V.G.; Kirienko, A.A.; Kharitonov, Yu.Ya.

    1987-02-01

    The peroxidase activity of complexes of manganese(II) with polyamines has been characterized. A comparison of the original and literature data has led to the conclusion that the oxidation of organic substrates having some complexing ability with respect to Manganese(II) in Mn(II)-ligand-H/sub 2/O/sub 2/-S systems takes place according to an inner-sphere ion-molecule mechanism. In cases in which the substrate does not have any complexing ability with respect to Manganese(II), the oxidation process takes place according to an outer-sphere mechanism.

  3. Phenolic mediators enhance the manganese peroxidase catalyzed oxidation of recalcitrant lignin model compounds and synthetic lignin.

    PubMed

    Nousiainen, Paula; Kontro, Jussi; Manner, Helmiina; Hatakka, Annele; Sipilä, Jussi

    2014-11-01

    Fungal oxidative enzymes, such as peroxidases and laccases, are the key catalysts in lignin biodegradation in vivo, and consequently provide an important source for industrial ligninolytic biocatalysts. Recently, it has been shown that some syringyl-type phenolics have potential as industrial co-oxidants or mediators, in laccase-catalyzed modification of lignocellulosic material. We have now studied the effect of such mediators with ligninolytic peroxidases on oxidation of the most recalcitrant lignin model compounds. We found that they are able to enhance the manganese peroxidase (MnP) catalyzed oxidation reactions of small non-phenolic compounds, veratryl alcohol and veratrylglycerol β-guaiacyl ether (adlerol), which are not usually oxidized by manganese peroxidases alone. In these experiments we compared two peroxidases from white-rot fungi, MnP from Phlebia sp. Nf b19 and versatile peroxidase (VP) from Bjerkandera adusta under two oxidation conditions: (i) the Mn(III) initiated mediated oxidation by syringyl compounds and (ii) the system involving MnP-dependent lipid peroxidation, both with production of (hydrogen) peroxides in situ to maintain the peroxidase catalytic cycle. It was found that both peroxidases produced α-carbonyl oxidation product of veratryl alcohol in clearly higher yields in reactions mediated by phenoxy radicals than in lipid-peroxyl radical system. The oxidation of adlerol, on the other hand, was more efficient in lipid-peroxidation-system. VP was more efficient than MnP in the oxidation of veratryl alcohol and showed its lignin peroxidase type activity in the reaction conditions indicated by some cleavage of Cα-Cβ-bond of adlerol. Finally, the mediator assisted oxidation conditions were applied in the oxidation of synthetic lignin (DHP) and the structural analysis of the oxidized polymers showed clear modifications in the polymer outcome, e.g. the oxidation resulted in reduced amount of aliphatic hydroxyls indicated by (31)P NMR. PMID

  4. Enhanced mercury removal from fix-bed reactor by lamella manganese oxide sorbents

    NASA Astrophysics Data System (ADS)

    Cheng, H. W.; Yu, C. T.

    2015-12-01

    Mercury (Hg) is an extremely hazardous metal and attracted more concern because of its high toxicity and bioaccumulation. Several manganese-oxide-containing sorbents prepared by co-precipitation method could exhibit the mercury removal activities toward Hg0. The mercury removal test at the temperature of 300°C has the highest removal efficiency. Under this temperature, the maximum absorption equivalent of Mg-Al-Mn and Mn-Al were up to 90.9 and 247 μg/g, then gradually decreased at 400°C. The mercury removal efficiency declined in the following sequence: Mn-Al > Mg-Al-Mn > Mg-Al-Mn/ACA = Mn/AC(p)> Mn/AC(g), due to the manganese-oxide content formed on the sorbents.

  5. Hybrid ternary rice paper-manganese oxide-carbon nanotube nanocomposites for flexible supercapacitors

    NASA Astrophysics Data System (ADS)

    Jiang, Wenchao; Zhang, Kaixi; Wei, Li; Yu, Dingshan; Wei, Jun; Chen, Yuan

    2013-10-01

    Modern portable electronic devices create a strong demand for flexible energy storage devices. Paper based nanocomposites are attractive as sustainable materials for such applications. Here, we directly explored the hydroxyl chemistry of cellulose fibers to synthesize hybrid ternary nanocomposites, comprised of rice paper, single-walled carbon nanotubes (SWCNTs) and manganese oxide nanoparticles. The functional groups on cellulose fibers can react with adsorbed permanganate ions, resulting in uniform deposition of manganese oxide nanoparticles. SWCNTs coated on top of manganese oxide nanoparticles form a highly conductive network connecting individual manganese oxide particles. By using the hybrid ternary composites as electrodes, the assembled two-electrode supercapacitors demonstrated high capacitance (260.2 F g-1), energy (9.0 W h kg-1), power (59.7 kW kg-1), and cycle stability (12% drop after 3000 cycles). In addition, the nanocomposites show good strength and excellent mechanical flexibility, and their capacitance shows negligible changes after bending more than 100 times. These findings suggest that opportunities exist to further explore the rich chemistry of cellulose fibers for innovative energy applications.Modern portable electronic devices create a strong demand for flexible energy storage devices. Paper based nanocomposites are attractive as sustainable materials for such applications. Here, we directly explored the hydroxyl chemistry of cellulose fibers to synthesize hybrid ternary nanocomposites, comprised of rice paper, single-walled carbon nanotubes (SWCNTs) and manganese oxide nanoparticles. The functional groups on cellulose fibers can react with adsorbed permanganate ions, resulting in uniform deposition of manganese oxide nanoparticles. SWCNTs coated on top of manganese oxide nanoparticles form a highly conductive network connecting individual manganese oxide particles. By using the hybrid ternary composites as electrodes, the assembled two

  6. Phase stability and properties of manganese oxide polymorphs: Assessment and insights from diffusion Monte Carlo

    NASA Astrophysics Data System (ADS)

    Schiller, Joshua A.; Wagner, Lucas K.; Ertekin, Elif

    2015-12-01

    We present an analysis of the polymorphic energy ordering and properties of the rocksalt and zinc-blende structures of manganese oxide using fixed node diffusion Monte Carlo (DMC). Manganese oxide is a correlated, antiferromagnetic material that has proven to be challenging to model from first principles across a variety of approaches. Unlike conventional density functional theory and some hybrid functionals, fixed node diffusion Monte Carlo finds the rocksalt structure to be more stable than the zinc-blende structure, and thus recovers the correct energy ordering. Analysis of the site-resolved charge fluctuations of the wave functions according to DMC and other electronic structure descriptions gives insights into elements that are missing in other theories. While the calculated band gaps within DMC are in agreement with predictions that the zinc-blende polymorph has a lower band gap, the gaps themselves overestimate reported experimental values.

  7. Hydrothermal synthesis of layered sodium manganese oxide nanowires and their electrochemical performance.

    PubMed

    Liu, Xian-Ming; Huang, Zhen-Dong; Oh, Sei-Woon; Ma, Peng-Cheng; Ma, Jun; Li, Bao-Hua; Kim, Jang-Kyo

    2010-11-01

    A new method for preparing black birnessite nanowires is introduced. Layer-structured manganese oxide nanowires were synthesized by a facile hydrothermal method, and using both NaMnO4 and CH3CH2OH as the precursors in a concentrated NaOH solution. The structure, composition, appearance and electrochemical performance of the product were characterized by means of X-ray diffraction (XRD), transmission electron microscopy (TEM), energy diffraction (ED), high-resolution transmission electron microscopy (HRTEM), thermogravimetric analysis (TGA) and constant current charge/discharge. The XRD patterns showed a single phase corresponding to a crystalline birnessite-based manganese oxide. TEM studies suggested their wire-like structures. The TGA measurement demonstrated that they possessed an excellent thermal stability up to 400 degrees C. In the potential window of 2.0-4.3 V, the product exhibited excellent cyclic stability and rapid charge-discharge performance. PMID:21137939

  8. Bare and Polymer-Coated Indium Tin Oxide as Working Electrodes for Manganese Cathodic Stripping Voltammetry.

    PubMed

    Rusinek, Cory A; Bange, Adam; Warren, Mercedes; Kang, Wenjing; Nahan, Keaton; Papautsky, Ian; Heineman, William R

    2016-04-19

    Though an essential metal in the body, manganese (Mn) has a number of health implications when found in excess that are magnified by chronic exposure. These health complications include neurotoxicity, memory loss, infertility in males, and development of a neurologic psychiatric disorder, manganism. Thus, trace detection in environmental samples is increasingly important. Few electrode materials are able to reach the negative reductive potential of Mn required for anodic stripping voltammetry (ASV), so cathodic stripping voltammetry (CSV) has been shown to be a viable alternative. We demonstrate Mn CSV using an indium tin oxide (ITO) working electrode both bare and coated with a sulfonated charge selective polymer film, polystyrene-block-poly(ethylene-ran-butylene)-block-polystyrene-sulfonate (SSEBS). ITO itself proved to be an excellent electrode material for Mn CSV, achieving a calculated detection limit of 5 nM (0.3 ppb) with a deposition time of 3 min. Coating the ITO with the SSEBS polymer was found to increase the sensitivity and lower the detection limit to 1 nM (0.06 ppb). This polymer modified electrode offers excellent selectivity for Mn as no interferences were observed from other metal ions tested (Zn(2+), Cd(2+), Pb(2+), In(3+), Sb(3+), Al(3+), Ba(2+), Co(2+), Cu(2+), Ni(3+), Bi(3+), and Sn(2+)) except Fe(2+), which was found to interfere with the analytical signal for Mn(2+) at a ratio 20:1 (Fe(2+)/Mn(2+)). The applicability of this procedure to the analysis of tap, river, and pond water samples was demonstrated. This simple, sensitive analytical method using ITO and SSEBS-ITO could be applied to a number of electroactive transition metals detectable by CSV. PMID:26980322

  9. Diphenyl Diselenide Protects Against Mortality, Locomotor Deficits and Oxidative Stress in Drosophila melanogaster Model of Manganese-Induced Neurotoxicity.

    PubMed

    Adedara, Isaac A; Abolaji, Amos O; Rocha, Joao B T; Farombi, Ebenezer O

    2016-06-01

    Several experimental and epidemiological reports have associated manganese exposure with induction of oxidative stress and locomotor dysfunctions. Diphenyl diselenide (DPDS) is widely reported to exhibit antioxidant, anti-inflammatory and neuroprotective effects in in vitro and in vivo studies via multiple biochemical mechanisms. The present study investigated the protective effect of DPDS on manganese-induced toxicity in Drosophila melanogaster. The flies were exposed, in a dietary regimen, to manganese alone (30 mmol per kg) or in combination with DPDS (10 and 20 µmol per kg) for 7 consecutive days. Exposure to manganese significantly (p < 0.05) increased flies mortality, whereas the survivors exhibited significant locomotor deficits with increased acetylcholinesterase (AChE) activity. However, dietary supplementation with DPDS caused a significant decrease in mortality, improvement in locomotor activity and restoration of AChE activity in manganese-exposed flies. Additionally, the significant decreases in the total thiol level, activities of catalase and glutathione-S-transferase were accompanied with significant increases in the generation of reactive oxygen and nitrogen species and thiobarbituric acid reactive substances in flies exposed to manganese alone. Dietary supplementation with DPDS significantly augmented the antioxidant status and prevented manganese-induced oxidative stress in the treated flies. Collectively, the present data highlight that DPDS may be a promising chemopreventive drug candidate against neurotoxicity resulting from acute manganese exposure. PMID:26875733

  10. Effect of enhanced manganese oxidation in the hyporheic zone on basin-scale geochemical mass balance

    NASA Astrophysics Data System (ADS)

    Harvey, Judson W.; Fuller, Christopher C.

    1998-04-01

    We determined the role of the hyporheic zone (the subsurface zone where stream water and shallow groundwater mix) in enhancing microbially mediated oxidation of dissolved manganese (to form manganese precipitates) in a drainage basin contaminated by copper mining. The fate of manganese is of overall importance to water quality in Pinal Creek Basin, Arizona, because manganese reactions affect the transport of trace metals. The basin-scale role of the hyporheic zone is difficult to quantify because stream-tracer studies do not always reliably characterize the cumulative effects of the hyporheic zone. This study determined cumulative effects of hyporheic reactions in Pinal Creek basin by characterizing manganese uptake at several spatial scales (stream-reach scale, hyporheic-flow-path scale, and sediment-grain scale). At the stream-reach scale a one-dimensional stream-transport model (including storage zones to represent hyporheic flow paths) was used to determine a reach-averaged time constant for manganese uptake in hyporheic zones, 1/λs, of 1.3 hours, which was somewhat faster but still similar to manganese uptake time constants that were measured directly in centimeter-scale hyporheic flow paths (1/λh = 2.6 hours), and in laboratory batch experiments using streambed sediment (1/λ = 2.7 hours). The modeled depths of subsurface storage zones (ds = 4-17 cm) and modeled residence times of water in storage zones (ts = 3-12 min) were both consistent with direct measurements in hyporheic flow paths (dh = 0-15 cm, th = 1-25 min). There was also good agreement between reach-scale modeling and direct measurements of the percentage removal of dissolved manganese in hyporheic flow paths (fs = 8.9%, andfh = 9.3%rpar;. Manganese uptake experiments in the laboratory using sediment from Pinal Creek demonstrated (through comparison of poisoned and unpoisoned treatments) that the manganese removal process was enhanced by microbially mediated oxidation. The cumulative effect of

  11. Effect of enhanced manganese oxidation in the hyporheic zone on basin-scale geochemical mass balance

    USGS Publications Warehouse

    Harvey, J.W.; Fuller, C.C.

    1998-01-01

    We determined the role of the hyporheic zone (the subsurface zone where stream water and shallow groundwater mix) in enhancing microbially mediated oxidation of dissolved manganese (to form manganese precipitates) in a drainage basin contaminated by copper mining. The fate of manganese is of overall importance to water quality in Pinal Creek Basin, Arizona, because manganese reactions affect the transport of trace metals. The basin-scale role of the hyporheic zone is difficult to quantify because stream-tracer studies do not always reliably characterize the cumulative effects of the hyporheic zone. This study determined cumulative effects of hyporheic reactions in Pinal Creek basin by characterizing manganese uptake at several spatial scales (stream-reach scale, hyporheicflow-path scale, and sediment-grain scale). At the stream-reach scale a one-dimensional stream-transport model (including storage zones to represent hyporheic flow paths) was used to determine a reach-averaged time constant for manganese uptake in hyporheic zones, 1/??(s), of 1.3 hours, which was somewhat faster but still similar to manganese uptake time constants that were measured directly in centimeter-scale hyporheic flow paths (1/??(h) = 2.6 hours), and in laboratory batch experiments using streambed sediment (1/?? = 2.7 hours). The modeled depths of subsurface storage zones (d(s) = 4-17 cm) and modeled residence times of water in storage zones (t(s) = 3-12 min) were both consistent with direct measurements in hyporheic flow paths (d(h) = 0-15 cm, and t(h) = 1-25 min). There was also good agreement between reach-scale modeling and direct measurements of the percentage removal of dissolved manganese in hyporheic flow paths (f(s) = 8.9%, and f(h) = 9.3%). Manganese uptake experiments in the laboratory using sediment from Pinal Creek demonstrated (through comparison of poisoned and unpoisoned treatments) that the manganese removal process was enhanced by microbially mediated oxidation. The

  12. CHROMIUM TRANSPORT, OXIDATION, AND ADSORPTION IN MANGANESE-COATED SAND

    EPA Science Inventory

    We examine how the processes of advection, dispersion, oxidation-reduction, and adsorption combine to affect the transport of chromium through columns packed with pyrolusite (P-MnO$-coated sand. We find that P-Mn02 effectively oxidizes Cr@I) to Cr(VI) and that the extent of oxida...

  13. Manganese phosphide thin films and nanorods grown on gallium phosphide and on glass substrates

    NASA Astrophysics Data System (ADS)

    Nateghi, N.; Lambert-Milot, S.; Ménard, D.; Masut, R. A.

    2016-05-01

    We report a simple and fast route to grow ferromagnetic manganese phosphide polycrystalline films and nanorods on GaP and on glass substrates using metalorganic vapor phase deposition. Increasing the growth temperature (≥600 °C) and growth time (≥30 min) results in nucleation of secondary MnP crystals on the primary grains. The secondary crystals grow faster along a specific direction of orthorhombic MnP (c-axis) and form long rods (up to ~10 μm) whose diameters are in the nanoscale (20-100 nm). The nanorods can be easily detached from the glass substrate. The films exhibit ferromagnetic behavior with a range of transition temperatures, depending on the growth conditions.

  14. Manganese bismuth films with narrow transfer characteristics for Curie-point switching

    NASA Technical Reports Server (NTRS)

    Lewicki, G. W.; Guisinger, J. E. (Inventor)

    1974-01-01

    Manganese bismuth films having improved characteristics for recording information in analogue form, can be produced by a vacuum deposition of Bi and Mn with an atomic ratio of Mn to Bi between 2 and 3.5 or 1.4 and 1.6, followed by a specialized heat treatment which includes very brief exposure to a temperature between about 275 deg and 300 C. Similar MnBi films can be produced more reliably and reproducibly if the initial Bi layer is annealed prior to deposition of the Mn layer. Such an annealing step renders most other factors of the processing relatively non-critical. Deposition of both initial layers is preferably carried out in a vacuum approaching 10 to the -8th power Torr.

  15. Upgrading of Low-Grade Manganese Ore by Selective Reduction of Iron Oxide and Magnetic Separation

    NASA Astrophysics Data System (ADS)

    Gao, Yubo; Olivas-Martinez, M.; Sohn, H. Y.; Kim, Hang Goo; Kim, Chan Wook

    2012-12-01

    The utilization of low-grade manganese ores has become necessary due to the intensive mining of high-grade ores for a long time. In this study, calcined ferruginous low-grade manganese ore was selectively reduced by CO, which converted hematite to magnetite, while manganese oxide was reduced to MnO. The iron-rich component was then separated by magnetic separation. The effects of the various reduction parameters such as particle size, reduction time, temperature, and CO content on the efficiency of magnetic separation were studied by single-factor experiments and by a comprehensive full factorial experiment. Under the best experimental conditions tested, the manganese content in the ore increased from around 36 wt pct to more than 44 wt pct, and almost 50 wt pct of iron was removed at a Mn loss of around 5 pct. The results of the full factorial experiments allowed the identification of the significant effects and yielded regression equations for pct Fe removed, Mn/Fe, and pct Mn loss that characterize the efficiency of the upgrading process.

  16. Growth and magnetic property of antiperovskite manganese nitride films doped with Cu by molecular beam epitaxy

    SciTech Connect

    Yu, Fengmei; Ren, Lizhu; Meng, Meng; Wang, Yunjia; Yang, Mei; Wu, Shuxiang; Li, Shuwei

    2014-04-07

    Manganese nitrides thin films on MgO (100) substrates with and without Cu-doping have been fabricated by plasma assisted molecular beam epitaxy. Antiperovskite compounds Mn{sub 3.6}Cu{sub 0.4}N have been grown in the case of Cu-doping, and the pure Mn{sub 3}N{sub 2} single crystal has been obtained without Cu-doping. The Mn{sub 3.6}Cu{sub 0.4}N exhibits ferrimagnetism, and the magnetization of Mn{sub 3.6}Cu{sub 0.4}N increases upon the temperature decreasing from 300 K to 5 K, similar to Mn{sub 4}N. The exchange bias (EB) effects emerge in the Mn{sub 3.6}Cu{sub 0.4}N films. The EB behavior is originated from the interfaces between ferrimagnetic Mn{sub 3.6}Cu{sub 0.4}N and antiferromagnetic metal Mn, which is verified to be formed by the data of x-ray photoelectron spectroscopy. The present results not only provide a strategy for producing functional antiperovskite manganese nitrides, but also shed promising light on fabricating the exchange bias part of spintronic devices.

  17. Catalytic Role of Manganese Oxides in Prebiotic Nucleobases Synthesis from Formamide.

    PubMed

    Bhushan, Brij; Nayak, Arunima; Kamaluddin

    2016-06-01

    Origin of life processes might have begun with the formation of important biomonomers, such as amino acids and nucleotides, from simple molecules present in the prebiotic environment and their subsequent condensation to biopolymers. While studying the prebiotic synthesis of naturally occurring purine and pyrimidine derivatives from formamide, the manganese oxides demonstrated not only good binding for formamide but demonstrated novel catalytic activity. A novel one pot manganese oxide catalyzed synthesis of pyrimidine nucleobases like thymine is reported along with the formation of other nucleobases like purine, 9-(hydroxyacetyl) purine, cytosine, 4(3 H)-pyrimidinone and adenine in acceptable amounts. The work reported is significant in the sense that the synthesis of thymine has exhibited difficulties especially under one pot conditions and also such has been reported only under the catalytic activity of TiO2. The lower oxides of manganese were reported to show higher potential as catalysts and their existence were favored by the reducing atmospheric conditions prevalent on early Earth; thereby confirming the hypothesis that mineral having metals in reduced form might have been more active during the course of chemical evolution. Our results further confirm the role of formamide as a probable precursor for the formation of purine and pyrimidine bases during the course of chemical evolution and origin of life. PMID:26758444

  18. Morphological development of oxide-sulfide scales on iron and iron-manganese alloys

    SciTech Connect

    McAdam, G.; Young, D.J.

    1987-10-01

    Pure iron and alloys containing 2, 15, 25, and 50 wt.% manganese have been reacted at 1073 K in controlled gas atmospheres of SO/sub 2/-CO/sub 2/-CO-N/sub 2/. Equilibrium gas compositions were such that (1) FeS was stable but not FeO, or (2) both FeS and FeO were stable, or (3) FeO was stable but not FeS; in all cases, both MnS and MnO were stable. Under all reaction conditions, pure iron corroded to produce both sulfide and oxide. The resultant scale morphologies were consistent with local solid-gas equilibrium for the case in which both oxide and sulfide were stable but in the other cases indicated that equilibrium was not achieved and that direct reaction with SO/sub 2/(g) was responsible for corrosion. Additions of manganese did not greatly alter the scale morphologies. Under reaction conditions that were oxidizing and sulfidizing, very high levels of manganese were required to reduce the corrosion rate. On the other hand, relatively low levels had a beneficial effect both when FeO but not FeS was thermodynamically stable and similarly when FeS but not FeO was stable.

  19. Reversible aqueous zinc/manganese oxide energy storage from conversion reactions

    NASA Astrophysics Data System (ADS)

    Pan, Huilin; Shao, Yuyan; Yan, Pengfei; Cheng, Yingwen; Han, Kee Sung; Nie, Zimin; Wang, Chongmin; Yang, Jihui; Li, Xiaolin; Bhattacharya, Priyanka; Mueller, Karl T.; Liu, Jun

    2016-05-01

    Rechargeable aqueous batteries such as alkaline zinc/manganese oxide batteries are highly desirable for large-scale energy storage owing to their low cost and high safety; however, cycling stability is a major issue for their applications. Here we demonstrate a highly reversible zinc/manganese oxide system in which optimal mild aqueous ZnSO4-based solution is used as the electrolyte, and nanofibres of a manganese oxide phase, α-MnO2, are used as the cathode. We show that a chemical conversion reaction mechanism between α-MnO2 and H+ is mainly responsible for the good performance of the system. This includes an operating voltage of 1.44 V, a capacity of 285 mAh g‑1 (MnO2), and capacity retention of 92% over 5,000 cycles. The Zn metal anode also shows high stability. This finding opens new opportunities for the development of low-cost, high-performance rechargeable aqueous batteries.

  20. Fischer-Tropsch kinetic studies with cobalt-manganese oxide catalysts

    SciTech Connect

    Keyser, M.J.; Everson, R.C.; Espinoza, R.L.

    2000-01-01

    An investigation was undertaken to establish the reaction mechanism for the Fischer-Tropsch reaction, in the presence of the water-gas shift reaction, over a cobalt-manganese oxide catalyst under conditions favoring the formation of gaseous, liquid, and solid (waxes) hydrocarbons (210--250 C and 6--26 bar). A micro-fixed-bed reactor was used with a cobalt-manganese oxide catalyst prepared by a coprecipitation method. An integral reactor model involving both Fischer-Tropsch and water-gas shift reaction kinetics was used to describe the overall performance. Reaction rate equations based on Langmuir-Hinshelwood-Hougen-Watson models for the Fischer-Tropsch reaction (hydrocarbon forming) and empirical reaction rate equations for the water-gas shift reaction from the literature were tested. Different combinations of the reaction rate equation were evaluated with the aid of a nonlinear regression procedure. It was found that a reaction rate equation for the Fischer-Tropsch reaction based on the enolic theory performed slightly better than a reaction rate equation based on the carbide theory. Reaction rate constants for the cobalt-manganese oxide catalyst are reported, and it is concluded that this catalyst also behaves very much like iron-based catalysts.

  1. Catalytic Role of Manganese Oxides in Prebiotic Nucleobases Synthesis from Formamide

    NASA Astrophysics Data System (ADS)

    Bhushan, Brij; Nayak, Arunima; Kamaluddin

    2016-06-01

    Origin of life processes might have begun with the formation of important biomonomers, such as amino acids and nucleotides, from simple molecules present in the prebiotic environment and their subsequent condensation to biopolymers. While studying the prebiotic synthesis of naturally occurring purine and pyrimidine derivatives from formamide, the manganese oxides demonstrated not only good binding for formamide but demonstrated novel catalytic activity. A novel one pot manganese oxide catalyzed synthesis of pyrimidine nucleobases like thymine is reported along with the formation of other nucleobases like purine, 9-(hydroxyacetyl) purine, cytosine, 4(3 H)-pyrimidinone and adenine in acceptable amounts. The work reported is significant in the sense that the synthesis of thymine has exhibited difficulties especially under one pot conditions and also such has been reported only under the catalytic activity of TiO2. The lower oxides of manganese were reported to show higher potential as catalysts and their existence were favored by the reducing atmospheric conditions prevalent on early Earth; thereby confirming the hypothesis that mineral having metals in reduced form might have been more active during the course of chemical evolution. Our results further confirm the role of formamide as a probable precursor for the formation of purine and pyrimidine bases during the course of chemical evolution and origin of life.

  2. Synthesis and Electrochemical Analyses of Manganese Oxides for Super-Capacitors.

    PubMed

    Kim, Taewoo; Hwang, Hyein; Jang, Jaeyong; Park, Inyeong; Shim, Sang Eun; Baeck, Sung-Hyeon

    2015-11-01

    δ-Phase and α-phase manganese oxides were prepared using a hydrothermal method and their electrochemical properties were characterized. The influence of calcination temperature on the properties of manganese oxides was studied. Crystallinities were studied by X-ray diffraction, and scanning and transmission electron microscopy were utilized to examine morphologies. Average pore sizes and specific surface areas of samples were analyzed using the Barret-Joyner-Halenda and Brunauer-Emmett-Teller methods, respectively. After calcination in the range 300 degrees C to 600 degrees C, changes in morphology and crystallinity were observed. The flower-like shape of as synthesized samples became nanorod-like and the δ-phase changed to the α-phase. These changes may have been due to the removal of water during calcination. Furthermore, a transition stage in which the two phases coexisted was observed. Synthesized manganese oxides were mixed with carbon by sonification, to increase electric conductivity and to induce a synergistic effect between pseudo-capacitor and electric double layer capacitor (EDLC). Specific capacitances and rate durability of each composite were investigated by cyclic voltammetry in 1 M Na2SO4 electrolyte at different scan rates. MnO2 calcined at 400 degrees C exhibited the highest capacitance, probably due to its high surface area and more porous structure. PMID:26726613

  3. Raman microscopy of lithium-manganese-rich transition metal oxide cathodes

    SciTech Connect

    Ruther, Rose E.; Callender, Andrew F.; Zhou, Hui; Martha, Surendra K.; Nanda, Jagjit

    2014-11-15

    Lithium-rich and manganese-rich (LMR) layered transition metal (TM) oxide composites with general formula xLi2MnO3·(1-x)LiMO2 (M = Ni, Co, Mn) are promising cathode candidates for high energy density lithium ion batteries. Lithium-manganese-rich TM oxides crystallize as a nanocomposite layered phase whose structure further evolves with electrochemical cycling. Raman spectroscopy is a powerful tool to monitor the crystal chemistry and correlate phase changes with electrochemical behavior. While several groups have reported Raman spectra of lithium rich TM oxides, the data show considerable variability in terms of both the vibrational features observed and their interpretation. In this paper, Raman microscopy is used to investigate lithium-rich and manganese-rich TM cathodes as a function of voltage and electrochemical cycling at various temperatures. No growth of a spinel phase is observed within the cycling conditions. However, analysis of the Raman spectra does indicate the structure of LMR-NMC deviates significantly from an ideal layered phase. Finally, the results also highlight the importance of using low laser power and large sample sizes to obtain consistent data sets.

  4. Raman microscopy of lithium-manganese-rich transition metal oxide cathodes

    DOE PAGESBeta

    Ruther, Rose E.; Callender, Andrew F.; Zhou, Hui; Martha, Surendra K.; Nanda, Jagjit

    2014-11-15

    Lithium-rich and manganese-rich (LMR) layered transition metal (TM) oxide composites with general formula xLi2MnO3·(1-x)LiMO2 (M = Ni, Co, Mn) are promising cathode candidates for high energy density lithium ion batteries. Lithium-manganese-rich TM oxides crystallize as a nanocomposite layered phase whose structure further evolves with electrochemical cycling. Raman spectroscopy is a powerful tool to monitor the crystal chemistry and correlate phase changes with electrochemical behavior. While several groups have reported Raman spectra of lithium rich TM oxides, the data show considerable variability in terms of both the vibrational features observed and their interpretation. In this paper, Raman microscopy is used tomore » investigate lithium-rich and manganese-rich TM cathodes as a function of voltage and electrochemical cycling at various temperatures. No growth of a spinel phase is observed within the cycling conditions. However, analysis of the Raman spectra does indicate the structure of LMR-NMC deviates significantly from an ideal layered phase. Finally, the results also highlight the importance of using low laser power and large sample sizes to obtain consistent data sets.« less

  5. Oxidative Transformation of Controlled Substances by Manganese Dioxide.

    PubMed

    Lai, Webber Wei-Po; Lin, Angela Yu-Chen; Yang, Sheng-Yao; Huang, Ching-Hua

    2015-01-01

    This study investigated the oxidative transformation of four controlled substances (ketamine, methamphetamine, morphine, and codeine) by synthesized MnO2 (δ-MnO2) in aqueous environments. The results indicated that ketamine and methamphetamine were negligibly oxidized by MnO2 and, thus, may be persistent in the aqueous environment. However, morphine and codeine were able to be oxidized by MnO2, which indicated that they are likely naturally attenuated in aqueous environments. Overall, lower solution pH values, lower initial compound concentrations, and higher MnO2 loading resulted in a faster reaction rate. The oxidation of morphine was inhibited in the presence of metal ions (Mn(2+), Fe(3+), Ca(2+), and Mg(2+)) and fulvic acid. However, the addition of Fe(3+) and fulvic acid enhanced codeine oxidation. A second-order kinetics model described the oxidation of morphine and codeine by MnO2; it suggested that the formation of a surface precursor complex between the target compound and the MnO2 surface was the rate-limiting step. Although the target compounds were degraded, the slow TOC removal indicated that several byproducts were formed and persist against further MnO2 oxidation. PMID:26078991

  6. Sorption of ferric iron from ferrioxamine B to synthetic and biogenic layer type manganese oxides

    NASA Astrophysics Data System (ADS)

    Duckworth, Owen W.; Bargar, John R.; Sposito, Garrison

    2008-07-01

    Siderophores are biogenic chelating agents produced in terrestrial and marine environments that increase the bioavailability of ferric iron. Recent work has suggested that both aqueous and solid-phase Mn(III) may affect siderophore-mediated iron transport, but scant information appears to be available about the potential roles of layer type manganese oxides, which are relatively abundant in soils and the oligotrophic marine water column. To probe the effects of layer type manganese oxides on the stability of aqueous Fe-siderophore complexes, we studied the sorption of ferrioxamine B [Fe(III)HDFOB +, an Fe(III) chelate of the trihydroxamate siderophore desferrioxamine B (DFOB)] to two synthetic birnessites [layer type Mn(III,IV) oxides] and a biogenic birnessite produced by Pseudomonas putida GB-1. We found that all of these predominantly Mn(IV) oxides greatly reduced the aqueous concentration of Fe(III)HDFOB + at pH 8. Analysis of Fe K-edge EXAFS spectra indicated that a dominant fraction of Fe(III) associated with the Mn(IV) oxides is not complexed by DFOB as in solution, but instead Fe(III) is specifically adsorbed to the mineral structure at multiple sites, thus indicating that the Mn(IV) oxides displaced Fe(III) from the siderophore complex. These results indicate that layer type manganese oxides, including biogenic minerals, may sequester iron from soluble ferric complexes. We conclude that the sorption of iron-siderophore complexes may play a significant role in the bioavailability and biogeochemical cycling of iron in marine and terrestrial environments.

  7. Kinetics and spectroscopic observations of atrazine dealkylation on manganese oxides

    SciTech Connect

    Malengreau, N.; Sposito, G.; Cheney, M.A.; Crowley, D.E.

    1997-12-31

    Abiotic transformations of organic pollutants are often neglected in remediation scenarios but nonetheless can contribute significantly to detoxification. Mn oxide minerals are capable of degrading organic pollutants adsorbed to their surfaces by both redox and proton-promoted mechanisms. Concurrently with calorimetric, gas-pressure, chromatographic, and ESR methods, we used ICP, DRS, DRIFT, and FTIR spectroscopies to investigate atrazine degradation on three Mn oxides. We found that N-dealkylation can occur abiotically, leading to the formation of deethylatrazine and deisopropylatrazine. The Mn extractability after degradation of atrazine was highly dependent on the Mn oxide. Extractable Mn increased with time for cryptomelane, was constant for pyrolusite, and remained very low for birnessite. The extractable Mn is Mn(II). UV signatures of atrazine by-products were different from one another and were used to trace degradation products at the Mn oxide surface. Mechanistic interpretation of the in situ reaction kinetics and thermodynamics will be discussed.

  8. Simultaneous stripping recovery of ammonia-nitrogen and precipitation of manganese from electrolytic manganese residue by air under calcium oxide assist.

    PubMed

    Chen, Hongliang; Liu, Renlong; Shu, Jiancheng; Li, Wensheng

    2015-01-01

    Leaching tests of electrolytic manganese residue (EMR) indicated that high contents of soluble manganese and ammonia-nitrogen posed a high environmental risk. This work reports the results of simultaneous stripping recovery of ammonia-nitrogen and precipitation of manganese by air under calcium oxide assist. The ammonia-nitrogen stripping rate increased with the dosage of CaO, the air flow rate and the temperature of EMR slurry. Stripped ammonia-nitrogen was absorbed by a solution of sulfuric acid and formed soluble (NH4)2SO4 and (NH4)3H(SO4)3. The major parameters that effected soluble manganese precipitation were the dosage of added CaO and the slurry temperature. Considering these two aspects, the efficient operation conditions should be conducted with 8 wt.% added CaO, 60°C, 800 mL min(-1) air flow rate and 60-min reaction time. Under these conditions 99.99% of the soluble manganese was precipitated as Mn3O4, which was confirmed by XRD and SEM-EDS analyses. In addition, the stripping rate of ammonia-nitrogen was 99.73%. Leaching tests showed the leached toxic substances concentrations of the treated EMR met the integrated wastewater discharge standard of China (GB8978-1996). PMID:26301855

  9. Manganese-oxidizing photosynthesis before the rise of cyanobacteria

    PubMed Central

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

    2013-01-01

    The emergence of oxygen-producing (oxygenic) photosynthesis fundamentally transformed our planet; however, the processes that led to the evolution of biological water splitting have remained largely unknown. To illuminate this history, we examined the behavior of the ancient Mn cycle using newly obtained scientific drill cores through an early Paleoproterozoic succession (2.415 Ga) preserved in South Africa. These strata contain substantial Mn enrichments (up to ∼17 wt %) well before those associated with the rise of oxygen such as the ∼2.2 Ga Kalahari Mn deposit. Using microscale X-ray spectroscopic techniques coupled to optical and electron microscopy and carbon isotope ratios, we demonstrate that the Mn is hosted exclusively in carbonate mineral phases derived from reduction of Mn oxides during diagenesis of primary sediments. Additional observations of independent proxies for O2—multiple S isotopes (measured by isotope-ratio mass spectrometry and secondary ion mass spectrometry) and redox-sensitive detrital grains—reveal that the original Mn-oxide phases were not produced by reactions with O2, which points to a different high-potential oxidant. These results show that the oxidative branch of the Mn cycle predates the rise of oxygen, and provide strong support for the hypothesis that the water-oxidizing complex of photosystem II evolved from a former transitional photosystem capable of single-electron oxidation reactions of Mn. PMID:23798417

  10. Manganese-oxidizing photosynthesis before the rise of cyanobacteria.

    PubMed

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

    2013-07-01

    The emergence of oxygen-producing (oxygenic) photosynthesis fundamentally transformed our planet; however, the processes that led to the evolution of biological water splitting have remained largely unknown. To illuminate this history, we examined the behavior of the ancient Mn cycle using newly obtained scientific drill cores through an early Paleoproterozoic succession (2.415 Ga) preserved in South Africa. These strata contain substantial Mn enrichments (up to ∼17 wt %) well before those associated with the rise of oxygen such as the ∼2.2 Ga Kalahari Mn deposit. Using microscale X-ray spectroscopic techniques coupled to optical and electron microscopy and carbon isotope ratios, we demonstrate that the Mn is hosted exclusively in carbonate mineral phases derived from reduction of Mn oxides during diagenesis of primary sediments. Additional observations of independent proxies for O2--multiple S isotopes (measured by isotope-ratio mass spectrometry and secondary ion mass spectrometry) and redox-sensitive detrital grains--reveal that the original Mn-oxide phases were not produced by reactions with O2, which points to a different high-potential oxidant. These results show that the oxidative branch of the Mn cycle predates the rise of oxygen, and provide strong support for the hypothesis that the water-oxidizing complex of photosystem II evolved from a former transitional photosystem capable of single-electron oxidation reactions of Mn. PMID:23798417

  11. Adsorption of Ribose Nucleotides on Manganese Oxides with Varied Mn/O Ratio: Implications for Chemical Evolution

    NASA Astrophysics Data System (ADS)

    Bhushan, Brij; Shanker, Uma; Kamaluddin

    2011-10-01

    Manganese exists in different oxidation states under different environmental conditions with respect to redox potential. Various forms of manganese oxides, namely, Manganosite (MnO), Bixbyite (Mn2O3), Hausmannite (Mn3O4) and Pyrolusite (MnO2) were synthesized and their possible role in chemical evolution studied. Adsorption studies of ribose nucleotides (5'-AMP, 5'-GMP, 5'-CMP and 5'-UMP) on these manganese oxides at neutral pH, revealed a higher binding affinity to manganosite (MnO) compared to the other manganese oxides. That manganese oxides having a lower Mn-O ratio show higher binding affinity for the ribonucleotides indirectly implies that such oxides may have provided a surface onto which biomonomers could have been concentrated through selective adsorption. Purine nucleotides were adsorbed to a greater extent compared to the pyrimidine nucleotides. Adsorption data followed Langmuir adsorption isotherms, and X m and K L values were calculated. The nature of the interaction and mechanism was elucidated by infrared spectral studies conducted on the metal-oxide and ribonucleotide-metal-oxide adducts.

  12. Adsorption of ribose nucleotides on manganese oxides with varied mn/o ratio: implications for chemical evolution.

    PubMed

    Bhushan, Brij; Shanker, Uma; Kamaluddin

    2011-10-01

    Manganese exists in different oxidation states under different environmental conditions with respect to redox potential. Various forms of manganese oxides, namely, Manganosite (MnO), Bixbyite (Mn(2)O(3)), Hausmannite (Mn(3)O(4)) and Pyrolusite (MnO(2)) were synthesized and their possible role in chemical evolution studied. Adsorption studies of ribose nucleotides (5'-AMP, 5'-GMP, 5'-CMP and 5'-UMP) on these manganese oxides at neutral pH, revealed a higher binding affinity to manganosite (MnO) compared to the other manganese oxides. That manganese oxides having a lower Mn-O ratio show higher binding affinity for the ribonucleotides indirectly implies that such oxides may have provided a surface onto which biomonomers could have been concentrated through selective adsorption. Purine nucleotides were adsorbed to a greater extent compared to the pyrimidine nucleotides. Adsorption data followed Langmuir adsorption isotherms, and X( m ) and K( L ) values were calculated. The nature of the interaction and mechanism was elucidated by infrared spectral studies conducted on the metal-oxide and ribonucleotide-metal-oxide adducts. PMID:21626404

  13. Manganese sulfide formation via concomitant microbial manganese oxide and thiosulfate reduction.

    SciTech Connect

    Lee, Ji-Hoon; Kennedy, David W.; Dohnalkova, Alice; Moore, Dean A.; Nachimuthu, Ponnusamy; Reed, Samantha B.; Fredrickson, Jim K.

    2011-09-27

    The dissimilatory metal-reducing bacterium, Shewanella oneidensis MR-1 produced γ-MnS (rambergite) nanoparticles under the concurrent reduction of synthetic MnO2 and thiosulfate coupled to H2 oxidation. Using two MR-1 mutants defective in outer membrane c-type cytochromes (ΔmtrC/ΔomcA and ΔmtrC/ΔomcA/ΔmtrF) to eliminate the direct reduction pathway for solid electron acceptors, it was determined that respiratory reduction of MnO2 was dominant relative to chemical reduction by biogenic sulfide generated from bacterial thiosulfate reduction. Although bicarbonate was excluded from the medium, incubations of MR-1 using lactate as the sole electron donor produced MnCO3 (rhodochrosite) as well as MnS in nearly equivalent amounts as estimated by micro X-ray diffraction (micro-XRD) analysis. It was concluded that carbonate released from lactate metabolism promoted MnCO3 formation and that Mn(II) mineralogy was strongly affected by carbonate ions even in the presence of abundant sulfide and weakly alkaline conditions that favor the precipitation of MnS. Formation of the biogenic MnS, as determined by a combination of micro-XRD, transmission electron microscopy, energy dispersive X-ray spectroscopy, and selected area electron diffraction analyses was consistent with equilibrium speciation modeling predictions. Although biogenic MnS likely only forms and is stable over a relatively narrow range of conditions, it may be a significant sink for Mn in anoxic marine basins and terrestrial subsurface sediments where Mn and sulfur compounds are undergoing concurrent reduction.

  14. Manganese (Mn) Oxidation Increases Intracellular Mn in Pseudomonas putida GB-1

    PubMed Central

    Banh, Andy; Chavez, Valarie; Doi, Julia; Nguyen, Allison; Hernandez, Sophia; Ha, Vu; Jimenez, Peter; Espinoza, Fernanda; Johnson, Hope A.

    2013-01-01

    Bacterial manganese (Mn) oxidation plays an important role in the global biogeochemical cycling of Mn and other compounds, and the diversity and prevalence of Mn oxidizers have been well established. Despite many hypotheses of why these bacteria may oxidize Mn, the physiological reasons remain elusive. Intracellular Mn levels were determined for Pseudomonas putida GB-1 grown in the presence or absence of Mn by inductively coupled plasma mass spectrometry (ICP-MS). Mn oxidizing wild type P. putida GB-1 had higher intracellular Mn than non Mn oxidizing mutants grown under the same conditions. P. putida GB-1 had a 5 fold increase in intracellular Mn compared to the non Mn oxidizing mutant P. putida GB-1-007 and a 59 fold increase in intracellular Mn compared to P. putida GB-1 ∆2665 ∆2447. The intracellular Mn is primarily associated with the less than 3 kDa fraction, suggesting it is not bound to protein. Protein oxidation levels in Mn oxidizing and non oxidizing cultures were relatively similar, yet Mn oxidation did increase survival of P. putida GB-1 when oxidatively stressed. This study is the first to link Mn oxidation to Mn homeostasis and oxidative stress protection. PMID:24147089

  15. Manganese oxide phases and morphologies: A study on calcination temperature and atmospheric dependence

    PubMed Central

    Fenske, Daniela; Bardenhagen, Ingo; Westphal, Anne; Knipper, Martin; Plaggenborg, Thorsten; Kolny-Olesiak, Joanna; Parisi, Jürgen

    2015-01-01

    Summary Manganese oxides are one of the most important groups of materials in energy storage science. In order to fully leverage their application potential, precise control of their properties such as particle size, surface area and Mnx + oxidation state is required. Here, Mn3O4 and Mn5O8 nanoparticles as well as mesoporous α-Mn2O3 particles were synthesized by calcination of Mn(II) glycolate nanoparticles obtained through an economical route based on a polyol synthesis. The preparation of the different manganese oxides via one route facilitates assigning actual structure–property relationships. The oxidation process related to the different MnOx species was observed by in situ X-ray diffraction (XRD) measurements showing time- and temperature-dependent phase transformations occurring during oxidation of the Mn(II) glycolate precursor to α-Mn2O3 via Mn3O4 and Mn5O8 in O2 atmosphere. Detailed structural and morphological investigations using transmission electron microscopy (TEM) and powder XRD revealed the dependence of the lattice constants and particle sizes of the MnOx species on the calcination temperature and the presence of an oxidizing or neutral atmosphere. Furthermore, to demonstrate the application potential of the synthesized MnOx species, we studied their catalytic activity for the oxygen reduction reaction in aprotic media. Linear sweep voltammetry revealed the best performance for the mesoporous α-Mn2O3 species. PMID:25671151

  16. Manganese oxide phases and morphologies: A study on calcination temperature and atmospheric dependence.

    PubMed

    Augustin, Matthias; Fenske, Daniela; Bardenhagen, Ingo; Westphal, Anne; Knipper, Martin; Plaggenborg, Thorsten; Kolny-Olesiak, Joanna; Parisi, Jürgen

    2015-01-01

    Manganese oxides are one of the most important groups of materials in energy storage science. In order to fully leverage their application potential, precise control of their properties such as particle size, surface area and Mn (x) (+) oxidation state is required. Here, Mn3O4 and Mn5O8 nanoparticles as well as mesoporous α-Mn2O3 particles were synthesized by calcination of Mn(II) glycolate nanoparticles obtained through an economical route based on a polyol synthesis. The preparation of the different manganese oxides via one route facilitates assigning actual structure-property relationships. The oxidation process related to the different MnO x species was observed by in situ X-ray diffraction (XRD) measurements showing time- and temperature-dependent phase transformations occurring during oxidation of the Mn(II) glycolate precursor to α-Mn2O3 via Mn3O4 and Mn5O8 in O2 atmosphere. Detailed structural and morphological investigations using transmission electron microscopy (TEM) and powder XRD revealed the dependence of the lattice constants and particle sizes of the MnO x species on the calcination temperature and the presence of an oxidizing or neutral atmosphere. Furthermore, to demonstrate the application potential of the synthesized MnO x species, we studied their catalytic activity for the oxygen reduction reaction in aprotic media. Linear sweep voltammetry revealed the best performance for the mesoporous α-Mn2O3 species. PMID:25671151

  17. Characterization of Manganese Oxide Precipitates from Appalachian Coal Mine Mine Drainage Treatment Systems

    SciTech Connect

    Tan, H.; Zhang, G; Heaney, P; Webb, S; Burgos, W

    2010-01-01

    The removal of Mn(II) from coal mine drainage (CMD) by chemical addition/active treatment can significantly increase treatment costs. Passive treatment for Mn removal involves promotion of biological oxidative precipitation of manganese oxides (MnO{sub x}). Manganese(II) removal was studied in three passive treatment systems in western Pennsylvania that differed based on their influent Mn(II) concentrations (20-150 mg/L), system construction ({+-}inoculation with patented Mn(II)-oxidizing bacteria), and bed materials (limestone vs. sandstone). Manganese(II) removal occurred at pH values as low as 5.0 and temperatures as low as 2 C, but was enhanced at circumneutral pH and warmer temperatures. Trace metals such as Zn, Ni and Co were removed effectively, in most cases preferentially, into the MnO{sub x} precipitates. Based on synchrotron radiation X-ray diffraction and Mn K-edge extended X-ray absorption fine structure spectroscopy, the predominant Mn oxides at all sites were poorly crystalline hexagonal birnessite, triclinic birnessite and todorokite. The surface morphology of the MnOx precipitates from all sites was coarse and 'sponge-like' composed of nm-sized lathes and thin sheets. Based on scanning electron microscopy (SEM), MnO{sub x} precipitates were found in close proximity to both prokaryotic and eukaryotic organisms. The greatest removal efficiency of Mn(II) occurred at the one site with a higher pH in the bed and a higher influent total organic C (TOC) concentration (provided by an upstream wetland). Biological oxidation of Mn(II) driven by heterotrophic activity was most likely the predominant Mn removal mechanism in these systems. Influent water chemistry and Mn(II) oxidation kinetics affected the relative distribution of MnOx mineral assemblages in CMD treatment systems.

  18. Thin film hydrous metal oxide catalysts

    DOEpatents

    Dosch, Robert G.; Stephens, Howard P.

    1995-01-01

    Thin film (<100 nm) hydrous metal oxide catalysts are prepared by 1) synthesis of a hydrous metal oxide, 2) deposition of the hydrous metal oxide upon an inert support surface, 3) ion exchange with catalytically active metals, and 4) activating the hydrous metal oxide catalysts.

  19. c-Type Cytochromes and Manganese Oxidation in Pseudomonas putida MnB1

    PubMed Central

    Caspi, Ron; Tebo, Bradley M.; Haygood, M. G.

    1998-01-01

    Pseudomonas putida MnB1 is an isolate from an Mn oxide-encrusted pipeline that can oxidize Mn(II) to Mn oxides. We used transposon mutagenesis to construct mutants of strain MnB1 that are unable to oxidize manganese, and we characterized some of these mutants. The mutants were divided into three groups: mutants defective in the biogenesis of c-type cytochromes, mutants defective in genes that encode key enzymes of the tricarboxylic acid cycle, and mutants defective in the biosynthesis of tryptophan. The mutants in the first two groups were cytochrome c oxidase negative and did not contain c-type cytochromes. Mn(II) oxidation capability could be recovered in a c-type cytochrome biogenesis-defective mutant by complementation of the mutation. PMID:9758766

  20. c-Type cytochromes and manganese oxidation in Pseudomonas putida MnB1

    SciTech Connect

    Caspi, R.; Tebo, B.M.; Haygood, M.G.

    1998-10-01

    Pseudomonas putida MnB1 is an isolate from an Mn oxide-encrusted pipeline that can oxidize Mn(II) to Mn oxides. The authors used transposon mutagenesis to construct mutants of strain MnB1 that are unable to oxidize manganese, and they characterized some of these mutants. The mutants were divided into three groups: mutants defective in the biogenesis of c-type cytochromes, mutants defective in genes that encode key enzymes of the tricarboxylic acid cycle, and mutants defective in the biosynthesis of tryptophan. The mutants in the first two groups were cytochrome c oxidase negative and did not contain c-type cytochromes. Mn(II) oxidation capability could be recovered in a c-type cytochrome biogenesis-defective mutant by complementation of the mutation.

  1. Secondary cell with orthorhombic alkali metal/manganese oxide phase active cathode material

    DOEpatents

    Doeff, M.M.; Peng, M.Y.; Ma, Y.; Visco, S.J.; DeJonghe, L.C.

    1996-09-24

    An alkali metal manganese oxide secondary cell is disclosed which can provide a high rate of discharge, good cycling capabilities, good stability of the cathode material, high specific energy (energy per unit of weight) and high energy density (energy per unit volume). The active material in the anode is an alkali metal and the active material in the cathode comprises an orthorhombic alkali metal manganese oxide which undergoes intercalation and deintercalation without a change in phase, resulting in a substantially linear change in voltage with change in the state of charge of the cell. The active material in the cathode is an orthorhombic structure having the formula M{sub x}Z{sub y}Mn{sub (1{minus}y)}O{sub 2}, where M is an alkali metal; Z is a metal capable of substituting for manganese in the orthorhombic structure such as iron, cobalt or titanium; x ranges from about 0.2 in the fully charged state to about 0.75 in the fully discharged state, and y ranges from 0 to 60 atomic %. Preferably, the cell is constructed with a solid electrolyte, but a liquid or gelatinous electrolyte may also be used in the cell. 11 figs.

  2. Active manganese oxide: a novel adsorbent for treatment of wastewater containing azo dye.

    PubMed

    Chakrabarti, S; Dutta, B K; Apak, R

    2009-01-01

    A new variety of active manganese oxide was prepared, characterized, and tested for its potential of adsorbing Congo Red, a dis-azo dye, from aqueous solutions. Both equilibrium and kinetics were investigated over different values of process parameters such as temperature (25-45 degrees C), adsorbent loading (0.4-0.6%), initial dye concentration (50-500 mg/L), presence of salts (sodium sulphate, 500 mg/L) and the oxygen content (MnO(x), x=1.2, 1.33 and 2) of the adsorbent. The equilibrium adsorption data were fitted to Langmuir and Freundlich isotherms. Langmuir adsorption capacity of the sorbent (x=1.33) for Congo Red was 38.6 mg/g at room temperature which is substantially higher than those for commercial manganese dioxide, red mud, coir pith, activated carbon, and fly ash. The kinetic data were best interpreted using a pseudo-second order model. The results show that the active manganese oxide used in this work removes the dye by reversible adsorption and has the potential for practical use for remediation of textile industry effluents. PMID:19955624

  3. Secondary cell with orthorhombic alkali metal/manganese oxide phase active cathode material

    DOEpatents

    Doeff, Marca M.; Peng, Marcus Y.; Ma, Yanping; Visco, Steven J.; DeJonghe, Lutgard C.

    1996-01-01

    An alkali metal manganese oxide secondary cell is disclosed which can provide a high rate of discharge, good cycling capabilities, good stability of the cathode material, high specific energy (energy per unit of weight) and high energy density (energy per unit volume). The active material in the anode is an alkali metal and the active material in the cathode comprises an orthorhombic alkali metal manganese oxide which undergoes intercalation and deintercalation without a change in phase, resulting in a substantially linear change in voltage with change in the state of charge of the cell. The active material in the cathode is an orthorhombic structure having the formula M.sub.x Z.sub.y Mn.sub.(1-y) O.sub.2, where M is an alkali metal; Z is a metal capable of substituting for manganese in the orthorhombic structure such as iron, cobalt or titanium; x ranges from about 0.2 in the fully charged state to about 0.75 in the fully discharged state, and y ranges from 0 to 60 atomic %. Preferably, the cell is constructed with a solid electrolyte, but a liquid or gelatinous electrolyte may also be used in the cell.

  4. Microbial reduction of manganese oxides - Interactions with iron and sulfur

    NASA Technical Reports Server (NTRS)

    Myers, Charles R.; Nealson, Kenneth H.

    1988-01-01

    Alteromonas putrefaciens (strain MR-1) is capable of rapid Mn(IV) reduction under conditions of neutral pH and temperatures characteristic of the Oneida Lake, New York, sediments from which it was isolated. MR-1 also reduces Fe(3+) to Fe(2+), and disproportionates thiosulfate to sulfide and sulfite; independently, the Fe(2+) and sulfide act as rapid reductants of Mn. The addition of Fe(3+) or thiosulfate to cultures of MR-1 in the presence of oxidized Mn increases the rate and the extent of Mn reduction relative to that observed in the absence of Fe(3+) or thiosulfate. Furthermore, when Fe(3+) and Mn oxides are present conjointly, Fe(2+) does not appear until the reduction of the oxidized Mn is complete. These results demonstrate that the observed rates of Fe(2+) and sulfide production may underestimate the total rates of Fe and sulfate reduction in those environments containing oxidized Mn. These results also demonstrate the potential impact that a single microbe can exert on sediment geochemistry, and provide the basis for preliminary models of the complexity of microbial and geochemical interactions that occur.

  5. Formation of iodinated organic compounds by oxidation of iodide-containing waters with manganese dioxide.

    PubMed

    Gallard, Hervé; Allard, Sébastien; Nicolau, Rudy; von Gunten, Urs; Croué, Jean Philippe

    2009-09-15

    This study shows that iodinated organic compounds can be produced when iodide-containing waters are in contact with manganese oxide birnessite (delta-MnO2) in the pH range of 5-7. In the absence of natural organic matter (NOM), iodide is oxidized to iodate that is also adsorbed onto delta-MnO2. In the presence of iodide and NOM, adsordable organic iodine compounds (AOI) are formed at pH < 7 because of the oxidation of iodide to iodine by delta-MnO2 and the reactions of iodine with NOM. In addition, iodoacetic acid and iodoform have been identified as specific iodinated byproducts. Formation of iodoform is not observed for high NOM/delta-MnO2 ratios due to inhibition of the catalytic effect of delta-MnO2 by NOM poisoning. Experiments with model compounds such as resorcinol and 3,5-heptanedione confirmed that the delta-MnO2/l(-) system is very effective for the formation of iodinated organic compounds. These results suggest that birnessite acts as a catalyst through the oxidation of iodide to iodine and the polarization of the iodine molecule, which then reacts with NOM moieties. Furthermore, our results indicate that during water treatment in the presence of manganese oxide, iodinated organic compounds may be formed, which may lead to taste and odor or toxicological problems. PMID:19806734

  6. Manganese-oxidizing photosynthesis before the rise of cyanobacteria

    NASA Astrophysics Data System (ADS)

    Johnson, J. E.; Webb, S.; Thomas, K. S.; Ono, S.; Kirschvink, J. L.; Fischer, W. W.

    2012-12-01

    The evolution of oxygenic photosynthesis was a singularity that fundamentally transformed our planet's core biogeochemical cycles and changed the redox structure of Earth's surface, crust, and mantle. To date, understanding the evolution of this molecular machinery has largely been derived from comparative biology. Several biochemical innovations enabled water-splitting, including a central photosynthetic pigment with a higher redox potential and coupled photosystems. However the critical photochemical invention was the water oxidizing complex (WOC) of photosystem II, a cubane cluster of four redox-active Mn atoms and a Ca atom bound by oxo bridges, that couple the single electron photochemistry of the photosystem to the four-electron oxidation of water to O2. Transitional forms of the WOC have been postulated, including an Mn-containing catalase-like peptide using an H2O2 donor, or uptake and integration of environmental Mn-oxides. One attractive hypothesis from the perspective of modern photo-assembly of the WOC posits an initial Mn(II)-oxidizing photosystem as a precursor to the WOC (Zubay, 1996; Allen and Martin, 2007). To test these hypotheses, we studied the behavior of the ancient Mn cycle captured by 2415 ± 6 Ma scientific drill cores retrieved by the Agouron Drilling Project through the Koegas Subgroup in Griqualand West, South Africa. This succession contains substantial Mn-enrichments (up to 17 wt.% in bulk). To better understand the petrogenesis and textural context of these deposits, we employed a novel X-ray absorption spectroscopy microprobe to make redox maps of ultra-thin sample sections at a 2μm scale. Coupled to light and electron microscopy and C isotopic measurements, we observe that all of the Mn is present as Mn(II), contained within carbonate minerals produced from early diagenetic reduction of Mn-oxide phases with organic matter. To assay the environmental oxidant responsible for the production of the Mn-oxides we examined two independent

  7. 4-(Trifluoromethyl)-benzonitrile: A novel electrolyte additive for lithium nickel manganese oxide cathode of high voltage lithium ion battery

    NASA Astrophysics Data System (ADS)

    Huang, Wenna; Xing, Lidan; Wang, Yating; Xu, Mengqing; Li, Weishan; Xie, Fengchao; Xia, Shengan

    2014-12-01

    In this work, 4-(Trifluoromethyl)-benzonitrile (4-TB) is used as a novel electrolyte additive for LiNi0.5Mn1.5O4 cathode of high voltage lithium ion battery. Charge-discharge tests show that the cyclic stability of LiNi0.5Mn1.5O4 is significantly improved by using 0.5 wt.% 4-TB. With using 4-TB, LiNi0.5Mn1.5O4 delivers an initial capacity of 133 mAh g-1 and maintains 121 mAh g-1 after 300 cycles with a capacity retention of 91%, compared to the 75% of that using base electrolyte (1 M LiPF6 in ethylene carbonate(EC)/dimethyl carbonate(DMC)). The results from linear sweep voltammetry, density functional theory calculations, electrochemical impedance spectroscopy, scanning electron microscope, energy dispersive spectroscopy, Fourier transform infrared, and inductively coupled plasma, indicate that 4-TB has lower oxidative stability than EC and DMC, and is preferentially oxidized on LiNi0.5Mn1.5O4 forming a low-impedance protective film, which prevents the subsequent oxidation decomposition of the electrolyte and suppresses the manganese dissolution from LiNi0.5Mn1.5O4.

  8. Manganese oxide-supported iron Fischer-Tropsch synthesis catalysts: physical and catalytic characterization

    SciTech Connect

    Kreitman, K.M.

    1986-01-01

    In this study, manganese oxide-supported iron (Fe/MnO) was prepared by impregnation of powdered manganese (II) oxide with aqueous iron(III) nitrate and subjected to various calcination and reduction treatments. It was then employed as a catalyst for Fischer-Tropsch Synthesis (FTS) and its steady-state activity and selectivity behavior was observed. The FTS reaction studies were run with nearly equimolal carbon monoxide/hydrogen feed at 515 and 540 K, 7.9 and 14.8 bar pressure. Feed conversion level was kept low in order to avoid transport limitations, and was varied by adjusting space velocity. The FTS reaction rate decreased strongly with increasing conversion. Compared to unpromoted iron catalysts, the Fe/MnO catalysts were more active for the water-gas shift reaction and less selective for methane and alcohols, especially at higher conversion, lower temperature and higher pressure. The olefin selectivity was high and secondary hydrogenation was not apparent. Catalysts calcined at higher temperature exhibited stronger effects of promotion, and yielded unusually high selectivity for C/sub 2/ to C/sub 4/ hydrocarbons at low temperature and high pressure. The general conclusion is that manganese promotion or iron can promote FTS selectivity towards low molecular weight olefins, but at the expense of high carbon dioxide formation. The Fe/MnO was also physically examined using Moessbauer spectroscopy and X-ray diffraction. Iron and manganese were found to interact strongly in the calcined catalyst, though extensive phase separation occurred during reduction. The promoting effects are apparently due to partial surface coverage of iron with MnO, the extent of which is enhanced by wetter reducing conditions.

  9. Magnetoactive feature of in-situ polymerised polyaniline film developed on the surface of manganese-zinc ferrite

    NASA Astrophysics Data System (ADS)

    Babayan, V.; Kazantseva, N. E.; Sapurina, I.; Moučka, R.; Vilčáková, J.; Stejskal, J.

    2012-07-01

    A polyaniline film exhibits magnetoactive properties when deposited on the surface of multidomain particles of manganese-zinc ferrite during in-situ polymerisation of aniline. This is reflected in the increased coercivity and thermomagnetic stability of an in-situ prepared composite compared with bare ferrite and its mixed composite with polyaniline. In addition, the deposition of a polyaniline film results in a shift of the complex-permeability dispersion region towards ultrahigh frequency band. These changes in the magnetic properties of polyaniline-coated ferrite are attributed to the increased value of the inner demagnetisation factor, which results from stress-induced magnetic anisotropy due to the pinning of domain walls appearing on the surface of ferrite. This study is focused on the mechanism of pinning of domain walls and its influence on the magnetic properties of in-situ prepared composites in terms of the molecular mechanism of oxidative polymerisation of aniline. Ferrite stimulates the propagation of polyaniline chains, which start to grow on the domain walls on the ferrite surface. It leads to the pinning of domain walls and restricts their mobility in a magnetic field. The further increase in the coercivity and the resonance frequency of polyaniline-coated ferrite due to film shrinkage after deprotonation of polyaniline makes it obvious that polyaniline coating induces elastic stresses in a ferrite particle that stimulate the growth of the effective magnetic anisotropy. Stress-induced magnetic anisotropy contributes to the reorientation of the magnetisation vectors in domains with respect to the new directions of easy magnetisation, given by magnetoelastic stresses, which leads to complex changes in the magnetic properties of in-situ prepared composites.

  10. Manganese Oxides: Parallels between Abiotic and Biotic Structures

    SciTech Connect

    Saratovksy, Ian; Wightman, Peter G.; Pasten, Pablo A.; Gaillard, Jean-Francois; Poeppelmeier, Kenneth R.

    2008-10-06

    A large number of microorganisms are responsible for the oxidation of Mn{sub (aq)}{sup 2+} to insoluble Mn{sup 3+/4+} oxides (MnO{sub x}) in natural aquatic systems. This paper reports the structure of the biogenic MnO{sub x}, including a quantitative analysis of cation vacancies, formed by the freshwater bacterium Leptothrix discophora SP6 (SP6-MnO{sub x}). The structure and the morphology of SP6-MnO{sub x} were characterized by transmission electron microscopy (TEM), X-ray absorption spectroscopy (XAS), including full multiple-scattering analysis, and powder X-ray diffraction (XRD). The biogenic precipitate consists of nanoparticles that are approximately 10 nm by 100 nm in dimension with a fibrillar morphology that resembles twisted sheets. The results demonstrate that this biogenic MnO{sub x} is composed of sheets of edge-sharing of Mn{sup 4+}O{sub 6} octahedra that form layers. The detailed analysis of the EXAFS spectra indicate that 12 {+-} 4% of the Mn{sup 4+} layer cation sites in SP6-MnO{sub x} are vacant, whereas the analysis of the XANES suggests that the average oxidation state of Mn is 3.8 {+-} 0.3. Therefore, the average chemical formula of SP6-MnO{sub x} is Mn{sub y}{sup n+}Mn{sub 0.12}{sup 3+}[{open_square}{sub 0.12}Mn{sub 0.88}{sup 4+}]O{sub 2} {center_dot} zH{sub 2}O, where M{sub y}{sup n+} represents hydrated interlayer cations, {open_square}{sub 0.12} represents Mn{sup 4+} cation vacancies within the layer, and Mn{sub 0.12}{sup 3+} represents hydrated cations that occupy sites above/below these cation vacancies.

  11. Manganese oxides: parallels between abiotic and biotic structures.

    PubMed

    Saratovsky, Ian; Wightman, Peter G; Pastén, Pablo A; Gaillard, Jean-François; Poeppelmeier, Kenneth R

    2006-08-30

    A large number of microorganisms are responsible for the oxidation of Mn(2+)((aq)) to insoluble Mn(3+/4+) oxides (MnO(x)()) in natural aquatic systems. This paper reports the structure of the biogenic MnO(x)(), including a quantitative analysis of cation vacancies, formed by the freshwater bacterium Leptothrix discophora SP6 (SP6-MnO(x)()). The structure and the morphology of SP6-MnO(x)() were characterized by transmission electron microscopy (TEM), X-ray absorption spectroscopy (XAS), including full multiple-scattering analysis, and powder X-ray diffraction (XRD). The biogenic precipitate consists of nanoparticles that are approximately 10 nm by 100 nm in dimension with a fibrillar morphology that resembles twisted sheets. The results dem-onstrate that this biogenic MnO(x)() is composed of sheets of edge-sharing of Mn(4+)O(6) octahedra that form layers. The detailed analysis of the EXAFS spectra indicate that 12 +/- 4% of the Mn(4+) layer cation sites in SP6-MnO(x)() are vacant, whereas the analysis of the XANES suggests that the average oxidation state of Mn is 3.8 +/- 0.3. Therefore, the average chemical formula of SP6-MnO(x)() is M(n)()(+)(y)()Mn(3+)(0.12)[ square(0.12)Mn(4+)(0.88)]O(2).zH(2)O, where M(n)()(+)(y)() represents hydrated interlayer cations, square(0.12) represents Mn(4+) cation vacancies within the layer, and Mn(3+)(0.12) represents hydrated cations that occupy sites above/below these cation vacancies. PMID:16925437

  12. Nanocrystalline todorokite-like manganese oxide produced by bacterial catalysis.

    PubMed

    Kim, Hack-Sung; Pastén, Pablo A; Gaillard, Jean-François; Stair, Peter C

    2003-11-26

    We describe the characterization of an unknown and difficult to identify but geochemically and environmentally significant MnOx structure produced by a freshwater bacterium, Leptothrix discophora SP-6, using combined transmission electron microscopy (TEM), extended X-ray absorption fine structure (EXAFS), and UV Raman spectroscopy. The large surface-to-volume ratio of the needle-shaped nanocrystalline MnO2 formed around the bacterial cells coupled to the porous, zeolite-like structure has the potential to catalyze reactions and oxidize and adsorb metals. PMID:14624570

  13. Solar driven water oxidation by a bioinspired manganese molecular catalyst.

    PubMed

    Brimblecombe, Robin; Koo, Annette; Dismukes, G Charles; Swiegers, Gerhard F; Spiccia, Leone

    2010-03-10

    A photoelectrochemical cell was designed that catalyzes the photooxidation of water using visible light as the sole energy source and a molecular catalyst, [Mn(4)O(4)L(6)](+) (1(+), L = bis(methoxyphenyl)phosphinate), synthesized from earth-abundant elements. The essential features include a photochemical charge separation system, [Ru(II)(bipy)(2)(bipy(COO)(2))], adhered to titania-coated FTO conductive glass, and 1(+) embedded within a proton-conducting membrane (Nafion). The complete photoanode represents a functional analogue of the water-oxidizing center of natural photosynthesis. PMID:20155923

  14. Cluster size and composition dependent water deprotonation by free manganese oxide clusters.

    PubMed

    Lang, Sandra M; Bernhardt, Thorsten M; Kiawi, Denis M; Bakker, Joost M; Barnett, Robert N; Landman, Uzi

    2016-06-21

    In the quest for cheap and earth abundant but highly effective and energy efficient water splitting catalysts, manganese oxide represents one of the materials of choice. In the framework of a new hierarchical modeling strategy we employ free non-ligated manganese oxide clusters MnxOx+y(+) (x = 2-5, y = -1, 0, 1, 2) as simplified molecular models to probe the interaction of water with nano-scale manganese oxide materials. Infrared multiple-photon dissociation (IR-MPD) spectroscopy in conjunction with first-principles spin density functional theory calculations is applied to study several series of MnxOx+y(H2O)n(+) complexes and reveal that the reaction of water with MnxOx+y(+) leads to the deprotonation of the water molecules via hydroxylation of the cluster oxo-bridges. This process is independent of the formal Mn oxidation state and occurs already for the first adsorbed water molecule and it proceeds until all oxo-bridges are hydroxylated. Additional water molecules are bound intact and favorably form H3O2 units with the hydroxylated oxo-bridges. Water adsorption and deprotonation is also found to induce structural transformations of the cluster core, including dimensionality crossover. Furthermore, the IR-MPD measurements reveal that clusters with one oxygen atom in excess MnxOx+1(+) contain a terminal O atom while clusters with two oxygen atoms in excess MnxOx+2(+) contain an intact O2 molecule which, however, dissociates upon adsorption of a minimum number of water molecules. These basic concepts could aid the future design of artificial water-splitting molecular catalysts. PMID:27226138

  15. Ab initio quantum Monte Carlo calculations of ground-state properties of manganese's oxides

    NASA Astrophysics Data System (ADS)

    Sharma, Vinit; Krogel, Jaron T.; Kent, P. R. C.; Reboredo, Fernando A.

    One of the critical scientific challenges of contemporary research is to obtain an accurate theoretical description of the electronic properties of strongly correlated systems such as transition metal oxides and rare-earth compounds, since state-of-art ab-initio methods based on approximate density functionals are not always sufficiently accurate. Quantum Monte Carlo (QMC) methods, which use statistical sampling to evaluate many-body wave functions, have the potential to answer this challenge. Owing to the few fundamental approximations made and the direct treatment of electron correlation, QMC methods are among the most accurate electronic structure methods available to date. We assess the accuracy of the diffusion Monte Carlo method in the case of rocksalt manganese oxide (MnO). We study the electronic properties of this strongly-correlated oxide, which has been identified as a suitable candidate for many applications ranging from catalysts to electronic devices. ``This work was supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Materials Sciences and Engineering Division.'' Ab initio quantum Monte Carlo calculations of ground-state properties of manganese's oxides.

  16. Effects of solar radiation on manganese oxide reactions with selected organic compounds

    SciTech Connect

    Bertino, D.J.; Zepp, R.G. )

    1991-07-01

    The effects of sunlight on aqueous redox reactions between manganese oxides (MnO{sub x}) and selected organic substances are reported. No sunlight-induced rate enhancement was observed for the MnO{sub x} oxidation of substituted phenols, anisole, o-dichlorobenzene, or p-chloroaniline. On the other hand, solar radiation did accelerate the reduction of manganese oxides by dissolved organic matter (DOM) from aquatic environments. The photoreduction of MnO{sub x} by DOM was little affected by molecular oxygen in air-saturated water (250 {mu}M), but was inhibited by 2,6-dichloroindophenol (0.5-6 {mu}M), and excellent electron acceptor. MnO{sub x} reduction also was photosensitized by anthraquinone-2-sulfonate. These results indicate that the photoreduction probably involves electron transfer from excited states of sorbed DOM to the oxide surface. Wavelength studies indicated that ultraviolet-B radiation (280-320 nm) plays an important role in this photoreduction.

  17. Oxidative transformation of tetrachlorophenols and trichlorophenols by manganese dioxide.

    PubMed

    Zhao, Ling; Yu, Zhiqiang; Peng, Ping'an; Huang, Weilin; Dong, Yuanhua

    2009-06-01

    This study examined the transformation kinetics of three tetrachlorophenols (TeCPs) and three trichlorophenols (TCPs) in the presence of MnO2 under different solution chemistry conditions. The reaction rate measured for each CP decreased as a function of solution pH, and under the same solution chemistry conditions, the measured rates may depend primarily on both the adsorbability at the MnO2 surfaces and the isomeric structures of the CPs. Isomeric effects indicated that chloro substituent on ortho or para positions exhibited faster rates of transformation than on meta positions. Gas chromatography-mass spectrometry analysis with a derivatization method showed that dimers including polychlorinated phenoxyphenols and chlorinated polyhydroxybiphenyl were among the major products for all CPs. Monomeric products were among the major products of 2,4,6-TCP, 2,3,4-TCP, and 2,3,4,6-TeCP, whereas trimeric products also were among the major products of 2,3,4-TCP and 2,4,5-TCP. It appeared that hydroxylation of CPs and formation of dimeric or trimeric products via oxidative coupling were the major reaction mechanisms involved in the oxidation of CPs by MnO2. PMID:19132822

  18. Metal Inhibition of Growth and Manganese Oxidation in Pseudomonas putida GB-1

    NASA Astrophysics Data System (ADS)

    Pena, J.; Sposito, G.

    2009-12-01

    Biogenic manganese oxides (MnO2) are ubiquitous nanoparticulate minerals that contribute to the adsorption of nutrient and toxicant metals, the oxidative degradation of various organic compounds, and the respiration of metal-reducing bacteria in aquatic and terrestrial environments. The formation of these minerals is catalyzed by a diverse and widely-distributed group of bacteria and fungi, often through the enzymatic oxidation of aqueous Mn(II) to Mn(IV). In metal-impacted ecosystems, toxicant metals may alter the viability and metabolic activity of Mn-oxidizing organisms, thereby limiting the conditions under which biogenic MnO2 can form and diminishing their potential as adsorbent materials. Pseudomonas putida GB-1 (P. putida GB-1) is a model Mn-oxidizing laboratory culture representative of freshwater and soil biofilm-forming bacteria. Manganese oxidation in P. putida GB-1 occurs via two single-electron-transfer reactions, involving a multicopper oxidase enzyme found on the bacterial outer membrane surface. Near the onset of the stationary phase of growth, dark brown MnO2 particles are deposited in a matrix of bacterial cells and extracellular polymeric substances, thus forming heterogeneous biomineral assemblages. In this study, we assessed the influence of various transition metals on microbial growth and manganese oxidation capacity in a P. putida GB-1 culture propagated in a nutrient-rich growth medium. The concentration-response behavior of actively growing P. putida GB-1 cells was investigated for Fe, Co, Ni, Cu and Zn at pH ≈ 6 in the presence and absence of 1 mM Mn. Toxicity parameters such as EC0, EC50 and Hillslope, and EC100 were obtained from the sigmoidal concentration-response curves. The extent of MnO2 formation in the presence of the various metal cations was documented 24, 50, 74 and 104 h after the metal-amended medium was inoculated. Toxicity values were compared to twelve physicochemical properties of the metals tested. Significant

  19. Influence of extractable soil manganese on oxidation capacity of different soils in Korea

    NASA Astrophysics Data System (ADS)

    Chon, Chul-Min; Kim, Jae Gon; Lee, Gyoo Ho; Kim, Tack Hyun

    2008-08-01

    We examined the relationship between soil oxidation capacity and extractable soil manganese, iron oxides, and other soil properties. The Korean soils examined in this study exhibited low to medium Cr oxidation capacities, oxidizing 0.00-0.47 mmol/kg, except for TG-4 soils, which had the highest capacity for oxidizing added Cr(III) [>1.01 mmol/kg of oxidized Cr(VI)]. TG and US soils, with high Mn contents, had relatively high oxidation capacities. The Mn amounts extracted by dithionite-citrate-bicarbonate (DCB) (Mnd), NH2OH·HCl (Mnh), and hydroquinone (Mnr) were generally very similar, except for the YS1 soils, and were well correlated. Only small proportions of either total Mn or DCB-extractable Mn were extracted by NH2OH·HCl and hydroquinone in the YS1 soils, suggesting inclusion of NH2OH·HCl and hydroquinone-resistant Mn oxides, because these extractants are weaker reductants than DCB. No Cr oxidation test results were closely related to total Mn concentrations, but Mnd, Mnh, and Mnr showed a relatively high correlation with the Cr tests ( r = 0.655-0.851; P < 0.01). The concentrations of Mnd and Mnh were better correlated with the Cr oxidation tests than was the Mnr concentration, suggesting that the oxidation capacity of our soil samples can be better explained by Mnd and Mnh than by Mnr. The first component in principal components analysis indicated that extractable soil Mn was a main factor controlling net Cr oxidation in the soils. Total soil Mn, Fe oxides, and the clay fraction are crucial for predicting the mobility of pollutants and heavy metals in soils. The second principal component indicated that the presence of Fe oxides in soils had a significant relationship with the clay fraction and total Mn oxide, and was also related to heavy-metal concentrations (Zn, Cd, and Cu, but not Pb).

  20. Kinetic and morphological development of oxide-sulfide scales on manganese at 1,073 K

    SciTech Connect

    McAdam, G.; Yound, D.J. )

    1992-04-01

    The corrosion behavior of manganese in controlled gas atmospheres of SO{sub 2}-CO{sub 2}-CO-N{sub 2} at 1073 K was studied. Under all conditions, the gas phase was slow to equilibrate, and catalysis of the gas affected the corrosion mechanism and resulting scale morphologies. Product scales invariably became detached from the metal during reaction, but the high manganese vapor pressure meant that no slowing of reaction resulted. Corrosion under conditions where MnS was the equilibrium reaction product led to the formation of a sulfide scale. At low p{sub s{sub 2}} values, this scale grew by reaction with either COS or SO{sub 2} according to parabolic kinetics. Gases with equilibrium compositions calculated to produce MnO, in fact corroded manganese to produce an inner layer of oxide plus sulfide, and an outer layer of MnO. The tendency to form sulfide was more marked at lower SO{sub 2} partial pressure and higher sulfur activities, the latter resulting from gas catalysis. These effects are due to the fact that SO{sub 2} is the principal reactant species.

  1. Manganese-oxide-supported iron Fischer-Tropsch synthesis catalysts: physical and catalytic characterization

    SciTech Connect

    Kreitman, K.M.; Baerns, M.; Butt, J.B.

    1987-06-01

    It has been claimed that catalysts containing iron and manganese are especially selective for production of low molecular weight olefins in the Fischer-Tropsch (FT) synthesis. In this study a new system, manganese-oxide-supported iron, Fe/MnO, was prepared, subjected to various calcination and reduction treatments, and then employed as a FT catalyst. Reaction studies were run with approximately 1/1: CO/H/sub 2/ feed at 515 and 540 K and 7.8 and 14.8 bar pressure. Although low conversions were employed, the synthesis rate decreased strongly with increasing conversion. Compared to conventional Fe catalysts, the Fe/MnO was more active for water-gas shift and less selective for methane and alcohols, especially at higher conversions, lower temperature, and higher pressure. Olefin selectivity was high, hydrogen chemisorption was depressed, and secondary hydrogenation was not apparent. In general it is concluded that the manganese-supported iron does promote FT selectivity for low molecular weight olefins, but at the expense of high CO/sub 2/ formation.

  2. Silicon oxide films grown in microwave discharge

    NASA Technical Reports Server (NTRS)

    Kraitchman, J.

    1968-01-01

    Silicon oxide films thicker than 1000 angstrom are produced in the dense plasma of a microwave discharge. The oxide growth is characterized by a rate limiting diffusion process modified by sputtering effects produced by the discharge. Silicon is rapidly oxidized at temperatures estimated to be 500 degrees C or lower.

  3. Manganese(II)-Oxidizing Bacillus Spores in Guaymas Basin Hydrothermal Sediments and Plumes

    PubMed Central

    Dick, Gregory J.; Lee, Yifan E.; Tebo, Bradley M.

    2006-01-01

    Microbial oxidation and precipitation of manganese at deep-sea hydrothermal vents are important oceanic biogeochemical processes, yet nothing is known about the types of microorganisms or mechanisms involved. Here we report isolation of a number of diverse spore-forming Mn(II)-oxidizing Bacillus species from Guaymas Basin, a deep-sea hydrothermal vent environment in the Gulf of California, where rapid microbially mediated Mn(II) oxidation was previously observed. mnxG multicopper oxidase genes involved in Mn(II) oxidation were amplified from all Mn(II)-oxidizing Bacillus spores isolated, suggesting that a copper-mediated mechanism of Mn(II) oxidation could be important at deep-sea hydrothermal vents. Phylogenetic analysis of 16S rRNA and mnxG genes revealed that while many of the deep-sea Mn(II)-oxidizing Bacillus species are very closely related to previously recognized isolates from coastal sediments, other organisms represent novel strains and clusters. The growth and Mn(II) oxidation properties of these Bacillus species suggest that in hydrothermal sediments they are likely present as spores that are active in oxidizing Mn(II) as it emerges from the seafloor. PMID:16672456

  4. Illumina sequencing of fungi associated with manganese oxide deposits in cave systems

    NASA Astrophysics Data System (ADS)

    Zorn, B. T.; Santelli, C. M.; Carmichael, S. K.; Pepe-Ranney, C. P.; Roble, L.; Carmichael, M.; Bräuer, S.

    2013-12-01

    The environmental cycling of manganese (Mn) remains relatively poorly characterized when compared with other metals such as iron. However, fungi have been observed to produce Mn(III/IV) oxides resembling buserite, birnessite, and todorokite on the periphery of vegetative hyphae, hyphal branching points and at the base of fruiting bodies. Recent studies indicate that some of these oxides may be generated by a two-stage reaction with soluble Mn(II) and biogenic reactive oxygen species for some groups of fungi, in particular the Ascomycota. These oxides can provide a versatile protective barrier or aid in the capture of trace metals in the environment, although the exact evolutionary function and trigger is unclear. In this study, two caves in the southern Appalachians, a pristine cave and an anthropogenically impacted cave, were compared by analyzing fungal community assemblages in manganese oxide rich deposits. Quantitative PCR data indicated that fungi are present in a low abundance (<1%) in all locations sampled within the caves. Among amplified DNA sequences retrieved in an 18S rDNA clone library, over 88% were representative of the phylum Basidiomycota (predominantly Agaricomycetes), 2.74% of Ascomycota, 2.28% of Blastocladiomycota and Chytridiomycota, 0.46% of Zygomycota, and 3.65% of Eukarya or Fungi incertae sedis. Using Illumina's MiSeq to sequence amplicons of the fungal ITS1 gene has yielded roughly 100,000-200,000 paired-end reads per sample. These data are currently being analyzed to compare fungal communities before and after induced Mn oxidation in the field. In addition, sites within the pristine cave are being compared with analogous sites in the impacted cave. Culturing efforts have thus far yielded Mn oxide producing members of the orders Glomerales and Pleosporales as well as two Genus incertae sedis (Fungal sp. YECT1, and Fungal sp. YECT3, growing on discarded electrical tape) that do not appear to be closely related to any other known Mn

  5. Coprecipitation and redox reactions of manganese oxides with copper and nickel

    USGS Publications Warehouse

    Hem, J.D.; Lind, Carol J.; Roberson, C.E.

    1989-01-01

    Open-system, continuous-titration experiments have been done in which a slow flux of ???0.02 molar solution of Mn2+ chloride, nitrate, or perchlorate with Cu2+ or Ni2+ in lesser concentrations was introduced into an aerated reactor solution held at constant temperature and at constant pH by a pH-stat titrator that added dilute NaOH. The resulting mixtures of metal oxyhydroxides and their native solutions were aged for periods as long as 2 1/2 years. Fresh and aged precipitates were characterized by chemical analysis, oxidation state determinations, X-ray and electron diffraction, and electron microscopy. The precipitates can be described as mixtures of oxide and oxyhydroxide species, using concepts of equilibrium and nonequilibrium chemical thermodynamics. The metal-ion content of the aged precipitates in systems that contained copper is distributed among three principal components. One of these is a mixed oxide Cu2Mn3O8 in which all Mn is in the 4+ oxidation state. A major component in all precipitates is feitknechtite, ??MnOOH. These forms are supplemented by CuO or by birnessite or ramsdellite forms of MnO2 where stoichiometry and thermodynamic calculations predict them. In systems that contained nickel and manganese, identifiable components included ??MnOOH, Ni(OH)2, and the same two forms of MnO2. The oxidation number of the precipitated manganese increased during aging, and the pH of the supernatant solution decreased. The maximum Mn oxidation number observed was 3.55 in an Mn + Cu precipitate aged for 18 months. Concentrations of Cu2+ and Ni2+ generally decreased to values substantially below those predicted by oxide or hydroxide equilibrium. Scavenging effects of this type are common in natural aqueous systems. ?? 1989.

  6. Development and Applications of Thallium isotopes: a new proxy tracking the extent of manganese oxide burial

    NASA Astrophysics Data System (ADS)

    Owens, J. D.; Nielsen, S.; Ostrander, C.; Peterson, L. C.; Anbar, A. D.

    2015-12-01

    Thallium (Tl) isotopes are a new and potential powerful paleoredox proxy with the possibility to track bottom water oxygen conditions based on the burial flux of manganese oxides. Thallium has a residence time of ~20 thousand years, which is long enough to render modern oxic seawater conservative with respect to concentration and isotopes. The isotopic signature of Tl in the global ocean is driven mainly by two outputs (1) adsorption onto manganese oxides and (2) low temperature oceanic crust alteration. Importantly, the isotopic inputs of Tl are all nearly the same value; thus, the isotopic composition and flux of the outputs almost exclusively set the seawater signature. For relatively short term redox events it is reasonable to assume that the dominant isotope fractionation process is associated with manganese oxide precipitation because low temperature alteration is controlled by long-term average ocean crust production rates. We present a broad range of modern samples that span several open ocean profiles combined with water column and sediment profiles from the permanently anoxic basins of the Black Sea and Cariaco Basins. The open ocean shows no variation in depth profiles that encompass most of the major water masses in the Atlantic and Southern Oceans. The anoxic basins, however, reveal Tl isotope signatures closer to their inputs, which is likely due to basinal restriction. The authigenic fraction of organic-rich sediments from the Black Sea and Cariaco Basin capture the Tl isotope value of the overlying water column, which shows that Tl isotopes could be applied as a faithful deep time redox proxy. For the first time, we will present new data showing that Tl isotopes is tracking bottom water ocean oxygenation. We are applying this isotope system to ancient samples, testing the spatial and temporal variability of ocean oxygenation coinciding with major biogeochemical events.

  7. Defect Physics, Delithiation Mechanism, and Electronic and Ionic Conduction in Layered Lithium Manganese Oxide Cathode Materials

    NASA Astrophysics Data System (ADS)

    Hoang, Khang

    2015-02-01

    Layered Li Mn O2 and Li2Mn O3 are of great interest for lithium-ion battery cathodes because of their high theoretical capacities. The practical application of these materials is, however, limited due to poor electrochemical performance. We herein report a comprehensive first-principles study of defect physics in Li Mn O2 and Li2Mn O3 using hybrid density-functional calculations. We find that manganese antisites have low formation energies in Li Mn O2 and may act as nucleation sites for the formation of impurity phases. The antisites can also occur with high concentrations in Li2Mn O3 ; however, unlike in Li Mn O2 , they can be eliminated by tuning the experimental conditions during preparation. Other intrinsic point defects may also occur and have an impact on the materials' properties and functioning. An analysis of the formation of lithium vacancies indicates that lithium extraction from Li Mn O2 is associated with oxidation at the manganese site, resulting in the formation of manganese small hole polarons; whereas in Li2Mn O3 the intrinsic delithiation mechanism involves oxidation at the oxygen site, leading to the formation of bound oxygen hole polarons ηO+ . The layered oxides are found to have no or negligible bandlike carriers, and they cannot be doped n or p type. The electronic conduction proceeds through hopping of hole and/or electron polarons; the ionic conduction occurs through lithium monovacancy and/or divacancy migration mechanisms. Since ηO+ is not stable in the absence of negatively charged lithium vacancies in bulk Li2Mn O3 , the electronic conduction near the start of delithiation is likely to be poor. We suggest that the electronic conduction associated with ηO+ and, hence, the electrochemical performance of Li2Mn O3 can be improved through nanostructuring and/or ion substitution.

  8. Facile synthesis and catalytic studies of CdS-manganese oxide nanocomposite

    NASA Astrophysics Data System (ADS)

    Kannan, R.; Karunakaran, K.; Vasanthkumar, S.

    2011-12-01

    Cadmium sulfide (CdS)-manganese oxide (MO) nanocomposite was synthesized by the ion exchange and ultrasonic irradiation methods. The synthesized nanocomposite was characterized by FTIR, powder X-ray diffractrogram (XRD), UV-Vis diffused reflectance spectra (UVDRS), photoluminescence (PL), transmission electron microscope (TEM) and energy dispersive X-ray analysis (EDX). The experimental results confirm the formation of CdS-MO nanocomposite. The luminescence of the nanocomposite exhibits a notable blue shift. The TEM results disclosed the size of the nanocomposite to be within 10-20 nm. The catalytic activity of the nanocomposite was evaluated by the degradation of methylene blue (MB) under visible light.

  9. Nanostructured and layered lithium manganese oxide and method of manufacturing the same

    NASA Technical Reports Server (NTRS)

    Singhal, Amit (Inventor); Skandan, Ganesh (Inventor)

    2005-01-01

    Nanostructured and layered lithium manganese oxide powders and methods of producing same. The powders are represented by the chemical formula, LixMn1-yMyO2, where 0.5

  10. Pathogenic prion protein is degraded by a manganese oxide mineral found in soils

    USGS Publications Warehouse

    Russo, F.; Johnson, C.J.; McKenzie, D.; Aiken, Judd M.; Pedersen, J.A.

    2009-01-01

    Prions, the aetiological agents of transmissible spongiform encephalopathies, exhibit extreme resistance to degradation. Soil can retain prion infectivity in the environment for years. Reactive soil components may, however, contribute to the inactivation of prions in soil. Members of the birnessite family of manganese oxides (MnO2) rank among the strongest natural oxidants in soils. Here, we report the abiotic degradation of pathogenic prion protein (PrPTSE) by a synthetic analogue of naturally occurring birnessite minerals. Aqueous MnO2 suspensions degraded the PrPTSE as evidenced by decreased immunoreactivity and diminished ability to seed protein misfolding cyclic amplification reactions. Birnessite-mediated PrPTSE degradation increased as a solution's pH decreased, consistent with the pH-dependence of the redox potential of MnO2. Exposure to 5.6 mg MnO2 ml-1 (PrPTSE:MnO2=1 : 110) decreased PrPTSE levels by ???4 orders of magnitude. Manganese oxides may contribute to prion degradation in soil environments rich in these minerals. ?? 2009 SGM.

  11. Highly Efficient Elimination of Carbon Monoxide with Binary Copper-Manganese Oxide Contained Ordered Nanoporous Silicas

    NASA Astrophysics Data System (ADS)

    Lee, Jiho; Kim, Hwayoun; Lee, Hyesun; Jang, Seojun; Chang, Jeong Ho

    2016-01-01

    Ordered nanoporous silicas containing various binary copper-manganese oxides were prepared as catalytic systems for effective carbon monoxide elimination. The carbon monoxide elimination efficiency was demonstrated as a function of the [Mn]/[Cu] ratio and reaction time. The prepared catalysts were characterized by Brunauer-Emmett-Teller (BET) method, small- and wide-angle X-ray diffraction (XRD), and high-resolution transmission electron microscopy (HR-TEM) for structural analysis. Moreover, quantitative analysis of the binary metal oxides within the nanoporous silica was achieved by inductively coupled plasma (ICP). The binary metal oxide-loaded nanoporous silica showed high room temperature catalytic efficiency with over 98 % elimination of carbon monoxide at higher concentration ratio of [Mn]/[Cu].

  12. Highly Efficient Elimination of Carbon Monoxide with Binary Copper-Manganese Oxide Contained Ordered Nanoporous Silicas.

    PubMed

    Lee, Jiho; Kim, Hwayoun; Lee, Hyesun; Jang, Seojun; Chang, Jeong Ho

    2016-12-01

    Ordered nanoporous silicas containing various binary copper-manganese oxides were prepared as catalytic systems for effective carbon monoxide elimination. The carbon monoxide elimination efficiency was demonstrated as a function of the [Mn]/[Cu] ratio and reaction time. The prepared catalysts were characterized by Brunauer-Emmett-Teller (BET) method, small- and wide-angle X-ray diffraction (XRD), and high-resolution transmission electron microscopy (HR-TEM) for structural analysis. Moreover, quantitative analysis of the binary metal oxides within the nanoporous silica was achieved by inductively coupled plasma (ICP). The binary metal oxide-loaded nanoporous silica showed high room temperature catalytic efficiency with over 98 % elimination of carbon monoxide at higher concentration ratio of [Mn]/[Cu]. PMID:26744146

  13. Electrochromism in copper oxide thin films

    SciTech Connect

    Richardson, T.J.; Slack, J.L.; Rubin, M.D.

    2000-08-15

    Transparent thin films of copper(I) oxide prepared on conductive SnO2:F glass substrates by anodic oxidation of sputtered copper films or by direct electrodeposition of Cu2O transformed reversibly to opaque metallic copper films when reduced in alkaline electrolyte. In addition, the same Cu2O films transform reversibly to black copper(II) oxide when cycled at more anodic potentials. Copper oxide-to-copper switching covered a large dynamic range, from 85% and 10% photopic transmittance, with a coloration efficiency of about 32 cm2/C. Gradual deterioration of the switching range occurred over 20 to 100 cycles. This is tentatively ascribed to coarsening of the film and contact degradation caused by the 65% volume change on conversion of Cu to Cu2O. Switching between the two copper oxides (which have similar volumes) was more stable and more efficient (CE = 60 cm2/C), but covered a smaller transmittance range (60% to 44% T). Due to their large electrochemical storage capacity and tolerance for alkaline electrolytes, these cathodically coloring films may be useful as counter electrodes for anodically coloring electrode films such as nickel oxide or metal hydrides.

  14. Trace metal-rich Quaternary hydrothermal manganese oxide and barite deposit, Milos Island, Greece

    USGS Publications Warehouse

    Hein, J.R.; Stamatakis, G.; Dowling, J.S.

    2000-01-01

    The Cape Vani Mn oxide and barite deposit on Milos Island offers an excellent opportunity to study the three-dimensional characteristics of a shallow-water hydrothermal system. Milos Island is part of the active Aegean volcanic arc. A 1 km long basin located between two dacitic domes in northwest Milos is filled with a 35-50 m thick section of Quaternary volcaniclastic and pyroclastic rocks capped by reef limestone that were hydrothermally mineralized by Mn oxides and barite. Manganese occurs as thin layers, as cement of sandstone and as metasomatic replacement of the limestone, including abundant fossil shells. Manganese minerals include chiefly δ-MnO2, pyrolusite and ramsdellite. The MnO contents for single beds range up to 60%. The Mn oxide deposits are rich in Pb (to 3.4%), BaO (to 3.1%), Zn (to 0.8%), As (to 0.3%), Sb (to 0.2%) and Ag (to 10 ppm). Strontium isotopic compositions of the Mn oxide deposits and sulphur isotopic compositions of the associated barite show that the mineralizing fluids were predominantly sea water. The Mn oxide deposit formed in close geographical proximity to sulphide-sulphate-Au-Ag deposits and the two deposit types probably formed from the same hydrothermal system. Precipitation of Mn oxide took place at shallow burial depths and was promoted by the mixing of modified sea water (hydrothermal fluid) from which the sulphides precipitated at depth and sea water that penetrated along faults and fractures in the Cape Vani volcaniclastic and tuff deposits. The hydrothermal fluid was formed from predominantly sea water that was enriched in metals leached from the basement and overlying volcanogenic rocks. The hydrothermal fluids were driven by convection sustained by heat from cooling magma chambers. Barite was deposited throughout the time of Mn oxide mineralization, which occurred in at least two episodes. Manganese mineralization occurred by both focused and diffuse flow, the fluids mineralizing the beds of greatest porosity and

  15. Role of Reactive Intermediates in Manganese Oxide Formation By Filamentous Ascomycete Fungi

    NASA Astrophysics Data System (ADS)

    Zeiner, C. A.; Anderton, C.; Wu, S.; Purvine, S.; Zink, E.; Paša-Tolić, L.; Santelli, C. M.; Hansel, C. M.

    2014-12-01

    Biogenic manganese (Mn) oxide minerals are ubiquitous in the environment, and their high reactivity can profoundly impact the fate of contaminants and cycling of carbon and nutrients. In contrast to bacteria, the pathways utilized by fungi to oxidize Mn(II) to Mn(III,IV) oxides remain largely unknown. Here, we explore the mechanisms of Mn(II) oxidation by a phylogenetically diverse group of filamentous Ascomycete fungi using a combination of chemical assays and bulk and spatially-resolved mass spectrometry. We show that the mechanisms of Mn(II) oxidation vary with fungal species, over time during secretome compositional changes, and in the presence of other fungi. Specifically, our work implicates a dynamic transition in Mn(II) oxidation pathways that varies between species. In particular, while reactive oxygen species (ROS) produced via transmembrane NADPH oxidases are involved in initial oxidation, over time, secreted enzymes become important Mn(II) oxidation mediators for some species. In addition, the overall secretome oxidation capacity varies with time and fungal species. Secretome analysis reveals a surprising absence of enzymes currently considered to be Mn(II)-oxidizing enzymes in these organisms, and instead highlights a wide variety of redox-active enzymes. Furthermore, we implicate fungal cell defense mechanisms in the formation of distinct Mn oxide patterns when fungi are grown in head-to-head competition. The identification and regulation of these secreted enzymes are under current investigation within the bulk secretome and within the interaction zone of structured fungal communities. Overall, our findings illustrate that Ascomycete Mn(II) oxidation mechanisms are highly variable and are dictated by complex environmental and ecological interactions. Future work will explore the connection between Ascomycete Mn(II) oxidation and the ability to degrade cellulose, a key carbon reservoir for biofuel production.

  16. Characterization of the manganese oxide produced by pseudomonas putida strain MnB1

    NASA Astrophysics Data System (ADS)

    Villalobos, Mario; Toner, Brandy; Bargar, John; Sposito, Garrison

    2003-07-01

    Manganese oxides form typically in natural aqueous environments via Mn(II) oxidation catalyzed by microorganisms, primarily bacteria, but little is known about the structure of the incipient solid-phase products. The Mn oxide produced by a Pseudomonas species representative of soils and freshwaters was characterized as to composition, average Mn oxidation number, and N 2 specific surface area. Electron microscopy, X-ray diffraction, and X-ray absorption near edge structure spectroscopy were applied to complement the physicochemical data with morphological and structural information. A series of synthetic Mn oxides also was analyzed by the same methods to gain better comparative understanding of the structure of the biogenic oxide. The latter was found to be a poorly crystalline layer type Mn(IV) oxide with hexagonal symmetry, significant negative structural charge arising from cation vacancies, and a relatively small number of randomly stacked octahedral sheets per particle. Its properties were comparable to those of δ-MnO 2 (vernadite) and a poorly crystalline hexagonal birnessite ("acid birnessite") synthesized by reduction of permanganate with HCl, but they were very different from those of crystalline triclinic birnessite. Overall, the structure and composition of the Mn oxide produced by P. putida were similar to what has been reported for other freshly precipitated Mn oxides in natural weathering environments, yielding further support to the predominance of biological oxidation as the pathway for Mn oxide formation. Despite variations in the degree of sheet stacking and Mn(III) content, all poorly crystalline oxides studied showed hexagonal symmetry. Thus, there is a need to distinguish layer type Mn oxides with structures similar to those of natural birnessites from the synthetic triclinic variety. We propose designating the unit cell symmetry as an addition to the current nomenclature for these minerals.

  17. Manganese Oxide Nanoarchitectures as Broad-Spectrum Sorbents for Toxic Gases.

    PubMed

    Long, Jeffrey W; Wallace, Jean M; Peterson, Gregory W; Huynh, Kim

    2016-01-20

    We demonstrate that sol-gel-derived manganese oxide (MnOx) nanoarchitectures exhibit broad-spectrum filtration activity for three chemically diverse toxic gases: NH3, SO2, and H2S. Manganese oxides are synthesized via the reaction of NaMnO4 and fumaric acid to form monolithic gels of disordered, mixed-valent Na-MnOx; incorporated Na(+) is readily exchanged for H(+) by subsequent acid rinsing to form a more crystalline H-MnOx phase. For both Na-MnOx and H-MnOx forms, controlled pore-fluid removal yields either densified, yet still mesoporous, xerogels or low-density aerogels (prepared by drying from supercritical CO2). The performance of these MnOx nanoarchitectures as filtration media is assessed using dynamic-challenge microbreakthrough protocols. We observe technologically relevant sorption capacities under both dry conditions and wet (80% relative humidity) for each of the three toxic industrial chemicals investigated. The Na-MnOx xerogels and aerogels provide optimal performance with the aerogel exhibiting maximum sorption capacities of 39, 200, and 680 mg g(-1) for NH3, SO2, and H2S, respectively. Postbreakthrough characterization using X-ray photoelectron spectroscopy (XPS) and diffuse-reflectance infrared Fourier transform spectroscopy (DRIFTS) confirms that NH3 is captured and partially protonated within the MnOx structure, while SO2 undergoes oxidation by the redox-active oxide to form adsorbed sulfate at the MnOx surface. Hydrogen sulfide is also oxidized to form a combination of sulfate and sulfur/polysulfide products, concomitant with a decrease in the average Mn oxidation state from 3.43 to 2.94 and generation of a MnOOH phase. PMID:26741498

  18. CVD diamond film oxidation resistance research

    NASA Astrophysics Data System (ADS)

    Jing, Longwei; Wang, Xiaoping; Wang, Lijun; Pan, Xiufang; Sun, Yiqing; Wang, Jinye; Sun, Hongtao

    2013-12-01

    Diamond films were deposited on a silicon substrate by microwave plasma chemical vapor deposition system, and its oxidation experiments were carried out in atmospheric environmental condition by using a muffle furnace. Inatmospheric environment (the temperature is from 400°C to 900°C) the oxidation resistance of diamond thin films was investigated. The results indicate that under the atmospheric environment diamond thin film surface morphology did not change after 6 hours at 400°C. Diamond thin film surface morphology began to change after 2 hours at 600°C, and when time was extended to 4 hours, the diamond thin film surface morphology changed significantly. The surface morphology of diamond films began to change after 15 minutes at a 700°C condition and when time was extended to 6 hours diamond films were all destroyed. All the diamond films on the silicon substrate disappeared completely in 20 minutes at 900°C. The intact crystal face is the reason that natural diamond has stable chemical property. The crystal face of synthetic diamond film has a lot of defects, especially on the side. Oxidation of the diamond films begin with the grain boundary and defects.

  19. High quality oxide films on substrates

    DOEpatents

    Ruckman, Mark W.; Strongin, Myron; Gao, Yong L.

    1994-01-01

    A method for providing an oxide film of a material on the surface of a substrate using a reactive deposition of the material onto the substrate surface in the presence of a solid or liquid layer of an oxidizing gas. The oxidizing gas is provided on the substrate surface in an amount sufficient to dissipate the latent heat of condensation occurring during deposition as well as creating a favorable oxidizing environment for the material.

  20. High quality oxide films on substrates

    DOEpatents

    Ruckman, M.W.; Strongin, M.; Gao, Y.L.

    1994-02-01

    A method is described for providing an oxide film of a material on the surface of a substrate using a reactive deposition of the material onto the substrate surface in the presence of a solid or liquid layer of an oxidizing gas. The oxidizing gas is provided on the substrate surface in an amount sufficient to dissipate the latent heat of condensation occurring during deposition as well as creating a favorable oxidizing environment for the material. 4 figures.

  1. The simple preparation of birnessite-type manganese oxide with flower-like microsphere morphology and its remarkable capacity retention

    SciTech Connect

    Zhu, Gang; Deng, Lingjuan; Wang, Jianfang; Kang, Liping; Liu, Zong-Huai

    2012-11-15

    Graphical abstract: Flower-like birnessite-type manganese oxide microspheres with large specific surface area and excellent electrochemical properties have been prepared by a facile hydrothermal method. Highlights: ► Birnessite-type manganese oxide with flower-like microsphere morphology and large specific surface area. ► A facile low-temperature hydrothermal method. ► Novel flower-like microsphere consists of the thin nano-platelets. ► Birnessite-type manganese oxide exhibits an ideal capacitive behavior and excellent cycling stability. -- Abstract: Birnessite-type manganese oxide with flower-like microsphere morphology and large specific surface area has been prepared by hydrothermal treating a mixture solution of KMnO{sub 4} and (NH{sub 4}){sub 2}SO{sub 4} at 90 °C for 24 h. The obtained material is characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy and N{sub 2} adsorption–desorption. Results indicate that the birnessite-type manganese oxide shows novel flower-like microsphere morphology and a specific surface area of 280 m{sup 2} g{sup −1}, and the flower-like microsphere consists of the thin nano-platelets. Electrochemical characterization indicates that the prepared material exhibits an ideal capacitive behavior with a capacitance value of 278 F g{sup −1} in 1 mol L{sup −1} Na{sub 2}SO{sub 4} aqueous solution at a scan rate of 5 mV s{sup −1}. Moreover, the prepared manganese oxide electrode shows excellent cycle stability, and the specific capacitance can maintain 98.6% of the initial one after 5000 cycles.

  2. Recovery of manganese oxides from spent alkaline and zinc–carbon batteries. An application as catalysts for VOCs elimination

    SciTech Connect

    Gallegos, María V.; Falco, Lorena R.; Peluso, Miguel A.; Sambeth, Jorge E.; Thomas, Horacio J.

    2013-06-15

    Highlights: • Manganese oxides were synthesized using spent batteries as raw materials. • Spent alkaline and zinc–carbon size AA batteries were used. • A biohydrometallurgical process was employed to bio-lixiviate batteries. • Manganese oxides were active in the oxidation of VOCs (ethanol and heptane). - Abstract: Manganese, in the form of oxide, was recovered from spent alkaline and zinc–carbon batteries employing a biohydrometallurgy process, using a pilot plant consisting in: an air-lift bioreactor (containing an acid-reducing medium produced by an Acidithiobacillus thiooxidans bacteria immobilized on elemental sulfur); a leaching reactor (were battery powder is mixed with the acid-reducing medium) and a recovery reactor. Two different manganese oxides were recovered from the leachate liquor: one of them by electrolysis (EMO) and the other by a chemical precipitation with KMnO{sub 4} solution (CMO). The non-leached solid residue was also studied (RMO). The solids were compared with a MnO{sub x} synthesized in our laboratory. The characterization by XRD, FTIR and XPS reveal the presence of Mn{sub 2}O{sub 3} in the EMO and the CMO samples, together with some Mn{sup 4+} cations. In the solid not extracted by acidic leaching (RMO) the main phase detected was Mn{sub 3}O{sub 4}. The catalytic performance of the oxides was studied in the complete oxidation of ethanol and heptane. Complete conversion of ethanol occurs at 200 °C, while heptane requires more than 400 °C. The CMO has the highest oxide selectivity to CO{sub 2}. The results show that manganese oxides obtained using spent alkaline and zinc–carbon batteries as raw materials, have an interesting performance as catalysts for elimination of VOCs.

  3. Pretreatment of algae-laden and manganese-containing waters by oxidation-assisted coagulation: Effects of oxidation on algal cell viability and manganese precipitation.

    PubMed

    Lin, Jr-Lin; Hua, Lap-Cuong; Wu, Yuting; Huang, Chihpin

    2016-02-01

    Preoxidation is manipulated to improve performance of algae and soluble manganese (Mn) removal by coagulation-sedimentation for water treatment plants (WTPs) when large amount of soluble Mn presents in algae-laden waters. This study aimed to investigate the effects of preoxidation on the performance of coagulation-sedimentation for the simultaneous removal of algae and soluble Mn, including ionic and complexed Mn. NaOCl, ClO2, and KMnO4 were used to pretreat such algae-laden and Mn containing waters. The variation of algal cell viability, residual cell counts, and concentrations of Mn species prior to and after coagulation-sedimentation step were investigated. Results show that NaOCl dosing was effective in reducing the viability of algae, but precipitated little Mn. ClO2 dosing had a strongest ability to lower algae viability and oxidize ionic and complexed soluble Mn, where KMnO4 dosing oxidized ionic and complexed Mn instead of reducing the viability of cells. Preoxidation by NaOCl only improved the algae removal by sedimentation, whereas most of soluble Mn still remained. On the other hand, ClO2 preoxidation substantially improved the performance of coagulation-sedimentation for simultaneous removal of algae and soluble Mn. Furthermore, KMnO4 preoxidation did improve the removal of algae by sedimentation, but left significant residual Mn in the supernatant. Images from FlowCAM showed changes in aspect ratio (AR) and transparency of algae-Mn flocs during oxidation-assisted coagulation, and indicates that an effective oxidation can improve the removal of most compact algae-Mn flocs by sedimentation. It suggests that an effective preoxidation for reducing algal cell viability and the concentration of soluble Mn is a crucial step for upgrading the performance of coagulation-sedimentation. PMID:26689663

  4. Deuterium and lithium-6 MAS NMR studies of manganese oxide electrode materials

    NASA Astrophysics Data System (ADS)

    Paik, Younkee

    Electrolytic manganese dioxide (EMD) is used world wide as the cathode materials in both lithium and alkaline primary (non-rechargeable) batteries. We have developed deuterium and lithium MAS NMR techniques to study EMD and related manganese oxides and hydroxides, where diffraction techniques are of limited value due to a highly defective nature of the structures. Deuterons in EMD, manganite, groutite, and deuterium-intercalated pyrolusite and ramsdellite were detected by NMR, for the first time, and their locations and motions in the structures were analyzed by applying variable temperature NMR techniques. Discharge mechanisms of EMD in alkaline (aqueous) electrolytes were studied, in conjunction with step potential electrochemical spectroscopic (SPECS) method, and five distinctive discharge processes were proposed. EMD is usually heat-treated at about 300--400°C to remove water to be used in lithium batteries. Details of the effects of heat-treatment, such as structural and compositional changes as a function of heat-treatment temperature, were studied by a combination of MAS NMR, XRD, and thermogravimetric analysis. Lithium local environments in heat-treated EMD (HEMD) that were discharged in lithium cells, were described in terms of related environments found in model compounds pyrolusite and ramsdellite where specific Li + sites were detected by MAS NMR and the hyperfine shift scale method of Grey et al. Acid-leaching of Li2MnO3 represents an approach for synthesizing new or modified manganese oxide electrode materials for lithium rechargeable batteries. Progressive removal of lithium from specific crystallographic sites, followed by a gradual change of the crystal structure, was monitored by a combination of NMR and XRD techniques.

  5. Manganese regulation of virulence factors and oxidative stress resistance in Neisseria gonorrhoeae

    PubMed Central

    Wu, Hsing-Ju; Seib, Kate L.; Srikhanta, Yogitha N.; Edwards, Jennifer; Kidd, Stephen P.; Maguire, Tina L .; Hamilton, Amanda; Pan, Kuan-Tin; Hsiao, He-Hsuan; Yao, Chen-Wen; Grimmond, Sean M.; Apicella, Michael A.; McEwan, Alastair G.; Wang, Andrew H-J.; Jennings, Michael P.

    2014-01-01

    Neisseria gonorrhoeae has evolved a complex and novel network of oxidative stress responses, including defense mechanisms that are dependent on manganese (Mn). We performed systematic analyses at the transcriptomic and proteomic (1D SDS-PAGE and Isotope-Coded Affinity Tag [ICAT]) levels to investigate the global expression changes that take place in a high Mn environment, which results in a Mn-dependent oxidative stress resistance phenotype. These studies revealed that 97 proteins are regulated at the post-transcriptional level under conditions of increased Mn concentration, including proteins involved in virulence (eg. Pilin, a key adhesin), oxidative stress defence (eg. superoxide dismutase), cellular metabolism, protein synthesis, RNA processing and cell division. Mn regulation of inorganic pyrophosphatase (Ppa) indicated the potential involvement of phosphate metabolism in the Mn-dependent oxidative stress defense. A detailed analysis of the role of Ppa and polyphosphate kinase (Ppk) in the gonococcal oxidative stress response revealed that ppk and ppa mutant strains showed increased resistance to oxidative stress. Investigation of these mutants grown with high Mn suggests that phosphate and pyrophosphate are involved in Mn-dependent oxidative stress resistance. PMID:20004262

  6. Mo;ecular Modeling of Biogenic Manganese Oxides Using ab Initio Density Functional Theory

    NASA Astrophysics Data System (ADS)

    Oconnor, M.; Sposito, G.; Refson, K.

    2003-12-01

    Layer type manganese oxides with short-range crystalline order (birnessites) are produced by many species of bacteria.Deposits of these oxides form a highly reactive catalytic surface that plays a major role in the destruction and sequestration of organic compounds and metals.Biogenic oxides also contain vacant Mn(IV)sites;these sites,with their associated negative charge, are the probable main cause of the high sorptive reactivity of the oxide surfaces. In order to acquire a deeper understanding of the molecular mechanisms involved in these processes, a model of a biogenic oxide was built and its structure was optimized using the CASTEP three-dimensional periodic system computational package. The resulting crystal structure shows good agreement with EXAFS data from crystals formed by a strain of the common soil and freshwater bacterium, Pseudomonas putida. The greatest challenge in modeling Mn oxides (like other transition metal oxides)comes in dealing with the electronic factors that lead to their magnetic and catalytic properties: they are highly correlated systems where the spin must be taken into account in order to obtain accurate predictions of their properties.

  7. Structure-Activity Relationships for Rates of Aromatic Amine Oxidation by Manganese Dioxide.

    PubMed

    Salter-Blanc, Alexandra J; Bylaska, Eric J; Lyon, Molly A; Ness, Stuart C; Tratnyek, Paul G

    2016-05-17

    New energetic compounds are designed to minimize their potential environmental impacts, which includes their transformation and the fate and effects of their transformation products. The nitro groups of energetic compounds are readily reduced to amines, and the resulting aromatic amines are subject to oxidation and coupling reactions. Manganese dioxide (MnO2) is a common environmental oxidant and model system for kinetic studies of aromatic amine oxidation. In this study, a training set of new and previously reported kinetic data for the oxidation of model and energetic-derived aromatic amines was assembled and subjected to correlation analysis against descriptor variables that ranged from general purpose [Hammett σ constants (σ(-)), pKas of the amines, and energies of the highest occupied molecular orbital (EHOMO)] to specific for the likely rate-limiting step [one-electron oxidation potentials (Eox)]. The selection of calculated descriptors (pKa, EHOMO, and Eox) was based on validation with experimental data. All of the correlations gave satisfactory quantitative structure-activity relationships (QSARs), but they improved with the specificity of the descriptor. The scope of correlation analysis was extended beyond MnO2 to include literature data on aromatic amine oxidation by other environmentally relevant oxidants (ozone, chlorine dioxide, and phosphate and carbonate radicals) by correlating relative rate constants (normalized to 4-chloroaniline) to EHOMO (calculated with a modest level of theory). PMID:27074054

  8. Development of a genetic system for a model manganese-oxidizing proteobacterium, Leptothrix discophora SS1.

    PubMed

    Bocioaga, Daniela; El Gheriany, Iman A; Lion, Leonard W; Ghiorse, William C; Shuler, Michael L; Hay, Anthony G

    2014-11-01

    Understanding the molecular underpinnings of manganese oxidation in Leptothrix discophora SS1 has been hampered by the lack of a genetic system. In this report, we describe the development of a genetic system for L. discophora SS1. The antibiotic sensitivity was characterized, and a procedure for transformation with exogenous DNA via conjugation was developed and optimized, resulting in a maximum transfer frequency of 5.2×10(-1) and a typical transfer frequency of the order of 1×10(-3) transconjugants per donor. Genetic manipulation of L. discophora SS1 was demonstrated by disrupting pyrF via chromosomal integration with a plasmid containing a R6Kγ origin of replication through homologous recombination. This resulted in resistance to 5-fluoroorotidine, which was abolished by complementation with an ectopically expressed copy of pyrF cloned into pBBR1MCS. This system is expected to be amenable to a systematic genetic analysis of L. discophora SS1, including those genes responsible for manganese oxidation. PMID:25149187

  9. Hydrothermal-reduction synthesis of manganese oxide nanomaterials for electrochemical supercapacitors.

    PubMed

    Zhang, Xiong; Chen, Yao; Yu, Peng; Ma, Yanwei

    2010-11-01

    In the present work, amorphous manganese oxide nanomaterials have been synthesized by a common hydrothermal method based on the redox reaction between MnO4(-) and Fe(2+) under an acidic condition. The synthesized MnO2 samples were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM), and electrochemical studies. XRD results showed that amorphous manganese oxide phase was obtained. XPS quantitative analysis revealed that the atomic ratio of Mn to Fe was 3.5 in the MnO2 samples. TEM images showed the porous structure of the samples. Electrochemical properties of the MnO2 electrodes were studied using cyclic voltammetry and galvanostatic charge-discharge cycling in 1 M Na2SO4 aqueous electrolyte, which showed excellent pseudocapacitance properties. A specific capacitance of 192 Fg(-1) at a current density of 0.5 Ag(-1) was obtained at the potential window from -0.1 to 0.9 V (vs. SCE). PMID:21138016

  10. Manganese oxide nanowires wrapped with nitrogen doped carbon layers for high performance supercapacitors.

    PubMed

    Li, Ying; Mei, Yuan; Zhang, Lin-Qun; Wang, Jian-Hai; Liu, An-Ran; Zhang, Yuan-Jian; Liu, Song-Qin

    2015-10-01

    In this study, manganese oxide nanowires wrapped by nitrogen-doped carbon layers (MnO(x)@NCs) were prepared by carbonization of poly(o-phenylenediamine) layer coated onto MnO2 nanowires for high performance supercapacitors. The component and structure of the MnO(x)@NCs were controlled through carbonization procedure under different temperatures. Results demonstrated that this composite combined the high conductivity and high specific surface area of nitrogen-doped carbon layers with the high pseudo-capacitance of manganese oxide nanowires. The as-prepared MnO(x)@NCs exhibited superior capacitive properties in 1 M Na2SO4 aqueous solution, such as high conductivity (4.167×10(-3) S cm(-1)), high specific capacitance (269 F g(-1) at 10 mV s(-1)) and long cycle life (134 F g(-1) after 1200 cycles at a scan rate of 50 mV s(-1)). It is reckoned that the present novel hybrid nanowires can serve as a promising electrode material for supercapacitors and other electrochemical devices. PMID:26070189

  11. Zinc oxide thin film acoustic sensor

    SciTech Connect

    Mohammed, Ali Jasim; Salih, Wafaa Mahdi; Hassan, Marwa Abdul Muhsien; Nusseif, Asmaa Deiaa; Kadhum, Haider Abdullah; Mansour, Hazim Louis

    2013-12-16

    This paper reports the implementation of (750 nm) thickness of Zinc Oxide (ZnO) thin film for the piezoelectric pressure sensors. The film was prepared and deposited employing the spray pyrolysis technique. XRD results show that the growth preferred orientation is the (002) plane. A polycrystalline thin film (close to mono crystallite like) was obtained. Depending on the Scanning Electron Microscopy photogram, the film homogeneity and thickness were shown. The resonance frequency measured (about 19 kHz) and the damping coefficient was calculated and its value was found to be about (2.5538), the thin film be haves as homogeneous for under and over damped. The thin film pressure sensing was approximately exponentially related with frequency, the thin film was observed to has a good response for mechanical stresses also it is a good material for the piezoelectric properties.

  12. Zinc oxide thin film acoustic sensor

    NASA Astrophysics Data System (ADS)

    Mohammed, Ali Jasim; Salih, Wafaa Mahdi; Hassan, Marwa Abdul Muhsien; Mansour, Hazim Louis; Nusseif, Asmaa Deiaa; Kadhum, Haider Abdullah

    2013-12-01

    This paper reports the implementation of (750 nm) thickness of Zinc Oxide (ZnO) thin film for the piezoelectric pressure sensors. The film was prepared and deposited employing the spray pyrolysis technique. XRD results show that the growth preferred orientation is the (002) plane. A polycrystalline thin film (close to mono crystallite like) was obtained. Depending on the Scanning Electron Microscopy photogram, the film homogeneity and thickness were shown. The resonance frequency measured (about 19 kHz) and the damping coefficient was calculated and its value was found to be about (2.5538), the thin film be haves as homogeneous for under and over damped. The thin film pressure sensing was approximately exponentially related with frequency, the thin film was observed to has a good response for mechanical stresses also it is a good material for the piezoelectric properties.

  13. Electrochemical impedance spectroscopy studies of lithium diffusion in doped manganese oxide

    SciTech Connect

    Johnson, B.J.; Doughty, D.H.; Voigt, J.A.; Boyle, T.J.

    1996-06-01

    Cathode performance is critical to lithium ion rechargeable battery performance; effects of doping lithium manganese oxide cathode materials on cathode performance are being investigated. In this paper, Li diffusion in Al-doped LiMn{sub 2}O{sub 4} was studied and found to be controlled by the quantity of Al dopant. Electrochemical cycling was conducted at 0.5mA/cm{sub 2}; electrochemical impedance spectra were taken at open circuit potential, with impedance being measured at 65 kHz-0.01 Hz. As the Al dopant level was increased, the Li diffusion rate decreased; this was attributed to the decreased lattice parameter of the doped oxide.

  14. Nano-sized Lithium Manganese Oxide Dispersed on Carbon Nanotubes for Energy Storage Applications

    SciTech Connect

    Bak, S.B.

    2009-08-01

    Nano-sized lithium manganese oxide (LMO) dispersed on carbon nanotubes (CNT) has been synthesized successfully via a microwave-assisted hydrothermal reaction at 200 C for 30 min using MnO{sub 2}-coated CNT and an aqueous LiOH solution. The initial specific capacity is 99.4 mAh/g at a 1.6 C-rate, and is maintained at 99.1 mAh/g even at a 16 C-rate. The initial specific capacity is also maintained up to the 50th cycle to give 97% capacity retention. The LMO/CNT nanocomposite shows excellent power performance and good structural reversibility as an electrode material in energy storage systems, such as lithium-ion batteries and electrochemical capacitors. This synthetic strategy opens a new avenue for the effective and facile synthesis of lithium transition metal oxide/CNT nanocomposite.

  15. Oxidation behavior of titanium nitride films

    NASA Astrophysics Data System (ADS)

    Chen, Hong-Ying; Lu, Fu-Hsing

    2005-07-01

    The oxidation behavior of titanium nitride (TiN) films has been investigated by using x-ray diffraction, Raman scattering spectroscopy, and field emission scanning electron microscopy. TiN films were deposited onto Si substrates by using cathodic arc plasma deposition technique. After that, the films were annealed in the air at 500-800 °C for 2 h. The x-ray diffraction spectra showed that rutile-TiO2 appeared above 600 °C. The relative intensity of TiO2 rapidly increased with temperatures. Only rutile-TiO2 was detected above 700 °C. Raman scattering spectra indicated the presence of rutile-TiO2 signals above 500 °C. Meanwhile an additional Si peak appeared at 700 °C in Raman spectra, above which only Si peak appeared. Many nano pores were found on the surface of films annealed at temperatures between 600 and 700 °C in field emission scanning electron microscopy, while the granular structure existed at 800 °C. The as-deposited TiN films had an apparent columnar structure. The thin and dense oxide overlayer appeared at 500 °C, and thicker oxide layer existed above 600 °C. The elongated grain structure with many voids existed in the film at 800 °C. These pores-voids might result from the nitrogen release during the oxidation of the nitride. The oxide layer obviously grows inward indicating the oxidation of TiN films belongs to an inward oxidation. The pre-exponential factor and the activation energy of the oxidation were evaluated by Arrhenius-type relation. These values were 2.2×10-6 cm2/s and 110+/-10 kJ/mol, which are consistent with those reports in the literature.

  16. Manganese-oxide minerals in fractures of the Crater Flat Tuff in drill core USW G-4, Yucca Mountain, Nevada

    SciTech Connect

    Carlos, B.A.; Bish, D.L.; Chipera, S.J.

    1990-07-01

    The Crater Flat Tuff is almost entirely below the water table in drill hole USW G-4 at Yucca Mountain, Nevada. Manganese-oxide minerals from the Crater Flat Tuff in USW G-4 were studied using optical, scanning electron microscopic, electron microprobe, and x-ray powder diffraction methods to determine their distribution, mineralogy, and chemistry. Manganese-oxide minerals coat fractures in all three members of the Crater Flat Tuff (Prow Pass, Bullfrog, and Tram), but they are most abundant in fractures in the densely welded devitrified intervals of these members. The coatings are mostly of the cryptomelane/hollandite mineral group, but the chemistry of these coatings varies considerably. Some of the chemical variations, particularly the presence of calcium, sodium, and strontium, can be explained by admixture with todorokite, seen in some x-ray powder diffraction patterns. Other chemical variations, particularly between Ba and Pb, demonstrate that considerable substitution of Pb for Ba occurs in hollandite. Manganese-oxide coatings are common in the 10-m interval that produced 75% of the water pumped from USW G-4 in a flow survey in 1983. Their presence in water-producing zones suggests that manganese oxides may exert a significant chemical effect on groundwater beneath Yucca Mountain. In particular, the ability of the manganese oxides found at Yucca Mountain to be easily reduced suggests that they may affect the redox conditions of the groundwater and may oxidize dissolved or suspended species. Although the Mn oxides at Yucca Mountain have low exchange capacities, these minerals may retard the migration of some radionuclides, particularly the actinides, through scavenging and coprecipitation. 23 refs., 21 figs., 2 tabs.

  17. Microstructural evolution of tungsten oxide thin films

    NASA Astrophysics Data System (ADS)

    Hembram, K. P. S. S.; Thomas, Rajesh; Rao, G. Mohan

    2009-10-01

    Tungsten oxide thin films are of great interest due to their promising applications in various optoelectronic thin film devices. We have investigated the microstructural evolution of tungsten oxide thin films grown by DC magnetron sputtering on silicon substrate. The structural characterization and surface morphology were carried out using X-ray diffraction and Scanning Electron Microscopy (SEM). The as deposited films were amorphous, where as, the films annealed above 400 °C were crystalline. In order to explain the microstructural changes due to annealing, we have proposed a "instability wheel" model for the evolution of the microstructure. This model explains the transformation of mater into various geometries within them selves, followed by external perturbation.

  18. Manganese As a Metal Accumulator

    EPA Science Inventory

    Manganese deposits in water distribution systems accumulate metals, radionuclides and oxyanions by a combination of surface complexation, adsorption and solid substitution, as well as a combination of oxidation followed by manganese reduction and sorption of the oxidized constitu...

  19. Preparation of anionic clay-birnessite manganese oxide composites by interlayer oxidation of oxalate ions by permanganate

    SciTech Connect

    Arulraj, James; Rajamathi, Michael

    2013-02-15

    Oxalate intercalated anionic clay-like nickel zinc hydroxysalt was obtained starting from nickel zinc hydroxyacetate, Ni{sub 3}Zn{sub 2}(OH){sub 8}(OAc){sub 2}{center_dot}2H{sub 2}O, by anion exchange. The intercalated oxalate species was reacted with potassium permanganate in such a way that the layered manganese oxide formed was within the interlayer region of the anionic clay resulting in a layered composite in which the negative charges on the birnessite type manganese oxide layers compensate the positive charges on the anionic clay layers. Birnessite to anionic clay ratio could be varied by varying the reaction time or the amount of potassium permanganate used. - Graphical abstract: Nickel zinc hydroxyoxalate was reacted with potassium permanganate to get nickel zinc hydroxide birnessite composites in which the positive charges on the hydroxide layers are neutralized by the negative charges on birnessite layers. Highlights: Black-Right-Pointing-Pointer Anionic and cationic layered solid composites prepared. Black-Right-Pointing-Pointer Ni-Zn hydroxyoxalate reacted with KMnO{sub 4} to deposit MnO{sub 2} in the interlayer. Black-Right-Pointing-Pointer Birnessite layers coexist with anionic clay layers in the composites. Black-Right-Pointing-Pointer Birnessite/anionic clay ratio controlled by amount of KMnO{sub 4} used and reaction time.

  20. Improved photoelectrochemical water oxidation by the WO3/CuWO4 composite with a manganese phosphate electrocatalyst.

    PubMed

    Nam, Ki Min; Cheon, Eun Ah; Shin, Won Jung; Bard, Allen J

    2015-10-01

    We describe a composite of the n-type semiconductors for the photoelectrochemical oxygen evolution reaction (OER). A simple drop-casting technique of mixed precursors and a one-step annealing process were used in the synthesis of the WO3/CuWO4 composite. The composite showed improved photocurrent for water oxidation compared to either of the two compounds individually. We discuss possible electron-hole separation mechanisms in two semiconductors comprising a primary photon-absorbing semiconductor of CuWO4 with a secondary semiconductor of WO3. When the WO3/CuWO4 composite is simultaneously irradiated, the photogenerated hole from the WO3 valence band transfers to CuWO4, which results in an enhanced charge separation of CuWO4. Furthermore, the OER catalytic activity of manganese phosphate (MnPO) was compared to manganese oxide nanoparticles (Mn2O3) by electrochemical measurements, showing that the manganese phosphate was more efficient for the OER reaction. To investigate the effect of catalysts on semiconductors, manganese phosphate was deposited on the WO3/CuWO4 composite. The result demonstrates the promise of manganese phosphate for improving the photocurrent as well as the stability of the WO3/CuWO4 composite. PMID:26371544

  1. Molecular-Level Processes Governing the Interaction of Contaminants with Iron and Manganese Oxides - Final Report

    SciTech Connect

    Brown Jr., G. E.; Chambers, S. A.

    1999-10-31

    Many of the inorganic and organic contaminants present in sediments at DOE sites can be altered or destroyed by reduction and oxidation (redox) reactions occurring at mineral surfaces. A fundamental understanding of such redox processes provided by molecular-level studies on structurally and compositionally well-defined mineral surfaces will lead to: (i) improved models of contaminant fate and transport in geochemical systems, and (ii) optimized manipulation of these processes for remediation purposes. To contribute to this understanding, we will study, both experimentally and theoretically, redox processes involving three important contaminants - chromate ion, carbon tetrachloride, and trichloroethene TCE, on the following iron and manganese oxides - hematite, magnetite, maghemite, and pyrolusite. These oxides and their hydroxylated analogs commonly occur as coatings on minerals or as interfaces in the subsurface environment. Single-crystal surfaces of these oxides will be synthesized in carefully controlled fashion by molecular beam epitaxy. These surfaces, as well as high surface are powdered samples of these oxides, will be used in spectroscopic and kinetic experiments in both aqueous and gas phases. Our goal is to identify products and to determine the kinetics and mechanisms of surface-catalyzed redox reaction of Cr(VI) and CR(III), and the reductive dechlorination of carbon tetrachloride and TCE. The combination of theory and experiment will provide the base information needed to scale from the molecular level to the microscopic grain level minerals.

  2. Superstructures and Electronic Properties of Manganese-Phthalocyanine Molecules on Au(110) from Submonolayer Coverage to Ultrathin Molecular Films.

    PubMed

    Topyła, M; Néel, N; Kröger, J

    2016-07-12

    The adsorption of manganese-phthalocyanine molecules on Au(110) was investigated using a low-temperature scanning tunneling microscope. A rich variety of commensurate superstructures was observed upon increasing the molecule coverage from submonolayers to ultrathin films. All structures were associated with reconstructions of the Au(110) substrate. Molecules adsorbed in the second molecular layer exhibited negative differential conductance occurring symmetrically around zero bias voltage. A double-barrier tunneling model rationalized this observation in terms of a peaked molecular resonance at the Fermi energy together with a voltage drop across the molecular film. PMID:27322189

  3. Characterization of Newly-Formed Manganese (Hydr)oxides in Biofilms in Pinal Creek, Arizona

    NASA Astrophysics Data System (ADS)

    Gilbert, H.; Conklin, M.; O'Day, P.

    2003-12-01

    Active, biologically mediated precipitation of manganese (hydr)oxides (Mn-oxides) in Pinal Creek, Arizona, a stream with a history of high manganese levels due to historic mining practices, was studied to determine the identity of newly formed phases and their ability to sequester other metals. Packages of crushed grains of eight clean mineral substrates, quartz, ilmenite, microcline, rutile, magnetite, hematite and labradorite, were placed in Pinal Creek for one to three months. Glass slides were set out as well in order to characterize biofilm formation. After retrieval and drying, the coating distributions were characterized using scanning electron microscopy (SEM), energy dispersive analysis, and X-ray absorption spectroscopy. Morphologically, coating material developed on the different substrates after one month appeared similar to those developed after two and three months. Overall, the SEM images indicate poorly crystalline, aggregated particles that are small (less than a few microns in general) and lack geometric regularity, although size estimates are somewhat hindered by particle aggregation. The coatings that formed on the microscope slides are characterized as biofilms, as numerous microorganisms were observed using microscopy, both confocal and SEM. Samples were further characterized using extended x-ray absorption fine structure spectroscopy (EXAFS) on coatings that had been separated from mineral substrates. EXAFS spectra of material from rutile and quartz substrates and the biofilm were analyzed and fit, using a natural and synthetic birnessite compounds as reference spectra. This analysis suggests that the rutile, quartz, and biofilm samples are composed of a disordered Mn-oxide that is similar in local structure to a natural birnessite of low symmetry. The formation of disordered, poorly crystalline birnessite is important, as it is an extremely efficient metal scavenger and the interlayer vacancies in the birnessite structure aids in metal

  4. Mesostructured amorphous manganese oxides: facile synthesis and highly durable elimination of low-concentration NO at room temperature in air.

    PubMed

    Du, Yanyan; Hua, Zile; Huang, Weimin; Wu, Meiying; Wang, Min; Wang, Jin; Cui, Xiangzhi; Zhang, Lingxia; Chen, Hangrong; Shi, Jianlin

    2015-04-01

    At a high space velocity of 120 000 mL g(-1) h(-1) and a relative humidity of 50-90%, 98% removal of 10 ppm NO has been achieved for over 237 h and no sign of deactivation was observed with mesostructured amorphous manganese oxides (AMO), due to the prevention of the catalyst active sites from deactivation. PMID:25728967

  5. High-temperature oxidation behavior of two-phase iron-manganese-aluminum alloys

    SciTech Connect

    Liu, S.Y.; Lee, C.L.; Kao, C.H.; Perng, T.P.

    2000-04-01

    Oxidation behavior of two series of two-phase Fe-Mn-Al alloys in air up to 800 C was investigated. For the first series of alloys with various ratios of ferrite-austenite, the oxidation resistance of these alloys increased as the ferrite content increased. Two layers of oxide were formed mainly on the austenite grains, and oxidation in the ferrite phase was much less severe. The other layer of the scale on austenite was enriched with Mn and Fe, while Al was concentrated in the inner layer. For the second series of alloys with nearly the same contents of ferrite and C but various contents of Cr, the addition of Cr changed the oxidation characteristics and increased the oxidation resistance. Cr assisted the formation of a dense film of alumina (Al{sub 2}O{sub 3}) to prevent further oxidation.

  6. Synthesis and characterization of carbon black/manganese oxide air cathodes for zinc-air batteries: Effects of the crystalline structure of manganese oxides

    NASA Astrophysics Data System (ADS)

    Li, Po-Chieh; Hu, Chi-Chang; Noda, Hiroyuki; Habazaki, Hiroki

    2015-12-01

    Manganese oxides (MnOx) in α-, β-, γ-, δ-MnO2 phases, Mn3O4, Mn2O3, and MnOOH are synthesized for systematically comparing their electrocatalytic activity of the oxygen reduction reaction (ORR) in the Zn-air battery application. The optimal MnOx/XC-72 mass ratio for the ORR is equal to 1 and the oxide crystalline structure effect on the ORR is compared. The order of composites with respect to decreasing the ORR activity is: α-MnO2/XC-72 > γ-MnO2/XC-72 > β-MnO2/XC-72 > δ-MnO2/XC-72 > Mn2O3/XC-72 > Mn3O4/XC-72 > MnOOH/XC-72. The textural properties of MnOx are investigated by scanning electron microscopy (SEM), transmission electron microscopy (TEM), N2 adsorption/desorption isotherms with Brunauer-Emmett-Teller (BET) analysis, X-ray diffraction (XRD), and thermogravimetric analysis (TGA). Electrochemical studies include linear sweep voltammetry (LSV), rotating ring-disk electrode (RRDE) voltammetry, and the full-cell discharge test. The discharge peak power density of Zn-air batteries varies from 61.5 mW cm-2 (α-MnO2/XC-72) to 47.1 mW cm-2 (Mn3O4/XC-72). The maximum peak power density is 102 mW cm-2 for the Zn-air battery with an air cathode containing α-MnO2/XC-72 under an oxygen atmosphere when the carbon paper is 10AA. The specific capacity of all full-cell tests is higher than 750 mAh g-1 at all discharge current densities.

  7. Emulsion-derived lithium manganese oxide powder for positive electrodes in lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Lu, Chung-Hsin; Lin, Shang-Wei

    Lithium manganese oxide (LiMn 2O 4) used as a positive-electrode material in lithium-ion batteries is prepared by a new water-in-oil emulsion process. An aqueous solution containing lithium and manganese cations is emulsified in kerosene by adding sorbitan monooleate as the surfactant. When the precursor solution is agitated by a magnetic mixer, impure products are obtained. LiMn 2O 4 is formed along with residual Mn 2O 3 at elevated temperatures because of insufficient dispersion and mixing of the reactive cations. When a homogenizer with a greater agitation speed is used, however, a well-mixed precursor solution is prepared, and pure LiMn 2O 4 with a Fd 3 m structure is synthesized after calcination at 800°C for 1 h. LiMn 2O 4 powder prepared by the homogenizer has higher crystallinity, smaller particle size, and narrower size distribution than that prepared by the magnetic stirrer. Compared with powder prepared by the solid-state method, the LiMn 2O 4 powder exhibits smaller particle size and less agglomeration. Moreover, the emulsion process significantly shortens the heating time required. The prepared LiMn 2O 4 powder has a high discharge capacity (120.4 mA h g -1) on the first cycle and good cycleability.

  8. Graphene oxide/manganese ferrite nanohybrids for magnetic resonance imaging, photothermal therapy and drug delivery.

    PubMed

    Yang, Yan; Shi, Haili; Wang, Yapei; Shi, Benzhao; Guo, Linlin; Wu, Dongmei; Yang, Shiping; Wu, Huixia

    2016-01-01

    Superparamagnetic manganese ferrite (MnFe2O4) nanoparticles have been deposited on graphene oxide (GO) by the thermal decomposition of manganese (II) acetylacetonate and iron (III) acetylacetonate precursors in triethylene glycol. The resulting GO/MnFe2O4 nanohybrids show very low cytotoxicity, negligible hemolytic activity, and imperceptible in vivo toxicity. In vitro and in vivo magnetic resonance imaging experiments demonstrate that GO/MnFe2O4 nanohybrids could be used as an effective T2 contrast agent. The strong optical absorbance in the near-infrared (NIR) region and good photothermal stability of GO/MnFe2O4 nanohybrids result in the highly efficient photothermal ablation of cancer cells. GO/MnFe2O4 nanohybrids can be further loaded with doxorubicin (DOX) by π-π conjugate effect for chemotherapy. DOX release from GO/MnFe2O4 is significantly influenced by pH and can be triggered by NIR laser. The enhanced cancer cell killing by GO/MnFe2O4/DOX composites has been achieved when irradiated with near-infrared light, suggesting that the nanohybrids could deliver both DOX chemotherapy and photothermal therapy with a synergistic effect. PMID:26296777

  9. Preparation of poly(aniline-co-o-anisidine)-intercalated mesostructured manganese oxide composites by exchange reaction

    SciTech Connect

    Wang Gengchao Yang Zhenyu; Li Xingwei; Li Chunzhong; Yuan Weikang

    2008-08-04

    Layered mesostructured manganese oxide (mesostructured MnO{sub 2}) was synthesized using manganese chloride and lithium hydroxide as the raw materials and cetyltrimethylammonium bromide (CTAB) as the structure-directing agent. Poly(aniline-co-o-anisidine)-intercalated mesostructured MnO{sub 2} composites (P(An-co-oAs)/MnO{sub 2}) were synthesized in an organic solvent through the exchange reaction between the CTAB in MnO{sub 2} gallery and the P(An-co-oAs). The interlayer spacing (I{sub c} values) of mesostructured MnO{sub 2} enlarged from 2.52 to 4.41 nm as the added amount of P(An-co-oAs) increased from 0 to 0.5 g per 0.5 g of mesostructured MnO{sub 2}. The regularity of the layered structure of the composites was firstly decreased due to intercalation of low amounts of P(An-co-oAs). However, with increasing the intercalated amount of P(An-co-oAs) the layered structure of the composites becomes more regular. The electrical conductivity of the composites is 10{sup 2} to 10{sup 3} times higher than that of the mesostructured MnO{sub 2}.

  10. Sorption of Ferric Iron from Ferrioxamine B to Synthetic and Biogenic Layer Type Manganese Oxides

    NASA Astrophysics Data System (ADS)

    Duckworth, O.; John, B.; Sposito, G.

    2006-12-01

    Siderophores are biogenic chelating agents produced in terrestrial and marine environments to increase the bioavailablity of ferric iron. Recent work has suggested that both aqueous and solid-phase Mn(III) may affect siderophore-mediated iron transport, but no information appears to be available about the effect of solid-phase Mn(IV). To probe the effects of predominantly Mn(IV) oxides, we studied the sorption reaction of ferrioxamine B [Fe(III)HDFOB+, an Fe(III) chelate of the trihydroxamate siderophore desferrioxamine B (DFOB)] with two synthetic birnessites [layer type Mn(III, IV) oxides] and a biogenic birnessite produced by Pseudomonas putida MnB1. We found that all of these predominantly Mn(IV) oxides greatly reduced the aqueous concentration of Fe(III)HDFOB+ over at pH 8. After 72 hours equilibration time, the sorption behavior for the synthetic birnessites could be accurately described by a Langmuir isotherm; for the biogenic oxide, a Freundlich isotherm was best utilized to model the sorption data. To study the molecular nature of the interaction between the Fe(III)HDFOB+ complex and the oxide surface, Fe K-edge extended X-ray absorption fine structure (EXAFS) spectroscopy was employed. Analysis of the EXAFS spectra indicated that Fe(III) associated with the Mn(IV) oxides is not complexed by DFOB as in solution, but instead Fe(III) is specifically adsorbed to into the mineral structure at multiple sites with no evidence of DFOB complexation, thus indicating that the Mn(IV) oxides displaced Fe(III) from the siderophore complex. These results indicate that manganese oxides, including biominerals, may strongly sequester iron from soluble ferric complexes and thus may play a significant role in the biogeochemical cycling of iron in marine and terrestrial environments.

  11. Purification and Characterization of the Manganese(II) Oxidizing Protein from Erythrobacter sp. SD-21

    NASA Astrophysics Data System (ADS)

    Nakama, K. R.; Lien, A.; Johnson, H. A.

    2013-12-01

    The manganese(II) oxidizing protein (Mop) found in the alpha-proteobacterium Erythrobacter sp. SD-21 catalyzes the formation of insoluble Mn(III/IV) oxides from soluble Mn(II). These Mn(III/IV) oxides formed are one of the strongest naturally occurring oxides, next to oxygen, and can be used to adsorb and oxidize toxic chemicals from the surrounding environment. Because of the beneficial use in the treatment of contaminated sources, the mechanism and biochemical properties of this novel enzyme are being studied. Due to low expression levels in the native host strain, purification of Mop has been problematic. To overcome this problem the gene encoding Mop, mopA, was cloned from the native host into a C-terminal histidine tag vector and expressed in Escherichia coli cells. Affinity chromatography under denaturing conditions have been applied in attempts to purify an active Mop. Western blots have confirmed that the protein is being expressed and is at the expected size of 250 kDa. Preliminary characterization on crude extract containing Mop has shown a Km and vmax value of 2453 uM and 0.025 uM min-1, respectively. Heme and pyrroloquinoline quinone can stimulate Mn(II) oxidizing activity, but hydrogen peroxide does not affect activity, despite the sequence similarity to animal heme peroxidase proteins. Research has been shown that calcium is essential for Mop activity. Purifying an active Mn(II) oxidizing protein will allow for a better understanding behind the enigmatic process of Mn(II) oxidation.

  12. Understanding the role of manganese dioxide in the oxidation of phenolic compounds by aqueous permanganate.

    PubMed

    Jiang, Jin; Gao, Yuan; Pang, Su-Yan; Lu, Xue-Ting; Zhou, Yang; Ma, Jun; Wang, Qiang

    2015-01-01

    Recent studies have shown that manganese dioxide (MnO2) can significantly accelerate the oxidation kinetics of phenolic compounds such as triclosan and chlorophenols by potassium permanganate (Mn(VII)) in slightly acidic solutions. However, the role of MnO2 (i.e., as an oxidant vs catalyst) is still unclear. In this work, it was demonstrated that Mn(VII) oxidized triclosan (i.e., trichloro-2-phenoxyphenol) and its analogue 2-phenoxyphenol, mainly generating ether bond cleavage products (i.e., 2,4-dichlorophenol and phenol, respectively), while MnO2 reacted with them producing appreciable dimers as well as hydroxylated and quinone-like products. Using these two phenoxyphenols as mechanistic probes, it was interestingly found that MnO2 formed in situ or prepared ex situ greatly accelerated the kinetics but negligibly affected the pathways of their oxidation by Mn(VII) at acidic pH 5. The yields (R) of indicative products 2,4-dichlorophenol and phenol from their respective probes (i.e., molar ratios of product formed to probe lost) under various experimental conditions were quantified. Comparable R values were obtained during the treatment by Mn(VII) in the absence vs presence of MnO2. Meanwhile, it was confirmed that MnO2 could accelerate the kinetics of Mn(VII) oxidation of refractory nitrophenols (i.e., 2-nitrophenol and 4-nitrophenol), which otherwise showed negligible reactivity toward Mn(VII) and MnO2 individually, and the effect of MnO2 was strongly dependent upon its concentration as well as solution pH. These results clearly rule out the role of MnO2 as a mild co-oxidant and suggest a potential catalytic effect on Mn(VII) oxidation of phenolic compounds regardless of their susceptibility to oxidation by MnO2. PMID:25437924

  13. Description of the first fungal dye-decolorizing peroxidase oxidizing manganese(II).

    PubMed

    Fernández-Fueyo, Elena; Linde, Dolores; Almendral, David; López-Lucendo, María F; Ruiz-Dueñas, Francisco J; Martínez, Angel T

    2015-11-01

    Two phylogenetically divergent genes of the new family of dye-decolorizing peroxidases (DyPs) were found during comparison of the four DyP genes identified in the Pleurotus ostreatus genome with over 200 DyP genes from other basidiomycete genomes. The heterologously expressed enzymes (Pleos-DyP1 and Pleos-DyP4, following the genome nomenclature) efficiently oxidize anthraquinoid dyes (such as Reactive Blue 19), which are characteristic DyP substrates, as well as low redox-potential dyes (such as 2,2-azinobis-(3-ethylbenzothiazoline-6-sulfonic acid)) and substituted phenols. However, only Pleos-DyP4 oxidizes the high redox-potential dye Reactive Black 5, at the same time that it displays high thermal and pH stability. Unexpectedly, both enzymes also oxidize Mn(2+) to Mn(3+), albeit with very different catalytic efficiencies. Pleos-DyP4 presents a Mn(2+) turnover (56 s(-1)) nearly in the same order of the two other Mn(2+)-oxidizing peroxidase families identified in the P. ostreatus genome: manganese peroxidases (100 s(-1) average turnover) and versatile peroxidases (145 s(-1) average turnover), whose genes were also heterologously expressed. Oxidation of Mn(2+) has been reported for an Amycolatopsis DyP (24 s(-1)) and claimed for other bacterial DyPs, albeit with lower activities, but this is the first time that Mn(2+) oxidation is reported for a fungal DyP. Interestingly, Pleos-DyP4 (together with ligninolytic peroxidases) is detected in the secretome of P. ostreatus grown on different lignocellulosic substrates. It is suggested that generation of Mn(3+) oxidizers plays a role in the P. ostreatus white-rot lifestyle since three different families of Mn(2+)-oxidizing peroxidase genes are present in its genome being expressed during lignocellulose degradation. PMID:25967658

  14. Coprecipitation mechanisms and products in manganese oxidation in the presence of cadmium

    USGS Publications Warehouse

    Hem, J.D.; Lind, Carol J.

    1991-01-01

    Manganese oxidation products were precipitated in an aerated open-aqueous system where a continuous influx of mixed Mn2+ and Cd2+ solution was supplied and pH was maintained with an automated pH-stat adding dilute NaOH. X-ray diffraction and electron diffraction identified the solids produced as mixtures of Cd2Mn34+O8, Mn2+2Mn4+3O8, MnO2 (ramsdellite), and CdCO3. Mean oxidation numbers of the total precipitated Mn as great as 3.6 were reached during titrations. During subsequent aging in solution, oxidation numbers between 3.8 and 3.9 were reached in some precipitates in less than 40 days. Conditional oxidation rate constants calculated from a crystal-growth equation applied to titration data showed the overall precipitation rate, without considering manganese oxidation state in the precipitate, was increased by a factor of ~4 to ~7 when the mole ratio (Cd/Mn + Cd) of cadmium in the feed solution was 0.40 compared with rate constants for hausmannite (Mn2+Mn23+O4 precipitation under similar conditions but without accessory metals. Kinetic experiments were made to test effects of various Cd/Mn + Cd mole ratios and rates of addition of the feed solution, different temperatures from 5.0 to 35??C, and pH from 8.0 to 9.0. Oxidation rates were slower when the Cd mole ratio was less than 0.40. The rate increased by a factor of ~10 when pH was raised one-half unit. The effect of temperature on the rate constants was also substantial, but the meaning of this is uncertain because the rate of formation of Mn4+ oxide in the absence of Cd or other accessory metals was too slow to be measurable in titration experiments. The increased rate of Mn4+ oxide formation in the presence of Cd2+ can be ascribed to the formation of a labile adsorbed intermediate, CdMn2O4 Int, an analog of hausmannite, formed on precipitate surfaces at the beginning of the oxidation process. The increased lability of this structure, resulting from coordination-chemical behavior of Cd2+ during the titration

  15. Electro-deposition of superconductor oxide films

    DOEpatents

    Bhattacharya, Raghu N.

    2001-01-01

    Methods for preparing high quality superconducting oxide precursors which are well suited for further oxidation and annealing to form superconducting oxide films. The method comprises forming a multilayered superconducting precursor on a substrate by providing an electrodeposition bath comprising an electrolyte medium and a substrate electrode, and providing to the bath a plurality of precursor metal salts which are capable of exhibiting superconducting properties upon subsequent treatment. The superconducting precursor is then formed by electrodepositing a first electrodeposited (ED) layer onto the substrate electrode, followed by depositing a layer of silver onto the first electrodeposited (ED) layer, and then electrodepositing a second electrodeposited (ED) layer onto the Ag layer. The multilayered superconducting precursor is suitable for oxidation at a sufficient annealing temperature in air or an oxygen-containing atmosphere to form a crystalline superconducting oxide film.

  16. Mesoporous iron–manganese oxides for sulphur mustard and soman degradation

    SciTech Connect

    Štengl, Václav; Grygar, Tomáš Matys; Bludská, Jana; Opluštil, František; Němec, Tomáš

    2012-12-15

    Graphical abstract: Display Omitted Highlights: ► New nanodispersive materials based on Fe and Mn oxides for degradations of warfare agents. ► The best activities for the degradation of sulphur mustard (97.9% in 64 min) and soman (97.9% in 64 min). ► One pot synthesis with friendly transformed to industrial conditions. -- Abstract: Substituted iron(III)–manganese(III, IV) oxides, ammonio-jarosite and birnessite, were prepared by a homogeneous hydrolysis of potassium permanganate and iron(III) sulphate with 2-chloroacetamide and urea, respectively. Synthesised oxides were characterised using Brunauer–Emmett–Teller (BET) surface area and Barrett–Joiner–Halenda porosity (BJH), X-ray diffraction (XRD), infrared spectroscopy (IR), Raman spectroscopy and scanning electron microscopy (SEM). The oxides were taken for an experimental evaluation of their reactivity against sulphur mustard (HD) and soman (GD). When ammonio-jarosite formation is suppressed by adding urea to the reaction mixture, the reaction products are mixtures of goethite, schwertmannite and ferrihydrite, and their degradation activity against soman considerably increases. The best activities for the degradation of sulphur mustard (97.9% in 64 min) and soman (97.9% in 64 min) were observed for FeMn{sub 7}5 with 32.6 wt.% Fe (36.8 wt.% Mn) and FeMn{sub 3}7U with 60.8 wt.% Fe (10.1 wt.% Mn) samples, respectively.

  17. Promotion effect of manganese oxide on the electrocatalytic activity of Pt/C for methanol oxidation in acid medium

    NASA Astrophysics Data System (ADS)

    Abdel Hameed, R. M.; Fetohi, Amani E.; Amin, R. S.; El-Khatib, K. M.

    2015-12-01

    The modification of Pt/C by incorporating metal oxides for electrocatalytic oxidation of methanol has gained major attention because of the efficiency loss during the course of long-time operation. This work describes the preparation of Pt-MnO2/C electrocatalysts through a chemical route using ethylene glycol or a mixture of ethylene glycol and sodium borohydride as a reducing agent. The crystallite structure and particle size of synthesized electrocatalysts are determined using X-ray diffraction (XRD) and transmission electron microscopy (TEM). The addition of MnO2 improves the dispersion of Pt nanoparticles. The electrocatalytic activity of Pt-MnO2/C towards methanol oxidation in H2SO4 solution is investigated using cyclic voltammetry and electrochemical impedance spectroscopy. The onset potential value of methanol oxidation peak is negatively shifted by 169 mV when MnO2 is introduced to Pt/C. Moreover, the charge transfer resistance value at Pt-MnO2/C is about 10 times as low as that at Pt/C. Chronoamperometry and chronopotentiometry show that CO tolerance is greatly improved at Pt-MnO2/C. The increased electrocatalytic activity and enhanced ability to clean platinum surface elect manganese oxide as a suitable promoter for the anode performance in direct methanol fuel cells (DMFCs).

  18. Heterologous Expression and Characterization of the Manganese-Oxidizing Protein from Erythrobacter sp. Strain SD21

    PubMed Central

    Nakama, Katherine; Medina, Michael; Lien, Ahn; Ruggieri, Jordan; Collins, Krystle

    2014-01-01

    The manganese (Mn)-oxidizing protein (MopA) from Erythrobacter sp. strain SD21 is part of a unique enzymatic family that is capable of oxidizing soluble Mn(II). This enzyme contains two domains, an animal heme peroxidase domain, which contains the catalytic site, followed by a C-terminal calcium binding domain. Different from the bacterial Mn-oxidizing multicopper oxidase enzymes, little is known about MopA. To gain a better understanding of MopA and its role in Mn(II) oxidation, the 238-kDa full-length protein and a 105-kDa truncated protein containing only the animal heme peroxidase domain were cloned and heterologously expressed in Escherichia coli. Despite having sequence similarity to a peroxidase, hydrogen peroxide did not stimulate activity, nor was activity significantly decreased in the presence of catalase. Both pyrroloquinoline quinone (PQQ) and hemin increased Mn-oxidizing activity, and calcium was required. The Km for Mn(II) of the full-length protein in cell extract was similar to that of the natively expressed protein, but the Km value for the truncated protein in cell extract was approximately 6-fold higher than that of the full-length protein, suggesting that the calcium binding domain may aid in binding Mn(II). Characterization of the heterologously expressed MopA has provided additional insight into the mechanism of bacterial Mn(II) oxidation, which will aid in understanding the role of MopA and Mn oxidation in bioremediation and biogeochemical cycling. PMID:25172859

  19. Heterologous expression and characterization of the manganese-oxidizing protein from Erythrobacter sp. strain SD21.

    PubMed

    Nakama, Katherine; Medina, Michael; Lien, Ahn; Ruggieri, Jordan; Collins, Krystle; Johnson, Hope A

    2014-11-01

    The manganese (Mn)-oxidizing protein (MopA) from Erythrobacter sp. strain SD21 is part of a unique enzymatic family that is capable of oxidizing soluble Mn(II). This enzyme contains two domains, an animal heme peroxidase domain, which contains the catalytic site, followed by a C-terminal calcium binding domain. Different from the bacterial Mn-oxidizing multicopper oxidase enzymes, little is known about MopA. To gain a better understanding of MopA and its role in Mn(II) oxidation, the 238-kDa full-length protein and a 105-kDa truncated protein containing only the animal heme peroxidase domain were cloned and heterologously expressed in Escherichia coli. Despite having sequence similarity to a peroxidase, hydrogen peroxide did not stimulate activity, nor was activity significantly decreased in the presence of catalase. Both pyrroloquinoline quinone (PQQ) and hemin increased Mn-oxidizing activity, and calcium was required. The Km for Mn(II) of the full-length protein in cell extract was similar to that of the natively expressed protein, but the Km value for the truncated protein in cell extract was approximately 6-fold higher than that of the full-length protein, suggesting that the calcium binding domain may aid in binding Mn(II). Characterization of the heterologously expressed MopA has provided additional insight into the mechanism of bacterial Mn(II) oxidation, which will aid in understanding the role of MopA and Mn oxidation in bioremediation and biogeochemical cycling. PMID:25172859

  20. Aerobic oxidation of anthracene in the presence of manganese porphyrinates and NaBH/sub 4/ reducing agent

    SciTech Connect

    Lukashova, E.A.; Solov'ev, A.B.; Chugreev, A.L.; Enikolopyan, N.S.

    1987-12-01

    The authors investigate the kinetics of anthracene oxidation by molecular oxygen in the presence of manganese, iron, and cobalt porphyrinate catalysts and a sodium borohydride reducing agent at room temperature in solutions of ethanol or ethanol with chloroform and benzene. Effective rate constants for the reactions are determined based on the amount of anthraquinone formed in the reaction. In all cases with the exception of cobalt tetraphenylporphyrinate the only oxidation product was anthraquinone. Its structure was verified by NMR and IR spectroscopy.

  1. Cation Intercalation in Manganese Oxide Nanosheets: Effects on Lithium and Sodium Storage.

    PubMed

    Lu, Ke; Hu, Ziyu; Xiang, Zhonghua; Ma, Jizhen; Song, Bin; Zhang, Jintao; Ma, Houyi

    2016-08-22

    The rapid development of advanced energy-storage devices requires significant improvements of the electrode performance and a detailed understanding of the fundamental energy-storage processes. In this work, the self-assembly of two-dimensional manganese oxide nanosheets with various metal cations is introduced as a general and effective method for the incorporation of different guest cations and the formation of sandwich structures with tunable interlayer distances, leading to the formation of 3D Mx MnO2 (M=Li, Na, K, Co, and Mg) cathodes. For sodium and lithium storage, these electrode materials exhibited different capacities and cycling stabilities. The efficiency of the storage process is influenced not only by the interlayer spacing but also by the interaction between the host cations and shutter ions, confirming the crucial role of the cations. These results provide promising ideas for the rational design of advanced electrodes for Li and Na storage. PMID:27458045

  2. Reaction of Formic Acid over Amorphous Manganese Oxide Catalytic Systems: An In Situ Study

    SciTech Connect

    Durand, Jason; Senanayake, Sanjaya D; Mullins, David R; Suib, Steven

    2010-01-01

    The interaction of formic acid with amorphous manganese oxide (AMO) is investigated using in situ photoelectron and infrared spectroscopy techniques. Soft X-ray photoelectron spectroscopy (sXPS) and in situ FTIR illustrate two possible modes of formate bound species at the AMO surface. Two peaks in the IR region from 1340-1390 cm{sup -1} are indicative of formate species bound to the surface in a bidentate configuration. However, a 224 cm{sup -1} band gap between v{sub s}OCO and v{sub as}OCO suggests formate is bound in a bridging configuration. Temperature-programmed desorption studies confirm the formate bound species desorbs as carbon dioxide from the surface at multiple binding sites. At temperatures above 700 K, the presence of K{sup +} {hor_ellipsis} OC complex suggests the bound species interacts at vacant sites related to framework oxygen and cation mobility.

  3. Reaction of Formic Acid over Amorphous Manganese Oxide Catalytic Systems: An In Situ Study

    SciTech Connect

    J Durand; S Senanayake; S Suib; D Mullins

    2011-12-31

    The interaction of formic acid with amorphous manganese oxide (AMO) is investigated using in situ photoelectron and infrared spectroscopy techniques. Soft X-ray photoelectron spectroscopy (sXPS) and in situ FTIR illustrate two possible modes of formate bound species at the AMO surface. Two peaks in the IR region from 1340-1390 cm{sup -1} are indicative of formate species bound to the surface in a bidentate configuration. However, a 224 cm{sup -1} band gap between v{sub s}OCO and v{sub as}OCO suggests formate is bound in a bridging configuration. Temperature-programmed desorption studies confirm the formate bound species desorbs as carbon dioxide from the surface at multiple binding sites. At temperatures above 700 K, the presence of K{sup +} {hor_ellipsis} OC complex suggests the bound species interacts at vacant sites related to framework oxygen and cation mobility.

  4. Theory of chemical bonds in metalloenzymes - Manganese oxides clusters in the oxygen evolution center -

    NASA Astrophysics Data System (ADS)

    Yamaguchi, K.; Shoji, M.; Saito, T.; Isobe, H.; Yamada, S.; Nishihara, S.; Kawakami, T.; Kitagawa, Y.; Yamanaka, S.; Okumura, M.

    2012-12-01

    In early 1980 we have initiated broken-symmetry (BS) MO theoretical calculations of transition-metal oxo species M = O (M = Ti,V,Cr,Mn,Fe,Ni,Cu) to elucidate the nature of dσ-pσ and dπ-pπ bonds. It has been concluded that high-valent M = O species such as [Mn(IV) = O]2+ and [Fe(IV) = O]2+ exhibit electrophilic property in a sharp contrast with nucleophilic character of low-valent M = O bonds: [M(II)O2-]0, and closed-shell dπ-pπ bonds of high-valent M = O species often suffer the triplet-instability, giving rise to open-shell (BS) configurations with significant metal-diradical (MDR) character: •M-O•: note that these bonds are therefore regarded as typical examples of strongly correlated electron systems. Because of the MDR character, 1,4-metal diradical mechanism was indeed preferable to four-centered mechanism in the case of addition reaction of naked Mn(IV) = O to ethylene. Recently the manganese-oxo species have been receiving renewed interest in relation to catalytic cycle of oxygen evolution from water molecules in the photosynthesis II (PSII) system. Accumulated experimental results indicate that this process is catalyzed with four manganese oxide clusters coordinated with calcium ion (CaMn4O4). Past decade we have performed BS MO theoretical investigations of manganese oxide clusters related to CaMn4O4. These calculations have elucidated that high-valent Mn(X) = O (X = IV,V) bonds exhibit intermediate MDR character (y=40-60%) in the case of total low-spin (LS) configuration but the MDR character decreases with coordination of Ca2+ and water molecules. While the MDR character of the Mn-oxo bonds becomes very high at the high-spin (HS) configuration. Our computational results enabled us to propose two possible mechanisms on the theoretical ground: (A) electrophilic (EP) mechanism and (B) radical coupling (RC) mechanism. The theoretical results indicate that the EP mechanism is preferable for the low-spin (LS) state in polar media like in the protein

  5. Rapid (<3 min) microwave synthesis of block copolymer templated ordered mesoporous metal oxide and carbonate films using nitrate-citric acid systems.

    PubMed

    Zhang, Yuanzhong; Bhaway, Sarang M; Wang, Yi; Cavicchi, Kevin A; Becker, Matthew L; Vogt, Bryan D

    2015-03-25

    Rapid chemical transformation from micelle templated precursors (metal nitrate and citric acid) to ordered mesoporous metal carbonates and oxides is demonstrated using microwave heating for cobalt, copper, manganese and zinc. Without aging requirements, <3 min of microwave processing yields highly ordered mesoporous films. PMID:25714045

  6. Recovery of manganese oxides from spent alkaline and zinc-carbon batteries. An application as catalysts for VOCs elimination.

    PubMed

    Gallegos, María V; Falco, Lorena R; Peluso, Miguel A; Sambeth, Jorge E; Thomas, Horacio J

    2013-06-01

    Manganese, in the form of oxide, was recovered from spent alkaline and zinc-carbon batteries employing a biohydrometallurgy process, using a pilot plant consisting in: an air-lift bioreactor (containing an acid-reducing medium produced by an Acidithiobacillus thiooxidans bacteria immobilized on elemental sulfur); a leaching reactor (were battery powder is mixed with the acid-reducing medium) and a recovery reactor. Two different manganese oxides were recovered from the leachate liquor: one of them by electrolysis (EMO) and the other by a chemical precipitation with KMnO4 solution (CMO). The non-leached solid residue was also studied (RMO). The solids were compared with a MnOx synthesized in our laboratory. The characterization by XRD, FTIR and XPS reveal the presence of Mn2O3 in the EMO and the CMO samples, together with some Mn(4+) cations. In the solid not extracted by acidic leaching (RMO) the main phase detected was Mn3O4. The catalytic performance of the oxides was studied in the complete oxidation of ethanol and heptane. Complete conversion of ethanol occurs at 200°C, while heptane requires more than 400°C. The CMO has the highest oxide selectivity to CO2. The results show that manganese oxides obtained using spent alkaline and zinc-carbon batteries as raw materials, have an interesting performance as catalysts for elimination of VOCs. PMID:23562448

  7. Chemical and structural investigations of the incorporation of metal manganese into ruthenium thin films for use as copper diffusion barrier layers

    SciTech Connect

    McCoy, A. P.; Casey, P.; Bogan, J.; Hughes, G.; Lozano, J. G.; Nellist, P. D.

    2012-12-03

    The incorporation of manganese into a 3 nm ruthenium thin-film is presented as a potential mechanism to improve its performance as a copper diffusion barrier. Manganese ({approx}1 nm) was deposited on an atomic layer deposited Ru film, and the Mn/Ru/SiO{sub 2} structure was subsequently thermally annealed. X-ray photoelectron spectroscopy studies reveal the chemical interaction of Mn with the SiO{sub 2} substrate to form manganese-silicate (MnSiO{sub 3}), implying the migration of the metal through the Ru film. Electron energy loss spectroscopy line profile measurements of the intensity of the Mn signal across the Ru film confirm the presence of Mn at the Ru/SiO{sub 2} interface.

  8. Associations among environmental exposure to manganese, neuropsychological performance, oxidative damage and kidney biomarkers in children.

    PubMed

    Nascimento, Sabrina; Baierle, Marília; Göethel, Gabriela; Barth, Anelise; Brucker, Natália; Charão, Mariele; Sauer, Elisa; Gauer, Bruna; Arbo, Marcelo Dutra; Altknecht, Louise; Jager, Márcia; Dias, Ana Cristina Garcia; de Salles, Jerusa Fumagalli; Saint' Pierre, Tatiana; Gioda, Adriana; Moresco, Rafael; Garcia, Solange Cristina

    2016-05-01

    Environmental exposure to manganese (Mn) results in several toxic effects, mainly neurotoxicity. This study investigated associations among Mn exposure, neuropsychological performance, biomarkers of oxidative damage and early kidney dysfunction in children aged 6-12 years old. Sixty-three children were enrolled in this study, being 43 from a rural area and 20 from an urban area. Manganese was quantified in blood (B-Mn), hair (H-Mn) and drinking water using inductively coupled plasma mass spectrometry (ICP-MS). The neuropsychological functions assessed were attention, perception, working memory, phonological awareness and executive functions - inhibition. The Intelligence quotient (IQ) was also evaluated. The biomarkers malondialdehyde (MDA), protein carbonyls (PCO), δ-aminolevulinate dehydratase (ALA-D), reactivation indexes with dithiothreitol (ALA-RE/DTT) and ZnCl2 (ALA-RE/ZnCl2), non-protein thiol groups, as well as microalbuminuria (mALB) level and N-acetyl-β-D-glucosaminidase (NAG) activity were assessed. The results demonstrated that Mn levels in blood, hair and drinking water were higher in rural children than in urban children (p<0.01). Adjusted for potential confounding factors, IQ, age, gender and parents' education, significant associations were observed mainly between B-Mn and visual attention (β=0.649; p<0.001). Moreover, B-Mn was negatively associated with visual perception and phonological awareness. H-Mn was inversely associated with working memory, and Mn levels from drinking water with written language and executive functions - inhibition. Rural children showed a significant increase in oxidative damage to proteins and lipids, as well as alteration in kidney function biomarkers (p<0.05). Moreover, significant associations were found between B-Mn, H-Mn and Mn levels in drinking water and biomarkers of oxidative damage and kidney function, besides between some oxidative stress biomarkers and neuropsychological tasks (p<0.05). The findings of this

  9. Graphene oxide film as solid lubricant.

    PubMed

    Liang, Hongyu; Bu, Yongfeng; Zhang, Junyan; Cao, Zhongyue; Liang, Aimin

    2013-07-10

    As a layered material, graphene oxide (GO) film is a good candidate for improving friction and antiwear performance of silicon-based MEMS devices. Via a green electrophoretic deposition (EPD) approach, GO films with tunable thickness in nanoscale are fabricated onto silicon wafer in a water solution. The morphology, microstructure, and mechanical properties as well as the friction coefficient and wear resistance of the films were investigated. The results indicated that the friction coefficient of silicon wafer was reduced to 1/6 its value, and the wear volume was reduced to 1/24 when using GO film as solid lubricant. These distinguished tribology performances suggest that GO films are expected to be good solid lubricants for silicon-based MEMS/NEMS devices. PMID:23786494

  10. Structure-property relationships in manganese oxide--mesoporous silica nanoparticles used for T1-weighted MRI and simultaneous anti-cancer drug delivery.

    PubMed

    Chen, Yu; Chen, Hangrong; Zhang, Shengjian; Chen, Feng; Sun, Shikuan; He, Qianjun; Ma, Ming; Wang, Xia; Wu, Huixia; Zhang, Lingxia; Zhang, Linlin; Shi, Jianlin

    2012-03-01

    The extremely low longitudinal relaxivity (r(1)) of manganese oxide has severely impeded their substitution for cytotoxic gadolinium-based contrast agents for safe clinical magnetic resonance imaging (MRI). Here, we report on a synthetic strategy of chemical oxidation/reduction reaction in-situ in mesopores, followed by hydrogen reduction, for the fabrication of non-toxic manganese oxide/MSNs-based MRI-T(1) contrast agents with highly comparable imaging performance to commercial Gd-based agents. This strategy involves a "soft-templating" process to prepare mesoporous silica nanoparticles, in-situ reduction of MnO(4)(-) by the "soft templates" in mesopores and heat treatment under reducing atmosphere, to disperse manganese oxide nanoparticles within mesopores. This special nanostructure combines the merits of nanopores for maximum manganese paramagnetic center accessibility for water molecules for enhanced MRI performance and encapsulation/sustained release/intracellular delivery of drugs. The synthesized manganese oxide/MSNs were successfully assessed as a high performance contrast agent for MRI-T(1) both in intro and in vivo, and meanwhile, was also demonstrated as an effective anti-cancer drug delivery (doxorubicin) vehicle, therefore, a family of manganese-based theranostics was successfully demonstrated based on the manganese oxide/MSNs composite. PMID:22177841

  11. Metals, Oxidative Stress and Neurodegeneration: A focus on Iron, Manganese and Mercury

    PubMed Central

    Farina, Marcelo; Avila, Daiana Silva; da Rocha, João Batista Teixeira

    2013-01-01

    Essential metals are crucial for the maintenance of cell homeostasis. Among the 23 elements that have known physiological functions in humans, 12 are metals, including iron (Fe) and manganese (Mn). Nevertheless, excessive exposure to these metals may lead to pathological conditions, including neurodegeneration. Similarly, exposure to metals that do not have known biological functions, such as mercury (Hg), also present great health concerns. This reviews focuses on the neurodegenerative mechanisms and effects of Fe, Mn and Hg. Oxidative stress (OS), particularly in mitochondria, is a common feature of Fe, Mn and Hg toxicity. However, the primary molecular targets triggering OS are distinct. Free cationic iron is a potent pro-oxidant and can initiate a set of reactions that form extremely reactive products, such as OH•. Mn can oxidize dopamine (DA), generating reactive species and also affect mitochondrial function, leading to accumulation of metabolites and culminating with OS. Cationic Hg forms have strong affinity for nucleophiles, such as –SH and –SeH. Therefore, they target critical thiol- and selenol-molecules with antioxidant properties. Finally, we address the main sources of exposure to these metals, their transport mechanisms into the brain, and therapeutic modalities to mitigate their neurotoxic effects. PMID:23266600

  12. Manganese Doping of Magnetic Iron Oxide Nanoparticles: Tailoring Surface Reactivity for a Regenerable Heavy Metal Sorbent

    SciTech Connect

    Warner, Cynthia L.; Chouyyok, Wilaiwan; Mackie, Katherine E.; Neiner, Doinita; Saraf, Laxmikant; Droubay, Timothy C.; Warner, Marvin G.; Addleman, Raymond S.

    2012-02-28

    A method for tuning the analyte affinity of magnetic, inorganic nanostructured sorbents for heavy metal contaminants is described. The manganese-doped iron oxide nanoparticle sorbents have a remarkably high affinity compared to the precursor material. Sorbent affinity can be tuned toward an analyte of interest simply by adjustment of the dopant quantity. The results show that following the Mn doping process there is a large increase in affinity and capacity for heavy metals (i.e., Co, Ni, Zn, As, Ag, Cd, Hg, and Tl). Capacity measurements were carried out for the removal of cadmium from river water and showed significantly higher loading than the relevant commercial sorbents tested for comparison. The reduction in Cd concentration from 100 ppb spiked river water to 1 ppb (less than the EPA drinking water limit of 5 ppb for Cd) was achieved following treatment with the Mn-doped iron oxide nanoparticles. The Mn-doped iron oxide nanoparticles were able to load 1 ppm of Cd followed by complete stripping and recovery of the Cd with a mild acid wash. The Cd loading and stripping is shown to be consistent through multiple cycles with no loss of sorbent performance.

  13. High quality transparent conducting oxide thin films

    DOEpatents

    Gessert, Timothy A.; Duenow, Joel N.; Barnes, Teresa; Coutts, Timothy J.

    2012-08-28

    A transparent conducting oxide (TCO) film comprising: a TCO layer, and dopants selected from the elements consisting of Vanadium, Molybdenum, Tantalum, Niobium, Antimony, Titanium, Zirconium, and Hafnium, wherein the elements are n-type dopants; and wherein the transparent conducting oxide is characterized by an improved electron mobility of about 42 cm.sup.2/V-sec while simultaneously maintaining a high carrier density of .about.4.4e.times.10.sup.20 cm.sup.-3.

  14. Patterning of Indium Tin Oxide Films

    NASA Technical Reports Server (NTRS)

    Immer, Christopher

    2008-01-01

    A relatively rapid, economical process has been devised for patterning a thin film of indium tin oxide (ITO) that has been deposited on a polyester film. ITO is a transparent, electrically conductive substance made from a mixture of indium oxide and tin oxide that is commonly used in touch panels, liquid-crystal and plasma display devices, gas sensors, and solar photovoltaic panels. In a typical application, the ITO film must be patterned to form electrodes, current collectors, and the like. Heretofore it has been common practice to pattern an ITO film by means of either a laser ablation process or a photolithography/etching process. The laser ablation process includes the use of expensive equipment to precisely position and focus a laser. The photolithography/etching process is time-consuming. The present process is a variant of the direct toner process an inexpensive but often highly effective process for patterning conductors for printed circuits. Relative to a conventional photolithography/ etching process, this process is simpler, takes less time, and is less expensive. This process involves equipment that costs less than $500 (at 2005 prices) and enables patterning of an ITO film in a process time of less than about a half hour.

  15. Characterisation, corrosion resistance and in vitro bioactivity of manganese-doped hydroxyapatite films electrodeposited on titanium.

    PubMed

    Huang, Yong; Ding, Qiongqiong; Han, Shuguang; Yan, Yajing; Pang, Xiaofeng

    2013-08-01

    This work elucidated the corrosion resistance and in vitro bioactivity of electroplated manganese-doped hydroxyapatite (MnHAp) film on NaOH-treated titanium (Ti). The NaOH treatment process was performed on Ti surface to enhance the adhesion of the MnHAp coating on Ti. Scanning electron microscopy images showed that the MnHAp coating had needle-like apatite crystals, and the approximately 10 μm thick layer was denser than HAp. Energy-dispersive X-ray spectroscopy analysis revealed that the MnHAp crystals were Ca-deficient and the Mn/P molar ratio was 0.048. X-ray diffraction confirmed the presence of single-phase MnHAp, which was aligned vertically to the substrate. Fourier transform infrared spectroscopy indicated the presence of phosphate bands ranging from 500 to 650 and 900 to 1,100 cm(-1), and a hydroxyl band at 3,571 cm(-1), which was characteristic of HAp. Bond strength test revealed that adhesion for the MnHAp coating was more enhanced than that of the HAp coating. Potentiodynamic polarisation test showed that the MnHAp-coated surface exhibited superior corrosion resistance over the HAp single-coated surface. Bioactivity test conducted by immersing the coatings in simulated body fluid showed that MnHAp coating can rapidly induce bone-like apatite nucleation and growth. Osteoblast cellular tests revealed that the MnHAp coating was better at improving the in vitro biocompatibility of Ti than the HAp coating. PMID:23686354

  16. Aluminum oxide film thickness and emittance

    SciTech Connect

    Thomas, J.K.; Ondrejcin, R.S.

    1991-11-01

    Aluminum reactor components which are not actively cooled could be subjected to high temperatures due to gamma heating after the core coolant level dropped during the ECS phase of a hypothetical LOCA event. Radiative heat transfer is the dominant heat transfer process in this scenario and therefore the emittance of these components is of interest. Of particular interest are the safety rod thimbles and Mark 60B blanket assemblies; for the K Reactor, these components have been exposed to low temperature (< 55{degrees}C) moderator for about a year. The average moderator temperature was assumed to be 30{degrees}C. The Al oxide film thickness at this temperature, after one year of exposure, is predicted to be 6.4 {mu}m {plus minus} 10%; insensitive to exposure time. Dehydration of the film during the gamma heating accident would result in a film thickness of 6.0 {mu}m {plus minus} 11%. Total hemispherical emittance is predicted to be 0.69 at 96{degrees}C, decreasing to 0.45 at 600{degrees}C. Some phenomena which would tend to yield thicker oxide films in the reactor environment relative to those obtained under experimental conditions were neglected and the predicted film thickness values are therefore conservative. The emittance values predicted for a given film thickness are also conservative. The conservativisms inherent in the predicted emittance are particularly relevant for uncertainty analysis of temperatures generated using these values.

  17. Aluminum oxide film thickness and emittance

    SciTech Connect

    Thomas, J.K.; Ondrejcin, R.S.

    1991-11-01

    Aluminum reactor components which are not actively cooled could be subjected to high temperatures due to gamma heating after the core coolant level dropped during the ECS phase of a hypothetical LOCA event. Radiative heat transfer is the dominant heat transfer process in this scenario and therefore the emittance of these components is of interest. Of particular interest are the safety rod thimbles and Mark 60B blanket assemblies; for the K Reactor, these components have been exposed to low temperature (< 55{degrees}C) moderator for about a year. The average moderator temperature was assumed to be 30{degrees}C. The Al oxide film thickness at this temperature, after one year of exposure, is predicted to be 6.4 {mu}m {plus_minus} 10%; insensitive to exposure time. Dehydration of the film during the gamma heating accident would result in a film thickness of 6.0 {mu}m {plus_minus} 11%. Total hemispherical emittance is predicted to be 0.69 at 96{degrees}C, decreasing to 0.45 at 600{degrees}C. Some phenomena which would tend to yield thicker oxide films in the reactor environment relative to those obtained under experimental conditions were neglected and the predicted film thickness values are therefore conservative. The emittance values predicted for a given film thickness are also conservative. The conservativisms inherent in the predicted emittance are particularly relevant for uncertainty analysis of temperatures generated using these values.

  18. Metal current collect protected by oxide film

    DOEpatents

    Jacobson, Craig P.; Visco, Steven J.; DeJonghe, Lutgard C.

    2004-05-25

    Provided are low-cost, mechanically strong, highly electronically conductive current collects and associated structures for solid-state electrochemical devices, techniques for forming these structures, and devices incorporating the structures. The invention provides solid state electrochemical devices having as current interconnects a ferritic steel felt or screen coated with a protective oxide film.

  19. Thin-Film Solid Oxide Fuel Cells

    NASA Technical Reports Server (NTRS)

    Chen, Xin; Wu, Nai-Juan; Ignatiev, Alex

    2009-01-01

    The development of thin-film solid oxide fuel cells (TFSOFCs) and a method of fabricating them have progressed to the prototype stage. This can result in the reduction of mass, volume, and the cost of materials for a given power level.

  20. Superoxide Production by a Manganese-Oxidizing Bacterium Facilitates Iodide Oxidation

    PubMed Central

    Li, Hsiu-Ping; Daniel, Benjamin; Creeley, Danielle; Grandbois, Russell; Zhang, Saijin; Xu, Chen; Ho, Yi-Fang; Schwehr, Kathy A.; Kaplan, Daniel I.; Santschi, Peter H.; Hansel, Colleen M.

    2014-01-01

    The release of radioactive iodine (i.e., iodine-129 and iodine-131) from nuclear reprocessing facilities is a potential threat to human health. The fate and transport of iodine are determined primarily by its redox status, but processes that affect iodine oxidation states in the environment are poorly characterized. Given the difficulty in removing electrons from iodide (I−), naturally occurring iodide oxidation processes require strong oxidants, such as Mn oxides or microbial enzymes. In this study, we examine iodide oxidation by a marine bacterium, Roseobacter sp. AzwK-3b, which promotes Mn(II) oxidation by catalyzing the production of extracellular superoxide (O2−). In the absence of Mn2+, Roseobacter sp. AzwK-3b cultures oxidized ∼90% of the provided iodide (10 μM) within 6 days, whereas in the presence of Mn(II), iodide oxidation occurred only after Mn(IV) formation ceased. Iodide oxidation was not observed during incubations in spent medium or with whole cells under anaerobic conditions or following heat treatment (boiling). Furthermore, iodide oxidation was significantly inhibited in the presence of superoxide dismutase and diphenylene iodonium (a general inhibitor of NADH oxidoreductases). In contrast, the addition of exogenous NADH enhanced iodide oxidation. Taken together, the results indicate that iodide oxidation was mediated primarily by extracellular superoxide generated by Roseobacter sp. AzwK-3b and not by the Mn oxides formed by this organism. Considering that extracellular superoxide formation is a widespread phenomenon among marine and terrestrial bacteria, this could represent an important pathway for iodide oxidation in some environments. PMID:24561582

  1. Formation of brominated phenolic contaminants from natural manganese oxides-catalyzed oxidation of phenol in the presence of Br(.).

    PubMed

    Lin, Kunde; Song, Lianghui; Zhou, Shiyang; Chen, Da; Gan, Jay

    2016-07-01

    Brominated phenolic compounds (BPCs) are a class of persistent and potentially toxic compounds ubiquitously present in the aquatic environment. However, the origin of BPCs is not clearly understood. In this study, we investigated the formation of BPCs from natural manganese oxides (MnOx)-catalyzed oxidation of phenol in the presence of Br(-). Experiments at ambient temperature clearly demonstrated that BPCs were readily produced via the oxidation of phenol by MnOx in the presence of Br(-). In the reaction of MnOx sand with 0.213 μmol/L phenol and 0.34 mmol/L Br(-) for 10 min, more than 60% of phenol and 56% of Br(-) were consumed to form BPCs. The yield of BPCs increased with increasing concentrations of phenol and Br(-). Overall, a total of 14 BPCs including simple bromophenols (4-bromophenol, 2,4-dibromophenol, and 2,4,6-tribromophenol), hydroxylated polybrominated diphenyl ethers (OH-PBDEs), and hydroxylated polybrominated biphenyls (OH-PBBs) were identified. The production of BPCs increased with increasing concentrations of Br(-) or phenol. It was deduced that Br(-) was first oxidized to form active bromine, leading to the subsequent bromination of phenol to form bromophenols. The further oxidation of bromophenols by MnOx resulted in the formation of OH-PBDEs and OH-PBBs. In view of the ubiquity of phenol, Br(-), and MnOx in the environment, MnOx-mediated oxidation may play a role on the natural production of BPCs. PMID:27131033

  2. The influence of diffusion temperature on the structural, optical and magnetic properties of manganese-doped zinc oxysulfide thin films

    NASA Astrophysics Data System (ADS)

    Polat, İ.; Aksu, S.; Altunbaş, M.; Yılmaz, S.; Bacaksız, E.

    2011-10-01

    We investigated the structural, optical and magnetic properties of Mn-doped zinc oxysulfide films. Zn(O,S) films were deposited by a spray pyrolysis method on glass substrate. A thin Mn layer evaporated on these films served as the source for the diffusion doping. The XRD pattern of undoped films revealed the presence of two wurtzite phases corresponding to ZnS and ZnO with a strong preferred orientation along the ZnS (0 0 2) hexagonal plane direction. SEM showed a similar surface morphology for the undoped and Mn-doped films, displaying regular arrays of hexagonal micro-rods perpendicular to the substrate. The optical transmission measurements showed that both undoped and Mn diffusion-doped films had a low average transmittance less than about 10%. The gap energy is decreased from 3.42 to 3.33 eV upon annealing at 400 °C. Photoluminescence studies at 300 K show that the incorporation of manganese leads to a decrease of deep level band intensity compared to undoped sample. Clear ferromagnetic loops were observed for the Mn-doped Zn(O,S) films, which might be due to the presence of point defects.

  3. Understanding the role of gold nanoparticles in enhancing the catalytic activity of manganese oxides in water oxidation reactions.

    PubMed

    Kuo, Chung-Hao; Li, Weikun; Pahalagedara, Lakshitha; El-Sawy, Abdelhamid M; Kriz, David; Genz, Nina; Guild, Curtis; Ressler, Thorsten; Suib, Steven L; He, Jie

    2015-02-16

    The Earth-abundant and inexpensive manganese oxides (MnOx) have emerged as an intriguing type of catalysts for the water oxidation reaction. However, the overall turnover frequencies of MnOx catalysts are still much lower than that of nanostructured IrO2 and RuO2 catalysts. Herein, we demonstrate that doping MnOx polymorphs with gold nanoparticles (AuNPs) can result in a strong enhancement of catalytic activity for the water oxidation reaction. It is observed that, for the first time, the catalytic activity of MnOx/AuNPs catalysts correlates strongly with the initial valence of the Mn centers. By promoting the formation of Mn(3+) species, a small amount of AuNPs (<5%) in α-MnO2/AuNP catalysts significantly improved the catalytic activity up to 8.2 times in the photochemical and 6 times in the electrochemical system, compared with the activity of pure α-MnO2. PMID:25284796

  4. Manganese Triazacyclononane Oxidation Catalysts Grafted under Reaction Conditions on Solid Co-Catalytic Supports

    SciTech Connect

    Schoenfeldt, Nicholas J.; Ni, Zhenjuan; Korinda, Andrew W.; Meyer, Randall J.; Notestein, Justin M.

    2012-01-23

    Manganese complexes of 1,4,7-trimethyl-1,4,7-triazacyclononane (tmtacn) are highly active and selective alkene oxidation catalysts with aqueous H{sub 2}O{sub 2}. Here, carboxylic acid-functionalized SiO{sub 2} simultaneously immobilizes and activates these complexes under oxidation reaction conditions. H{sub 2}O{sub 2} and the functionalized support are both necessary to transform the inactive [(tmtacn)Mn{sup IV}({mu}-O)3Mn{sup IV}(tmtacn)]{sup 2+} into the active, dicarboxylate-bridged [(tmtacn)Mn{sup III}({mu}-O)({mu}-RCOO){sub 2}Mn{sup III}(tmtacn)]{sup 2+}. This transformation is assigned on the basis of comparison of diffuse reflectance UV-visible spectra to known soluble models, assignment of oxidation state by Mn K-edge X-ray absorption near-edge spectroscopy, the dependence of rates on the acid/Mn ratios, and comparison of the surface structures derived from density functional theory with extended X-ray absorption fine structure. Productivity in cis-cyclooctene oxidation to epoxide and cis-diol with 2-10 equiv of solid cocatalytic supports is superior to that obtained with analogous soluble valeric acid cocatalysts, which require 1000-fold excess to reach similar levels at comparable times. Cyclooctene oxidation rates are near first order in H{sub 2}O{sub 2} and near zero order in all other species, including H{sub 2}O. These observations are consistent with a mechanism of substrate oxidation following rate-limiting H{sub 2}O{sub 2} activation on the hydrated, supported complex. This general mechanism and the observed alkene oxidation activation energy of 38 {+-} 6 kJ/mol are comparable to H{sub 2}O{sub 2} activation by related soluble catalysts. Undesired decomposition of H{sub 2}O{sub 2} is not a limiting factor for these solid catalysts, and as such, productivity remains high up to 25 C and initial H{sub 2}O{sub 2} concentration of 0.5 M, increasing reactor throughput. These results show that immobilized carboxylic acids can be utilized and understood

  5. Interfacial interactions between Np(V) and manganese oxide minerals manganite and hausmannite.

    PubMed

    Wilk, P A; Shaughnessy, D A; Wilson, R E; Nitsche, H

    2005-04-15

    Manganese oxides, present as minor phases in the vadose zone, have been previously shown to sequester large quantities of plutonium under environmental conditions. We are now continuing these studies with Np(V). Sorption onto manganite (MnOOH) and hausmannite (Mn3O4) at solid-to-solution ratios of 2.5-3.3 mg/mL has been studied as a function of neptunium concentration and pH. The sorption of Np increased as a function of pH for both minerals, attaining a maximum at neutral pH, and then decreased with increasing alkalinity. X-ray absorption fine structure spectroscopy (XAFS), taken at the Np L(III)-edge, has been used to determine the oxidation state of the sorbed Np. Our experimental results indicate reduction of the Np(V) because of interaction with the X-ray beam. These findings significantly impact the interpretation of results reported elsewhere on Np(V) investigated though the use of high-intensity X-ray beams. PMID:15884356

  6. In situ synthesis of manganese oxides on polyester fiber for formaldehyde decomposition at room temperature

    NASA Astrophysics Data System (ADS)

    Wang, Jinlong; Yunus, Rizwangul; Li, Jinge; Li, Peilin; Zhang, Pengyi; Kim, Jeonghyun

    2015-12-01

    Removal of low-level formaldehyde (HCHO) is of great interest for indoor air quality improvement. Supported materials especially those with low air pressure drop are of necessity for air purification. Manganese oxides (MnOx) was in situ deposited on the surface of fibers of a non-woven fabric made of polyethylene terephthalate (PET). As-synthesized MnOx/PET were characterized by SEM, XRD, TEM, ATR-FTIR and XPS analysis. The growth of MnOx layer on PET is thought to start with partial hydrolysis of PET, followed by surface oxidation by KMnO4 and then surface-deposition of MnOx particles from the bulk phase. The MnOx particles assembled with nanosheets were uniformly coated on the PET fibers. MnOx/PET showed good activity for HCHO decomposition at room temperature which followed the Mars-van Krevelen mechanism. The removal of HCHO was kept over 94% after 10 h continuous reaction under the conditions of inlet HCHO concentration ∼0.6 mg/m3, space velocity ∼17,000 h-1 and relative humidity∼50%. This research provides a facile method to deposit active MnOx onto polymers with low air resistance, and composite MnOx/PET material is promising for indoor air purification.

  7. Oxidative removal of bisphenol A by manganese dioxide: efficacy, products, and pathways.

    PubMed

    Lin, Kunde; Liu, Weiping; Gant, Jay

    2009-05-15

    Bisphenol A (BPA) is a ubiquitous environmental contaminant with endocrine disruption potential. In this study, exploiting the outstanding oxidative capacity of manganese dioxide (delta-MnO2), we explored forthe firsttime the efficacy and mechanisms of BPA removal by MnO2. In aqueous solutions, MnO2 demonstrated an extremely efficient capacity to remove BPA. Nearly all BPA (>99%) was eliminated in 6 min in a pH 4.5 solution initially containing 800 microM MnO2 and 4.4 microM BPA. While humic acid showed negligible inhibition on BPA removal, coexisting metal ions such as Mn2+, Ca2+, Mg2+, and Fe3+ displayed suppressive effects and the inhibitive capacityfollowed the order Mn2+ > Ca2+ > Mg2+ approximately Fe3+. A total of 11 products or intermediates were indentified and a detailed reaction scheme was suggested. The products could be ascribed to a suite of reactions of radical coupling, fragmentation, substitution, and elimination, triggered by the BPA radical formed through electron transfers to MnO2. The exceptional efficiency of MnO2 in removing BPA represents a potential use of MnO2 to treat waters containing phenolic compounds and also suggests a potentially important role of oxide-facilitated abiotic transformations in BPA attenuation in natural soil and sediment environments. PMID:19544899

  8. Nutrient input influences fungal community composition and size and can stimulate manganese (II) oxidation in caves.

    PubMed

    Carmichael, Sarah K; Zorn, Bryan T; Santelli, Cara M; Roble, Leigh A; Carmichael, Mary J; Bräuer, Suzanna L

    2015-08-01

    Little is known about the fungal role in biogeochemical cycling in oligotrophic ecosystems. This study compared fungal communities and assessed the role of exogenous carbon on microbial community structure and function in two southern Appalachian caves: an anthropogenically impacted cave and a near-pristine cave. Due to carbon input from shallow soils, the anthropogenically impacted cave had an order of magnitude greater fungal and bacterial quantitative-polymerase chain reaction (qPCR) gene copy numbers, had significantly greater community diversity, and was dominated by ascomycotal phylotypes common in early phase, labile organic matter decomposition. Fungal assemblages in the near-pristine cave samples were dominated by Basidiomycota typically found in deeper soils (and/or in late phase, recalcitrant organic matter decomposition), suggesting more oligotrophic conditions. In situ carbon and manganese (II) [Mn(II)] addition over 10 weeks resulted in growth of fungal mycelia followed by increased Mn(II) oxidation. A before/after comparison of the fungal communities indicated that this enrichment increased the quantity of fungal and bacterial cells, yet decreased overall fungal diversity. Anthropogenic carbon sources can therefore dramatically influence the diversity and quantity of fungi, impact microbial community function, and stimulate Mn(II) oxidation, resulting in a cascade of changes that can strongly influence nutrient and trace element biogeochemical cycles in karst aquifers. PMID:25865809

  9. Inducible nitric oxide synthase gene methylation and parkinsonism in manganese-exposed welders

    PubMed Central

    Nielsen, Susan Searles; Checkoway, Harvey; Criswell, Susan R.; Farin, Federico M.; Stapleton, Patricia L.; Sheppard, Lianne; Racette, Brad A.

    2015-01-01

    Introduction Neurologist-assessed parkinsonism signs are prevalent among workers exposed to manganese (Mn)-containing welding fume. Neuroinflammation may possibly play a role. Inducible nitric oxide synthase, coded by NOS2, is involved in inflammation, and particulate exposure increases the gene’s expression through methylation of CpG sites in the 5′ region. Methods We assessed DNA methylation at three CpG sites in the NOS2 exon 1 from blood from 201 welders. All were non-Hispanic Caucasian men 25–65 years old who were examined by a neurologist specializing in movement disorders. We categorized the workers according to their Unified Parkinson Disease Rating Scale motor subsection 3 (UPDRS3) scores as parkinsonism cases (UPDRS3 ≥ 15; n = 49), controls (UPDRS3 < 6; n = 103), or intermediate (UPDRS3 ≥6 to <15; n = 49). Results While accounting for age, examiner and experimental plate, parkinsonism cases had lower mean NOS2 methylation than controls (p-value for trend = 0.04), specifically at CpG site 8329 located in an exonic splicing enhancer of NOS2 (p-value for trend = 0.07). These associations were not observed for the intermediate UPDRS3 group (both p-value for trend ≥ 0.59). Conclusions Inflammation mediated by inducible nitric oxide synthase may possibly contribute to the association between welding fume and parkinsonism, but requires verification in a longitudinal study. PMID:25634431

  10. Studies of oxygen species in synthetic Todorokite-like manganese oxide octahedral molecular sieves

    SciTech Connect

    Yin, Yuan-Gen; Xu, Wen-Qing; Shen, Yan-Fei; Suib, S.L. ); O'Young, C.L. )

    1994-10-01

    Manganese oxide octahedral molecular sieves of 3 x 3 tunnel structure (OMS-1) doped with various cations possess high thermal stability and were studied by means of temperature-programmed desorption and reduction by H[sub 2] and CO. Different oxygen species can be discerned according to their peak positions in the temperature-programmed desorption and reduction and assigned to chemisorbed dioxygen, oxygen atoms bound to Mn[sup 2+], and those bound to Mn[sup 4+] ions in the framework. Differences in peak positions and availabilities of these species during TPD and TPR can be explained by creation of nascent Mn[sup 2+] ions during TPR. The effects of doping cations on the reactivity and availability of these oxygen species are demonstrated to be more pronounced in TPR in H[sub 2] or CO than in TPD. In some instances, the trends of changes in reactivity and availability of the oxygen species due to doping of Cu[sup 2+], Ni[sup 2+], Zn[sup 2+], and Mg[sup 2+] correlated with the changes in the heat of formation of oxides of these cations. Temperature-programmed reactions with methane show some reactivity of these doped OMS-1 materials. Pulse reactions with CO show higher reactivity of Cu-doped OM-1 than with butane. However, the recovery of Cu-doped OMS-1 by reoxidation with oxygen pulses seems rather incomplete at the same temperature. 27 refs., 9 figs.

  11. Catalytic ozonation of selected pharmaceuticals over mesoporous alumina-supported manganese oxide.

    PubMed

    Yang, Li; Hu, Chun; Nie, Yulun; Qu, Jiuhui

    2009-04-01

    Catalytic ozonation of five pharmaceutical compounds (PhACs)-phenazone, ibuprofen, diphenhydramine, phenytoin, and diclofenac sodium in alumina-supported manganese oxide (MnOx) suspension was carried out with a semicontinuous laboratory reactor. MnOx supported by mesoporous alumina (MnOx/MA) was highly effective in mineralizing the PhACs in aqueous solution. Fourier transform infrared (FTIR) spectroscopy and in situ attenuated total reflection FTIR (ATR-FTIR) spectroscopy were used to examine the interaction of ozone with different catalysts undervarious conditions. The crucial active sites, surface oxide species at 1380 cm(-1), were formed by the interaction of ozone with Lewis acid sites on the alumina surface. New surface hydroxyl groups at 2915 and 2845 cm(-1) were produced by the interaction of the catalyst and ozone in aqueous suspension and became active sites in the presence of MnOx. The introduction of MnOx enhanced the formation and activation of surface hydroxyl groups, causing higher catalytic reactivity. On the basis of these findings, a reaction mechanism is proposed for the catalytic ozonation of PhACs in MnOx/MA suspension. PMID:19452911

  12. Sapindus mukorossi mediated green synthesis of some manganese oxide nanoparticles interaction with aromatic amines

    NASA Astrophysics Data System (ADS)

    Jassal, Vidhisha; Shanker, Uma; Gahlot, Sweta; Kaith, B. S.; Kamaluddin; Iqubal, Md Asif; Samuel, Pankaj

    2016-04-01

    A green route was successfully used to synthesize some manganese oxides (MO) nanoparticles like MnO2, Mn2O3 and Mn3O4 with varied Mn/O ratio. This approach involved utilization of Sapindus mukorossi (raw reetha)-water as a natural surfactant-solvent system. The most important feature of present work was that during the synthesis of nanoparticles, no harmful toxic solvent or chemicals were used in order to follow the principles of green chemistry. The size of nanoparticles was recorded below 100 nm with different shapes and morphologies. MnO2 nanoparticles were found to have needle shape, Mn2O3: spherical and Mn3O4: cubic shape. The synthesized nanoparticles were characterized by powder X-ray diffraction, field-emission scanning electron microscopy, transmission electron microscopy and Fourier transform infrared spectroscopy. The synthesized MO nanoparticles were found to act as a solid support cum catalysts for the oxidation and polymerization of some aromatic amines like p-anisidine, p-toluidine, p-chloroaniline and aniline.

  13. Nanogold supported on manganese oxide doped alumina microspheres as a highly active and selective catalyst for CO oxidation in a H2-rich stream.

    PubMed

    Miao, Yu-Xin; Li, Wen-Cui; Sun, Qiang; Shi, Lei; He, Lei; Wang, Jing; Deng, Gao-Ming; Lu, An-Hui

    2015-12-28

    Manganese oxide-doped Al2O3 microspheres were synthesized via a redox method, and were then deposited with Au nanoparticles using a deposition-precipitation method. The obtained catalyst is not only highly active and selective for the preferential oxidation of CO in a H2-rich stream, but also shows excellent stability in the co-presence of H2O and CO2 at 80 °C. PMID:26489890

  14. Thermoluminescence evidence for light-induced oxidation of tyrosine and histidine residues in manganese-depleted photosystem II particles.

    PubMed

    Allakhverdiev, S I; Klimov, V V; Demeter, S

    1992-02-01

    In the thermoluminescence (TL) glow curve of photosystem II, particles depleted of manganese, a tyrosine modifier, 7-chloro-4-nitrobenz-2-oxa-1,3-diazole (NBD) abolishes the TL band appearing around -55 degrees C (TL-55). Addition of a histidine modifier, diethylpyrocarbonate results in the disappearance of the band peaking around -30 degrees C (TL-30). NBD treatment also abolishes the EPR signal IIfast of oxidized tyrosine donor, Yz, and inhibits the electron transport from diphenylcarbazide to 2,6-dichlorophenol-indophenol. It is concluded that the TL-55 and TL-30 bands can be assigned to oxidized tyrosine (Yz+) and histidine (His+) residues, respectively, which participate in electron transfer from manganese to the reaction center of chlorophyll, P680+. PMID:1551436

  15. Gold on Different Manganese Oxides: Ultra-Low-Temperature CO Oxidation over Colloidal Gold Supported on Bulk-MnO2 Nanomaterials.

    PubMed

    Gu, Dong; Tseng, Jo-Chi; Weidenthaler, Claudia; Bongard, Hans-Josef; Spliethoff, Bernd; Schmidt, Wolfgang; Soulimani, Fouad; Weckhuysen, Bert M; Schüth, Ferdi

    2016-08-01

    Nanoscopic gold particles have gained very high interest because of their promising catalytic activity for various chemicals reactions. Among these reactions, low-temperature CO oxidation is the most extensively studied one due to its practical relevance in environmental applications and the fundamental problems associated with its very high activity at low temperatures. Gold nanoparticles supported on manganese oxide belong to the most active gold catalysts for CO oxidation. Among a variety of manganese oxides, Mn2O3 is considered to be the most favorable support for gold nanoparticles with respect to catalytic activity. Gold on MnO2 has been shown to be significantly less active than gold on Mn2O3 in previous work. In contrast to these previous studies, in a comprehensive study of gold nanoparticles on different manganese oxides, we developed a gold catalyst on MnO2 nanostructures with extremely high activity. Nanosized gold particles (2-3 nm) were supported on α-MnO2 nanowires and mesoporous β-MnO2 nanowire arrays. The materials were extremely active at very low temperature (-80 °C) and also highly stable at 25 °C (70 h) under normal conditions for CO oxidation. The specific reaction rate of 2.8 molCO·h(-1)·gAu(-1) at a temperature as low as -85 °C is almost 30 times higher than that of the most active Au/Mn2O3 catalyst. PMID:27392203

  16. The role of electronic and ionic conductivities in the rate performance of tunnel structured manganese oxides in Li-ion batteries

    NASA Astrophysics Data System (ADS)

    Byles, B. W.; Palapati, N. K. R.; Subramanian, A.; Pomerantseva, E.

    2016-04-01

    Single nanowires of two manganese oxide polymorphs (α-MnO2 and todorokite manganese oxide), which display a controlled size variation in terms of their square structural tunnels, were isolated onto nanofabricated platforms using dielectrophoresis. This platform allowed for the measurement of the electronic conductivity of these manganese oxides, which was found to be higher in α-MnO2 as compared to that of the todorokite phase by a factor of ˜46. Despite this observation of substantially higher electronic conductivity in α-MnO2, the todorokite manganese oxide exhibited better electrochemical rate performance as a Li-ion battery cathode. The relationship between this electrochemical performance, the electronic conductivities of the manganese oxides, and their reported ionic conductivities is discussed for the first time, clearly revealing that the rate performance of these materials is limited by their Li+ diffusivity, and not by their electronic conductivity. This result reveals important new insights relevant for improving the power density of manganese oxides, which have shown promise as a low-cost, abundant, and safe alternative for next-generation cathode materials. Furthermore, the presented experimental approach is suitable for assessing a broader family of one-dimensional electrode active materials (in terms of their electronic and ionic conductivities) for both Li-ion batteries and for electrochemical systems utilizing charge-carrying ions beyond Li+.

  17. The role of electronic and ionic conductivities in the rate performance of tunnel structured manganese oxides in Li-ion batteries

    DOE PAGESBeta

    Byles, B. W.; Palapati, N. K. R.; Subramanian, A.; Pomerantseva, E.

    2016-04-29

    Single nanowires of two manganese oxide polymorphs (α-MnO2 and todorokite manganese oxide), which display a controlled size variation in terms of their square structural tunnels, were isolated onto nanofabricated platforms using dielectrophoresis. This platform allowed for the measurement of the electronic conductivity of these manganese oxides, which was found to be higher in α-MnO2 as compared to that of the todorokite phase by a factor of similar to 46. Despite this observation of substantially higher electronic conductivity in α-MnO2, the todorokite manganese oxide exhibited better electrochemical rate performance as a Li-ion battery cathode. The relationship between this electrochemical performance, themore » electronic conductivities of the manganese oxides, and their reported ionic conductivities is discussed for the first time, clearly revealing that the rate performance of these materials is limited by their Li+ diffusivity, and not by their electronic conductivity. This result reveals important new insights relevant for improving the power density of manganese oxides, which have shown promise as a low-cost, abundant, and safe alternative for next-generation cathode materials. Moreover, the presented experimental approach is suitable for assessing a broader family of one-dimensional electrode active materials (in terms of their electronic and ionic conductivities) for both Li-ion batteries and for electrochemical systems utilizing charge-carrying ions beyond Li+.« less

  18. Improvement in grade of minerals using simultaneous Bio-oxidation of invisible gold concentrate and deep-sea manganese crust

    NASA Astrophysics Data System (ADS)

    Myung, EunJi; Cho, Kang Hee; Kim, Hyun Soo; Park, Cheon Young

    2016-04-01

    Many sulfides of metal such as galena, sphalerite, chalcopyrite, and pyrite, are semiconductors. When two kinds of such minerals contact each other in an electrolyte, a galvanic couple, where the mineral of lower rest potential as anode, and that of higher rest potential as cathode forms. Manganese dioxide is also a semiconductor with much higher rest potential than all sulfides mentioned above, so that a galvanic couple in which both the minerals would dissolve simultaneously can form, when it contacts with any of the sulfides. The aim of this study was to investigate the improvement in grade of minerals using the simultaneous bio-oxidation of deep-sea manganese crust and invisible gold concentrate. The samples(deep-sea manganese crust and invisible gold concentrate) were characterized by chemical and XRD analysis. The primary components of the invisible gold concentrate was pyrite and quartz and the deep-sea manganese crust was amorphous material, as detected using XRD. The result of chemical analysis showed that Au, Ag, Te contents in the invisible gold concentrate 130.2, 954.1 and 1,043.6 mg/kg, respectively. and that Mn, Ni, Co contents in the deep-sea manganese crust 19,501.5, 151.9, 400.4 mg/kg, respectively. In order to increase the bacteria's tolerance of heavy metals, the bacteria using bio-oxidation experiments were repeatedly subcultured in an Cu adaptation-medium containing of 382.98 mg/l for 20 periods of 21 days. The improvement in grade of samples of in present adapted bacteria condition was greater than another conditions(control and in present non-adapted bacteria). The Au-Ag-Te contents in the invisible gold concentrate was enhanced in the order of physical oxidation, simultaneous/non-adaptive bio-oxidation, adaptive/bio-oxidation, simultaneous/adaptive bio-oxidation. If the bacteria is adapted to heavy metal ions and an optimization of conditions is found in future bio-oxidation-leaching processes. Acknowledgment : "This research was supported

  19. Oxidation of lignin in eucalyptus kraft pulp by manganese peroxidase from Bjerkandera sp. strain BOS55.

    PubMed

    Moreira, M T; Sierra-Alvarez, R; Lema, J M; Feijoo, G; Field, J A

    2001-05-01

    The white rot fungus Bjerkandera sp. strain BOS55 was shown in previous studies to cause high levels of kraft pulp bleaching and delignification under culture conditions in which manganese peroxidase (MnP) occurs as the dominant oxidative enzyme. In this study, the MnP of Bjerkadera was isolated and tested in vitro with eucalyptus oxygen-delignified kraft pulp (ODKP) based on measuring the reduction in kappa number as an indicator of lignin oxidation. The MnP preparation applied at 60 U/g pulp for 6 h caused a significant decrease of 11-13% in the kappa number in the ODKP under optimal conditions compared to parallel-incubated controls lacking enzyme. The effects of MnP dosage, Mn2+ concentration, organic acid buffer selection, pH and H2O2 addition were evaluated. The optimal Mn2+ concentration range for lignin oxidation in ODKP was 100-500 microM. In the presence of low oxalate concentrations (0.3-2 mM) the Bjerkandera MnP also significantly reduced the kappa number of ODKP by 6% without any Mn. This observation is in agreement with the fact that purified Bjerkandera MnP has Mn-independent activities. Under incubation conditions with added Mn2+, buffers composed of metal-complexing organic acids provided two-fold better kappa number reductions compared to the inert acetic acid. The optimal H2O2 dosage was found to be 0.017 micromol/min ml when added as semi-continuous pulses (every 30 min) or 0.2 micromol/min ml when generated continuously by glucose oxidase. Excess H2O2 caused severe inactivation of MnP during the incubations. Factors that improved the turnover of the enzyme, such as Mn2+ and metal-chelating acids, stabilized MnP against rapid inactivation. PMID:11265791

  20. Translocation of Inhaled Ultrafine Manganese Oxide Particles to the Central Nervous System

    PubMed Central

    Elder, Alison; Gelein, Robert; Silva, Vanessa; Feikert, Tessa; Opanashuk, Lisa; Carter, Janet; Potter, Russell; Maynard, Andrew; Ito, Yasuo; Finkelstein, Jacob; Oberdörster, Günter

    2006-01-01

    Background Studies in monkeys with intranasally instilled gold ultrafine particles (UFPs; < 100 nm) and in rats with inhaled carbon UFPs suggested that solid UFPs deposited in the nose travel along the olfactory nerve to the olfactory bulb. Methods To determine if olfactory translocation occurs for other solid metal UFPs and assess potential health effects, we exposed groups of rats to manganese (Mn) oxide UFPs (30 nm; ~ 500 μg/m3) with either both nostrils patent or the right nostril occluded. We analyzed Mn in lung, liver, olfactory bulb, and other brain regions, and we performed gene and protein analyses. Results After 12 days of exposure with both nostrils patent, Mn concentrations in the olfactory bulb increased 3.5-fold, whereas lung Mn concentrations doubled; there were also increases in striatum, frontal cortex, and cerebellum. Lung lavage analysis showed no indications of lung inflammation, whereas increases in olfactory bulb tumor necrosis factor-α mRNA (~ 8-fold) and protein (~ 30-fold) were found after 11 days of exposure and, to a lesser degree, in other brain regions with increased Mn levels. Macrophage inflammatory protein-2, glial fibrillary acidic protein, and neuronal cell adhesion molecule mRNA were also increased in olfactory bulb. With the right nostril occluded for a 2-day exposure, Mn accumulated only in the left olfactory bulb. Solubilization of the Mn oxide UFPs was < 1.5% per day. Conclusions We conclude that the olfactory neuronal pathway is efficient for translocating inhaled Mn oxide as solid UFPs to the central nervous system and that this can result in inflammatory changes. We suggest that despite differences between human and rodent olfactory systems, this pathway is relevant in humans. PMID:16882521

  1. Exfoliation reaction of birnessite-type manganese oxide by a host guest electrostatic repulsion in aqueous solution

    NASA Astrophysics Data System (ADS)

    Ma, Biehou; Hou, Wenyan; Han, Yinfeng; Sun, Runguang; Liu, Zong-Huai

    2008-02-01

    The birnessite-type manganese oxide (BirMO) intercalated with 11-aminoundecanoic acid (AUA) as pillared species (BirMO-AUA) was prepared by an ion-exchange method. The prepared BirMO-AUA material was successfully delaminated in an aqueous system by a novel host-guest repulsive interaction process. The delaminated manganese oxide nanosheets were confirmed by XRD, TEM, AFM, and IR analyses. XRD measurement on the slurry centrifuged from the solution showed an amorphous halo and the crystalline phase of BirMO-AUA lost its sharp reflections at pH = 12. Freeze-drying the slurry, the broad pattern was converted into a basal diffraction pattern, indicating the restacking of delaminated manganese oxide nanosheets. AFM and TEM images showed that a large part of BirMO-AUA material was delaminated into one elementary layer at least, and the delaminated nanosheet had a disk-like shape. IR results confirmed that the AUA molecules released from the interlayer accompanied with the delamination process and they could not be restacked into the interlayer by freeze-drying the delaminated nanosheets. The novel delamination process is favorable for negative inorganic layered materials with high layered charge density.

  2. Degradation of antibiotic amoxicillin using 1 x 1 molecular sieve-structured manganese oxide.

    PubMed

    Kuan, Wen-Hui; Hu, Ching-Yao; Liu, Bin-Sheng; Tzou, Yu-Min

    2013-01-01

    The kinetics and mechanism ofamoxicillin (AMO) degradation using a 1 x 1 molecular sieve-structured manganese oxide (MnO2) was studied. The presence of the buffer solution (i.e., NaHCO3, NaH2PO4 and KH2PO4) diminished AMO binding to MnO2, thus reducing AMO degradation in the pretest; therefore, all other experiments in this study were conducted without the addition of a buffer. Third-order rate constants, second-order on AMO and first-order on MnO2 increased with elevating pH level (2.81-7.23) from 0.54 to 9.17 M(-2) s(-1), and it decreased to 4.27 M(-2) s(-1) at pH 8.53 beyond the pk(a2) of AMO (7.3). The dissolution of the MnO2 suspension with and without AMO exhibited a similar trend; that is, Mn2+ concentration increased with decreasing pH. However, the dissolution of MnO2 with AMO was greater than that without AMO, except for the reaction occurring at pH 8.53, partially indicating that MnO2 acts as an oxidant in AMO degradation. The preliminary chromatogram data display different products with varying pH reaction s, implying that AMO elimination using this 1 x 1 molecular sieve-structured MnO2 is by adsorption as well as oxidative degradation. A complementary experiment indicates that the amount of oxidatively degraded AMO increases substantially from 65.5% at 4 h to 95% at 48 h, whereas the AMO adsorbed onto MnO2 decreases slightly from 4.5% at4 h to 2.4% at 48 h. The oxidative degradation accounted for more AMO removal than adsorption over the whole reaction course, indicating that the oxidative reaction of AMO on MnO2 dominated the AMO removal. PMID:24350501

  3. Interfacial Assembly of Graphene Oxide Films

    NASA Astrophysics Data System (ADS)

    Valtierrez, Cain; Ismail, Issam; Macosko, Christopher; Stottrup, Benjamin

    Controlled assembly of monolayer graphene-oxide (GO) films at the air/water interface is of interest for the development of transparent conductive thin films of chemically-derived graphene. We present experimental results from investigations of the assembly of polydisperse GO sheets at the air-water interface. GO nanosheets with lateral dimensions of greater than 10 microns were created using a modified Tour synthesis (Dimiev and Tour, 2014). GO films were generated with conventional Langmuir trough techniques to control lateral packing density. Film morphology was characterized in situ with Brewster angle microscopy. Films were transferred unto a substrate via the Langmuir-Blodgett deposition technique and imaged with fluorescence quenching microscopy. Through pH modulation of the aqueous subphase, it was found that GO's intrinsic surface activity to the interface increased with increasing subphase acidity. Finally, we found a dominant elastic contribution during uniaxial film deformation as measured by anisotropic pressure measurements. A. M. Dimiev, and J. M. Tour, ``Mechanism of GO Formation,'' ACS Nano, 8, (2014)

  4. Development of optically transparent water oxidation catalysts using manganese pyrophosphate compounds.

    PubMed

    Takashima, Toshihiro; Hotori, Yuki; Irie, Hiroshi

    2015-11-01

    One challenge in artificial photosynthetic systems is the development of active oxygen evolution catalysts composed of abundant elements. The oxygen evolution activities of manganese pyrophosphate compounds were examined in electrochemical and photochemical experiments. Electrocatalysis using calcium-manganese pyrophosphate exhibited good catalytic ability under neutral pH and an oxygen evolution reaction was driven with a small overpotential (η<100 mV). UV-vis diffuse reflectance measurements revealed that manganese pyrophosphates exhibit weak absorption in the visible light region while commonly used oxygen evolution catalysts exhibit intense absorption. Therefore, the efficient light absorption of a photocatalyst was retained even after surface modification with a manganese pyrophosphate, and photochemical oxygen evolution was achieved by using magnesium ferrite modified with manganese pyrophosphate nanoparticles under the illumination of visible light at wavelength of over 420 nm. PMID:25648929

  5. Influence of doping with third group oxides on properties of zinc oxide thin films

    SciTech Connect

    Palimar, Sowmya Bangera, Kasturi V.; Shivakumar, G. K.

    2013-03-15

    The study of modifications in structural, optical and electrical properties of vacuum evaporated zinc oxide thin films on doping with III group oxides namely aluminum oxide, gallium oxide and indium oxide are reported. It was observed that all the films have transmittance ranging from 85 to 95%. The variation in optical properties with dopants is discussed. On doping the film with III group oxides, the conductivity of the films showed an excellent improvement of the order of 10{sup 3} {Omega}{sup -1} cm{sup -1}. The measurements of activation energy showed that all three oxide doped films have 2 donor levels below the conduction band.

  6. Mutation in HFE gene decreases manganese accumulation and oxidative stress in the brain after olfactory manganese exposure.

    PubMed

    Ye, Qi; Kim, Jonghan

    2016-06-01

    Increased accumulation of manganese (Mn) in the brain is significantly associated with neurobehavioral deficits and impaired brain function. Airborne Mn has a high systemic bioavailability and can be directly taken up into the brain, making it highly neurotoxic. While Mn transport is in part mediated by several iron transporters, the expression of these transporters is altered by the iron regulatory gene, HFE. Mutations in the HFE gene are the major cause of the iron overload disorder, hereditary hemochromatosis, one of the prevalent genetic diseases in humans. However, whether or not HFE mutation modifies Mn-induced neurotoxicity has not been evaluated. Therefore, our goal was to define the role of HFE mutation in Mn deposition in the brain and the resultant neurotoxic effects after olfactory Mn exposure. Mice carrying the H67D HFE mutation, which is homologous to the H63D mutation in humans, and their control, wild-type mice, were intranasally instilled with MnCl2 with different doses (0, 0.2, 1.0 and 5.0 mg kg(-1)) daily for 3 days. Mn levels in the blood, liver and brain were determined using inductively-coupled plasma mass spectrometry (ICP-MS). H67D mutant mice showed significantly lower Mn levels in the blood, liver, and most brain regions, especially in the striatum, while mice fed an iron-overload diet did not. Moreover, mRNA expression of ferroportin, an essential exporter of iron and Mn, was up-regulated in the striatum. In addition, the levels of isoprostane, a marker of lipid peroxidation, were increased in the striatum after Mn exposure in wild-type mice, but were unchanged in H67D mice. Together, our results suggest that the H67D mutation provides decreased susceptibility to Mn accumulation in the brain and neurotoxicity induced by inhaled Mn. PMID:27295312

  7. Porous Nickel Oxide Film Sensor for Formaldehyde

    NASA Astrophysics Data System (ADS)

    Cindemir, U.; Topalian, Z.; Österlund, L.; Granqvist, C. G.; Niklasson, G. A.

    2014-11-01

    Formaldehyde is a volatile organic compound and a harmful indoor pollutant contributing to the "sick building syndrome". We used advanced gas deposition to fabricate highly porous nickel oxide (NiO) thin films for formaldehyde sensing. The films were deposited on Al2O3 substrates with prefabricated comb-structured electrodes and a resistive heater at the opposite face. The morphology and structure of the films were investigated with scanning electron microscopy and X-ray diffraction. Porosity was determined by nitrogen adsorption isotherms with the Brunauer-Emmett-Teller method. Gas sensing measurements were performed to demonstrate the resistive response of the sensors with respect to different concentrations of formaldehyde at 150 °C.

  8. Galvanostatic Ion Detrapping Rejuvenates Oxide Thin Films.

    PubMed

    Arvizu, Miguel A; Wen, Rui-Tao; Primetzhofer, Daniel; Klemberg-Sapieha, Jolanta E; Martinu, Ludvik; Niklasson, Gunnar A; Granqvist, Claes G

    2015-12-01

    Ion trapping under charge insertion-extraction is well-known to degrade the electrochemical performance of oxides. Galvanostatic treatment was recently shown capable to rejuvenate the oxide, but the detailed mechanism remained uncertain. Here we report on amorphous electrochromic (EC) WO3 thin films prepared by sputtering and electrochemically cycled in a lithium-containing electrolyte under conditions leading to severe loss of charge exchange capacity and optical modulation span. Time-of-flight elastic recoil detection analysis (ToF-ERDA) documented pronounced Li(+) trapping associated with the degradation of the EC properties and, importantly, that Li(+) detrapping, caused by a weak constant current drawn through the film for some time, could recover the original EC performance. Thus, ToF-ERDA provided direct and unambiguous evidence for Li(+) detrapping. PMID:26599729

  9. Metallic oxide switches using thick film technology

    NASA Technical Reports Server (NTRS)

    Patel, D. N.; Williams, L., Jr.

    1974-01-01

    Metallic oxide thick film switches were processed on alumina substrates using thick film technology. Vanadium pentoxide in powder form was mixed with other oxides e.g., barium, strontium copper and glass frit, ground to a fine powder. Pastes and screen printable inks were made using commercial conductive vehicles and appropriate thinners. Some switching devices were processed by conventional screen printing and firing of the inks and commercial cermet conductor terminals on 96% alumina substrates while others were made by applying small beads or dots of the pastes between platinum wires. Static, and dynamic volt-ampere, and pulse tests indicate that the switching and self-oscillatory characteristics of these devices could make them useful in memory element, oscillator, and automatic control applications.

  10. Aluminum manganese oxides with mixed crystal structure: high-energy-density cathodes for rechargeable sodium batteries.

    PubMed

    Han, Dong-Wook; Ku, Jun-Hwan; Kim, Ryoung-Hee; Yun, Dong-Jin; Lee, Seok-Soo; Doo, Seok-Gwang

    2014-07-01

    We report a new discovery for enhancing the energy density of manganese oxide (Nax MnO2 ) cathode materials for sodium rechargeable batteries by incorporation of aluminum. The Al incorporation results in NaAl(0.1) Mn(0.9) O2 with a mixture of tunnel and layered crystal structures. NaAl(0.1) Mn(0.9) O2 shows a much higher initial discharge capacity and superior cycling performance compared to pristine Na(0.65) MnO2 . We ascribe this enhancement in performance to the formation of a new orthorhombic layered NaMnO2 phase merged with a small amount of tunnel Na(0.44) MnO2 phase in NaAl(0.1) Mn(0.9) O2 , and to improvements in the surface stability of the NaAl(0.1) Mn(0.9) O2 particles caused by the formation of Al-O bonds on their surfaces. Our findings regarding the phase transformation and structure stabilization induced by incorporation of aluminum, closely related to the structural analogy between orthorhombic Na(0.44) MnO2 and NaAl(0.1) Mn(0.9) O2 , suggest a strategy for achieving sodium rechargeable batteries with high energy density and stability. PMID:24797956

  11. Direct and environmentally benign synthesis of manganese oxide/graphene composites from graphite for electrochemical capacitors

    NASA Astrophysics Data System (ADS)

    Lee, Hae-Min; Jeong, Gyoung Hwa; Kang, Doo Won; Kim, Sang-Wook; Kim, Chang-Koo

    2015-05-01

    We develop a direct and environmentally benign method to prepare manganese oxide (Mn3O4)/graphene composites via one-step hydrothermal synthesis from graphite without using strong acids and toxic reducing agents. Structural and morphological analyses reveals that the irregularly shaped Mn3O4 nanoparticles are well-dispersed on the graphene flakes. Cyclic voltammetry and galvanostatic charge-discharge tests indicate that the charge-storing mechanism of the Mn3O4/graphene composites is pseudocapacitive. The Mn3O4/graphene composite exhibits a specific capacitance of 367 F/g at a current density of 5 A/g. After 3000 charge-discharge cycles, the Mn3O4/graphene electrode retains 91.8% of its initial specific capacitance. From electrochemical impedance spectra, it is evident that the changes in both the equivalent series resistance and charge-transfer resistance of the Mn3O4/graphene electrode before and after 3000 charge-discharge cycles are small, indicating good cycling and electrochemical stability of the Mn3O4/graphene electrode.

  12. Manganese(III) corrole-oxidant adduct as the active intermediate in catalytic hydrogen atom transfer.

    PubMed

    Zdilla, Michael J; Abu-Omar, Mahdi M

    2008-11-17

    Hydrogen atom transfer (HAT) reactions from dihydroanthracene to ArINTs (Ar = 2- tert-butylsulfonyl)benzene and Ts = p-toluenesulfonyl) is catalyzed by Mn(tpfc) (tpfc = 5,10,15-tris(pentafluorophenyl)corrole). Kinetics of HAT was monitored by gas chromatography. Conversion to the major products anthracene, TsNH 2, and ArI is too fast to be explained by direct HAT from the terminal imido complex TsN=Mn(tpfc), which forms from the reaction of Mn(tpfc) with ArINTs. Steady-state kinetics, isotope effects, and variation of the initial catalyst form (Mn (III)(tpfc) vs TsN=Mn (V)(tpfc)) support a mechanism in which the active catalytic species is an adduct of manganese(III) with the oxidant, (ArINTs)Mn (III)(tpfc). This species was detected by rapid-scan stopped-flow absorption spectroscopy. Kinetic simulations demonstrated the viability of this mechanism in contrast to other proposals. PMID:18855381

  13. Layered manganese oxide intergrowth electrodes for rechargeable lithium batteries: Part 1-substitution with Co or Ni

    SciTech Connect

    Dolle, Mickael; Patoux, Sebastien; Doeff, Marca M.

    2004-09-08

    Lithium manganese oxides substituted with nickel or cobalt were characterized electrochemically in lithium cell configurations. The compounds studied were either single-phase layered structures with either primarily O2 or O3 stacking arrangements, or O2/O3 intergrowths, prepared from P2, P3 and P2/P3 sodium-containing precursors, respectively. The stacking arrangements are extremely sensitive to the Na/T. M. (T. M. = transition metal) ratios and the level of substitution. Phase diagrams showing the stability regions of the various arrangements for the Na-Ni-Mn-O system are presented. A possible correlation between vacancies and electrochemical performance is suggested. For high levels of substitution with Ni, fewer defects are possible for materials containing more O3 component and higher discharge capacities can be achieved, but spinel conversion upon cycling also occurs more rapidly as the O3 content increases. Intergrowths show intermediate behavior and represent a potential route towards designing stable, high capacity electrodes.

  14. Caldimonas manganoxidans gen. nov., sp. nov., a poly(3-hydroxybutyrate)-degrading, manganese-oxidizing thermophile.

    PubMed

    Takeda, Minoru; Kamagata, Yoichi; Ghiorse, William C; Hanada, Satoshi; Koizumi, Jun-ichi

    2002-05-01

    A poly(3-hydroxybutyrate) (PHB)-degrading, gram-negative, aerobic bacterium, strain HS(T), was isolated from a hot spring and chemotaxonomically and phylogenetically characterized. The oxidase-positive, weakly catalase-positive, non-pigmented cells (0.6 x 2.6 microm) exhibited a single polar flagellum and accumulated PHB granules. Strain HS(T) was capable of manganese oxidation. Highest growth rate was attained at 50 degrees C. The optimum pH for growth was 7-8. The major respiratory quinone was ubiquinone-8 and major cellular fatty acids were C16:0, C16:1 and C18:1. The G+C content of the DNA was 66.2 mol%. Comparative 16S rDNA analysis indicated that strain HS(T) is related to the Rubrivivax subgroup and the family Comamonadaceae. The nearest phylogenetic relatives were Ideonella dechloratans (92.1% similarity), Leptothrix discophora (93.6%), Roseateles depolymerans (92.4%) and Rubrivivax gelatinosus (92.2%). On the basis of its phylogenetic and phenotypic properties, it is proposed that this isolate be designated Caldimonas manganoxidans gen. nov., sp. nov.; the type strain is HS(T) (= JCM 10698T = IFO 16448T = ATCC BAA-369T). PMID:12054255

  15. The Influence of Manganese Oxide on the Sintering Behavior of Yttria Tetragonal Zirconia

    NASA Astrophysics Data System (ADS)

    Meenaloshini, S.; Amiriyan, M.; Sankar, U.; Tolouei, R.; Ramesh, S.

    2011-01-01

    The sintering behavior of yttria-stabilized zirconia, with the influence of small additions of MnO2 (up to 1 wt %) sintered over the temperature range from 1250° C to 1500° C was investigated. It was found that the mechanical properties of Y-TZP were dependent on the dopant amount and sintering temperature. The results revealed that relative densities above 97.5% of theoretical (i.e. >5.95 Mgm-3) could be obtained in Y-TZPs sintered at low temperatures, 1250° C and 1300° C, with the additions of ≤0.3 wt% MnO2. In comparison to the undoped samples, the additions of up to 1 wt% MnO2 and for sintering up to 1350° C was found to be beneficial in enhancing the Vickers hardness of the ceramic. The fracture toughness of Y-TZP however, was found to increase only in the 1 wt% MnO2-doped samples when sintered above 1400° C. The relation between the measured mechanical properties is discussed with the emphasis on the role of the manganese oxide.

  16. Higher-power supercapacitor electrodes based on mesoporous manganese oxide coating on vertically aligned carbon nanofibers.

    PubMed

    Klankowski, Steven A; Pandey, Gaind P; Malek, Gary; Thomas, Conor R; Bernasek, Steven L; Wu, Judy; Li, Jun

    2015-05-14

    A study on the development of high-power supercapacitor materials based on formation of thick mesoporous MnO2 shells on a highly conductive 3D template using vertically aligned carbon nanofibers (VACNFs). Coaxial manganese shells of 100 to 600 nm nominal thicknesses are sputter-coated on VACNFs and then electrochemically oxidized into rose-petal-like mesoporous MnO2 structure. Such a 3D MnO2/VACNF hybrid architecture provides enhanced ion diffusion throughout the whole MnO2 shell and yields excellent current collection capability through the VACNF electrode. These two effects collectively enable faster electrochemical reactions during charge-discharge of MnO2 in 1 M Na2SO4. Thick MnO2 shells (up to 200 nm in radial thickness) can be employed, giving a specific capacitance up to 437 F g(-1). More importantly, supercapacitors employing such a 3D MnO2/VACNF hybrid electrode illustrate more than one order of magnitude higher specific power than the state-of-the-art ones based on other MnO2 structures, reaching ∼240 kW kg(-1), while maintaining a comparable specific energy in the range of 1 to 10 Wh kg(-1). This hybrid approach demonstrates the potential of 3D core-shell architectures for high-power energy storage devices. PMID:25894255

  17. Manganese-oxide-coated alumina: a promising sorbent for defluoridation of water.

    PubMed

    Maliyekkal, Shihabudheen M; Sharma, Atul Kumar; Philip, Ligy

    2006-11-01

    In this study, adsorption potential of a new sorbent manganese-oxide-coated alumina (MOCA) was investigated for defluoridation of drinking water using batch and continuous mode experiments. The effects of different parameters such as pH, initial fluoride concentration and co-existing ions (usually present in groundwater sample) were studied to understand the adsorption behavior of the sorbent under various conditions. Optimum removal of fluoride ions occurred in a pH range of 4-7. Results of the present study indicate that fluoride adsorption rate and adsorption capacity of MOCA are far superior to that of activated alumina (AA), which was used as the base material for MOCA preparation. The MOCA can be effectively regenerated using 2.5% NaOH as eluent. The Langmuir equilibrium model was found to be suitable for describing the fluoride sorption on AA and MOCA. The maximum fluoride uptake capacity for MOCA and AA was found to be 2.85 and 1.08 mg g(-1), respectively. The kinetic results showed that the fluoride sorption to MOCA followed pseudo--second-order kinetics with a correlation coefficient greater than 0.98. The fluoride sorption capacity at breakthrough point for both the adsorbents was greatly influenced by bed depth. A bed depth service time (BDST) approach was adopted to describe the continuous flow system. The batch and column studies demonstrated the superiority of MOCA over AA in removing fluoride from the drinking water system. PMID:17011020

  18. Effect of pH on morphology and supercapacitive properties of manganese oxide/polypyrrole nanocomposite

    NASA Astrophysics Data System (ADS)

    Gan, John Kevin; Lim, Yee Seng; Huang, Nay Ming; Lim, Hong Ngee

    2015-12-01

    In the present work, manganese oxide/polypyrrole (MnO2/PPy) nanocomposites with compact sheet, fibrous-porous, and granular morphologies were successfully synthesized using a simple, one step in situ chemical synthesis method. Their morphologies were tunable by varying the pH of the reactant's solution, which was very simple and scalable. Moreover, their electrochemical behaviors were greatly influenced by the pH of the reactant's solution. The optimum pH condition was found to be 4.0, producing an MnO2/PPy nanocomposite with high porosity. The porosity of the nanocomposite effectively improved its specific surface area, and its pore accessibility enabled the rapid intercalation/deintercalation of the electrolyte. As a result, a high specific capacitance of up to 312 F g-1 at 10 mV s-1 was obtained for the porous nanocomposite. A symmetric supercapacitor device built from the porous MnO2/PPy nanocomposite yielded a specific capacitance of 142 F g-1 per mass of one electrode and exhibited remarkable cycling stability, with 93.2% capacitance retention over 1000 charge/discharge cycles. These features show the promise of porous MnO2/PPy nanocomposite as an electrode material for high-performance supercapacitors.

  19. Solar-thermal Water Splitting Using the Sodium Manganese Oxide Process & Preliminary H2A Analysis

    SciTech Connect

    Francis, Todd M; Lichty, Paul R; Perkins, Christopher; Tucker, Melinda; Kreider, Peter B; Funke, Hans H; Lewandowski, A; Weimer, Alan W

    2012-10-24

    There are three primary reactions in the sodium manganese oxide high temperature water splitting cycle. In the first reaction, Mn2O3 is decomposed to MnO at 1,500°C and 50 psig. This reaction occurs in a high temperature solar reactor and has a heat of reaction of 173,212 J/mol. Hydrogen is produced in the next step of this cycle. This step occurs at 700°C and 1 atm in the presence of sodium hydroxide. Finally, water is added in the hydrolysis step, which removes NaOH and regenerates the original reactant, Mn2O3. The high temperature solar-driven step for decomposing Mn2O3 to MnO can be carried out to high conversion without major complication in an inert environment. The second step to produce H2 in the presence of sodium hydroxide is also straightforward and can be completed. The third step, the low temperature step to recover the sodium hydroxide is the most difficult. The amount of energy required to essentially distill water to recover sodium hydroxide is prohibitive and too costly. Methods must be found for lower cost recovery. This report provides information on the use of ZnO as an additive to improve the recovery of sodium hydroxide.

  20. Electrochemical deposition of silver on manganese dioxide coated reduced graphene oxide for enhanced oxygen reduction reaction

    NASA Astrophysics Data System (ADS)

    Lee, Kyungmi; Ahmed, Mohammad Shamsuddin; Jeon, Seungwon

    2015-08-01

    We have prepared a reduced graphene oxide (rGO)-supported silver (Ag) and manganese dioxide (MnO2) deposited porous-like catalyst (denoted as rGO/MnO2/Ag) through a facile electrochemical deposition route and have been used as a cathode catalyst for oxygen reduction reaction (ORR) in alkaline fuel cells. The physical properties of rGO/MnO2/Ag have been investigated via several instrumental methods. This material exhibits a polycrystalline structure characterized by Ag/MnO2 microsphere formation as a result of Ostwald ripening. The X-ray diffraction and X-ray photoelectron spectroscopy data reveal that the MnO2 and Ag have been slightly alloyed and Mn presents with the dioxide form on rGO. The electrochemical properties of the electrocatalyst have been studied via several voltammetric methods. The results demonstrated that the rGO/MnO2/Ag has an excellent catalytic activity for ORR in alkaline media compared to the other tested electrodes. Particularly, it shows 1.2 times higher current density and better electron transfer rate at 0.3 V per O2 than that of 20 wt% Pt/C. The other kinetic analysis reveals that the O2 has reduced directly to H2O through a nearly four-electron pathway with better anodic fuel tolerance and duration performance than that of 20% Pt/C.

  1. Facile synthesis of manganese ferrite/graphene oxide nanocomposites for controlled targeted drug delivery

    NASA Astrophysics Data System (ADS)

    Wang, Guangshuo; Ma, Yingying; Zhang, Lina; Mu, Jingbo; Zhang, Zhixiao; Zhang, Xiaoliang; Che, Hongwei; Bai, Yongmei; Hou, Junxian

    2016-03-01

    In this study, manganese ferrite/graphene oxide (MnFe2O4/GO) nanocomposites as controlled targeted drug delivery were prepared by a facile sonochemical method. It was found that GO nanosheets were fully exfoliated and decorated with MnFe2O4 nanoparticles having diameters of 5-13 nm. The field-dependent magnetization curve indicated superparamagnetic behavior of the obtained MnFe2O4/GO with saturation magnetization of 34.9 emu/g at room temperature. The in vitro cytotoxicity testing exhibited negligible cytotoxicity of as-prepared MnFe2O4/GO even at the concentration as high as 150 μg/mL. Doxorubicin hydrochloride (DOX) as an anti-tumor model drug was utilized to explore the application potential of MnFe2O4/GO for controlled drug delivery. The drug loading capacity of this nanocarrier was as high as 0.97 mg/mg and the drug release behavior showed a sustained and pH-responsive way.

  2. Complexation and redox interactions between aqueous plutonium and manganese oxide interfaces

    SciTech Connect

    Shaughnessy, Dawn A.; Nitsche, Heino; Booth, Corwin H.; Shuh, David K.; Waychunas, Glenn A.; Wilson, Richard E.; Cantrell, Kirk J.; Serne, R. Jeffrey

    2001-11-01

    The sorption of Pu(VI) and Pu(V) onto manganite (MnOOH) and Hausmannite (Mn3O4) was studied at pH 5. Manganite sorbed 21-24% from a 1x10-4 M plutonium solution and the hausmannite removed between 43-66% of the plutonium. The increased sorption by hausmannite results from its larger surface area (about twice that of manganite) plus a larger number of active surface sites. X-ray absorption near-edge structure (XANES) spectra taken at the Pu LIII edge were compared to standard spectra of plutonium in single oxidation states. Based on these spectra, it appears that both manganite and hausmannite reduce the higher valent plutonium species to Pu(IV). Between 53-59% of the plutonium was present as Pu(IV) in the manganite samples while 55-61% of the plutonium complexed to the hausmannite had also been reduced to Pu(IV). The exact mechanism behind this redox interaction between the plutonium and the manganese needs to be identified.

  3. Manganese doped iron oxide theranostic nanoparticles for combined T1 magnetic resonance imaging and photothermal therapy.

    PubMed

    Zhang, Mengxin; Cao, Yuhua; Wang, Lina; Ma, Yufei; Tu, Xiaolong; Zhang, Zhijun

    2015-03-01

    Photothermal therapy (PTT) is a noninvasive and convenient way to ablate tumor tissues. Integrating PTT with imaging technique could precisely identify the location and the size of tumor regions, thereby significantly improving the therapeutic efficacy. Magnetic resonance imaging (MRI) is widely used in clinical diagnosis due to its superb spatial resolution and real-time monitoring feature. In our work, we developed a theranostic nanoplatform based on manganese doped iron oxide (MnIO) nanoparticles modified with denatured bovine serum albumin (MnIO-dBSA). The in vitro experiment revealed that the MnIO nanoparticles exhibited T1-weighted MRI capability (r1 = 8.24 mM(-1) s(-1), r2/r1 = 2.18) and good photothermal effect under near-infrared laser irradiation (808 nm). Using 4T1 tumor-bearing mice as an animal model, we further demonstrated that the MnIO-dBSA composites could significantly increase T1 MRI signal intensity at the tumor site (about two times) and effectively ablate tumor tissues with photoirradiation. Taken together, this work demonstrates the great potential of the MnIO nanoparticles as an ideal theranostic platform for efficient tumor MR imaging and photothermal therapy. PMID:25672225

  4. Modeling sorption of divalent metal cations on hydrous manganese oxide using the diffuse double layer model

    USGS Publications Warehouse

    Tonkin, J.W.; Balistrieri, L.S.; Murray, J.W.

    2004-01-01

    Manganese oxides are important scavengers of trace metals and other contaminants in the environment. The inclusion of Mn oxides in predictive models, however, has been difficult due to the lack of a comprehensive set of sorption reactions consistent with a given surface complexation model (SCM), and the discrepancies between published sorption data and predictions using the available models. The authors have compiled a set of surface complexation reactions for synthetic hydrous Mn oxide (HMO) using a two surface site model and the diffuse double layer SCM which complements databases developed for hydrous Fe (III) oxide, goethite and crystalline Al oxide. This compilation encompasses a range of data observed in the literature for the complex HMO surface and provides an error envelope for predictions not well defined by fitting parameters for single or limited data sets. Data describing surface characteristics and cation sorption were compiled from the literature for the synthetic HMO phases birnessite, vernadite and ??-MnO2. A specific surface area of 746 m2g-1 and a surface site density of 2.1 mmol g-1 were determined from crystallographic data and considered fixed parameters in the model. Potentiometric titration data sets were adjusted to a pH1EP value of 2.2. Two site types (???XOH and ???YOH) were used. The fraction of total sites attributed to ???XOH (??) and pKa2 were optimized for each of 7 published potentiometric titration data sets using the computer program FITEQL3.2. pKa2 values of 2.35??0.077 (???XOH) and 6.06??0.040 (???YOH) were determined at the 95% confidence level. The calculated average ?? value was 0.64, with high and low values ranging from 1.0 to 0.24, respectively. pKa2 and ?? values and published cation sorption data were used subsequently to determine equilibrium surface complexation constants for Ba2+, Ca2+, Cd 2+, Co2+, Cu2+, Mg2+, Mn 2+, Ni2+, Pb2+, Sr2+ and Zn 2+. In addition, average model parameters were used to predict additional

  5. Heavy metals and manganese oxides in the genesee watershed, New York state: effects of geology and land use

    USGS Publications Warehouse

    Whitney, P.R.

    1981-01-01

    Manganese oxide coatings on gravels from 255 sites on tributary streams in the Genesee River Watershed were analyzed for Mn, Fe, Zn, Cd, Co, Ni, Pb, and Cu. The results were compared with data on bedrock geology, surficial geology and land use, using factor analysis and stepwise multiple regression. All metals except Pb show strong positive correlation with Mn. This association results from the well-known tendency of Mn oxide precipitates to adsorb and incorporate dissolved trace metals. Pb may be present in a separate phase on the gravel surfaces; alternatively Pb abundance may be so strongly influenced by environmental factors that the effect of varying abundance of the carrier phase becomes relatively unimportant. When the effects of varying Mn abundance are allowed for, Pb and to a lesser extent Zn and Cu abundances are seen to be related to commercial, industrial and residential land use. In addition to this pollution effect, all the trace metals, Cd and Ni most strongly, tend to be more abundant in oxide coatings from streams in the forested uplands in the southern part of the area. This probably reflects increased geochemical mobility of the metals in the more acid soils and groundwater of the southern region. A strong Zn anomaly is present in streams draining areas underlain by the Lockport Formation. Oxide coatings in these streams contain up to 5% Zn, originating from disseminated sphalerite in the Lockport and secondary Zn concentrations in the overlying muck soils. The same group of metals, plus calcium and loss on ignition, were determined in the silt and clay (minus 230 mesh) fraction of stream sediments from 129 of the same sites, using a hot nitric acid leach. The amounts of manganese in the sediments are low (average 1020 ppm) and manganese oxides are, at most, of relatively minor significance in the trace-metal geochemistry of these sediments. The bulk of the trace metals in sediment appears to be associated with iron oxides, clays and organic

  6. Plasma deposition of aluminum oxide films

    NASA Astrophysics Data System (ADS)

    Catherine, Y.; Talebian, A.

    1988-03-01

    A plasma deposition technique for amorphous aluminum oxide films is discussed. A 450 kHz or 13.56 MHz power supply was used to generate the plasma and the deposition of the film was achieved at low plasma power using trimethyl-aluminum and carbon dioxide reactant sources. It has been found that for the low frequency plasma the growth is strongly dependent upon TMA concentration, indicating that the growth process is mass transport limited. On the other hand using the 13.56 MHz discharge results in a surface controlled growth rate. An increase in the deposition temperature up to 300° C makes the films more dense and lowers their etching rate. FTIR and ESCA measurements showed that oxidation is only completed with high CO2 concentrations and a deposition temperature above 250° C. The dielectric films were found to have a dielectric constant in the range 7.3=2-9 and a refractive index between 1.5 1.8 depending upon deposition conditions.

  7. Photo-catalytic Degradation and Sorption of Radio-cobalt from EDTA-Co Complexes Using Manganese Oxide Materials - 12220

    SciTech Connect

    Koivula, Risto; Harjula, Risto; Tusa, Esko

    2012-07-01

    The synthesised cryptomelane-type α-MnO{sub 2} was tested for its Co-57 uptake properties in UV-photo-reactor filled with 10 μM Co-EDTA solution with a background of 10 mM NaNO{sub 3}. High cobalt uptake of 96% was observed after 1 hour of UV irradiation. As for comparison, a well-known TiO{sub 2} (Degussa P25) was tested as reference material that showed about 92% cobalt uptake after six hours of irradiation in identical experiment conditions. It was also noted that the cobalt uptake on cryptomelane with out UV irradiation was modest, only about 10%. Decreasing the pH of the Co-EDTA solution had severe effects on the cobalt uptake mainly due to the rather high point of zero charge of the MnO{sub 2} surface (pzc at pH ∼4.5). Modifying the synthesis procedure we were able to produce a material that functioned well even in solution of pH 3 giving cobalt uptake of almost 99%. The known properties, catalytic and ion exchange, of manganese oxides were simultaneously used for the separation of EDTA complexed Co-57. Tunnel structured cryptomelane -type showed very fast and efficient Co uptake properties outperforming the well known and widely used Degussa P25 TiO{sub 2} in both counts. The layered structured manganese oxide, birnessite, reached also as high Co removal level as the reference material Degussa did but the reaction rate was considerably faster. Since the decontamination solutions are typically slightly acidic and the point of zero charge of the manganese oxides are rather high > pH 4.5 the material had to be modified. This modified material had tolerance to acidic solutions and it's Co uptake performance remained high in the solutions of lower pH (pH 3). Increasing the ion concentration of test solutions, background concentration, didn't affect the final Co uptake level; however, some changes in the uptake kinetics could be seen. The increase in EDTA/MoMO ratio was clearly reflected in the Co uptake curves. The obtained results of manganese oxide were

  8. Validation of In-Situ Iron-Manganese Oxide Coated Stream Pebbles as Sensors for Arsenic Source Monitoring

    NASA Astrophysics Data System (ADS)

    Blake, J.; Peters, S. C.; Casteel, A.

    2013-12-01

    Locating nonpoint source contaminant fluxes can be challenging due to the inherent heterogeneity of source and of the subsurface. Contaminants such as arsenic are a concern for drinking water quality and ecosystem health. Arsenic contamination can be the result of several natural and anthropogenic sources, and therefore it can be difficult to trace and identify major areas of arsenic in natural systems. Identifying a useful source indicator for arsenic is a crucial step for environmental remediation efforts. Previous studies have found iron-manganese oxide coated streambed pebbles as useful source indicators due to their high attraction for heavy metals in water. In this study, pebbles, surface water at baseflow and nearby rocks were sampled from the Pennypack Creek and its tributaries, in southwestern Pennsylvania, to test the ability of coated streambed pebbles as environmental source indicators for arsenic. Quartz pebbles, 5-7 cm in diameter, were sampled to minimize elemental contamination from rock chemistry. In addition, quartz provides an excellent substrate for iron and manganese coatings to form. These coatings were leached from pebbles using 4M nitric acid with 0.1% concentrated hydrochloric acid. Following sample processing, analyses were performed using an ICP-MS and the resulting data were spatially organized using ArcGIS software. Arsenic, iron and manganese concentrations in the leachate are normalized to pebble surface area and each location is reported as a ratio of arsenic to iron and manganese. Results suggest that iron-manganese coated stream pebbles are useful indicators of arsenic location within a watershed.

  9. Well-ordered organic-inorganic hybrid layered manganese oxide nanocomposites with excellent decolorization performance

    SciTech Connect

    Zhou, Junli; Yu, Lin; Sun, Ming; Ye, Fei; Lan, Bang; Diao, Guiqiang; He, Jun

    2013-02-15

    Well-ordered organic-inorganic hybrid layered manganese oxide nanocomposites (CTAB-Al-MO) with excellent decolorization performance were prepared through a two-step process. Specifically, the MnO{sub 2} nanosheets were self-assembled in the presence of CTAB, and subsequently pillared with Keggin ions. The obtained CTAB-Al-MO with the basal spacing of 1.59 nm could be stable at 300 Degree-Sign C for 2 h and also possesses high total pore volumes (0.41 cm Superscript-Three g{sup -1}) and high specific BET surface area (161 m{sup 2} g{sup -1}), which is nine times larger than that of the pristine (19 m{sup 2} g{sup -1}). Possible formation process for the highly thermal stable CTAB-Al-MO is proposed here. The decolorization experiments of methyl orange showed that the obtained CTAB-Al-MO exhibit excellent performance in wastewater treatment and the decolorization rate could reach 95% within 5 min. - Graphical Abstract: Well-ordered organic-inorganic hybrid LMO nanocomposites (CTAB-Al-MO) with excellent decolorization performance were prepared through a two-step process. Specifically, the MnO{sub 2} nanosheets were self-assembled by CTAB, and subsequently pillared with Keggin ions. Highlights: Black-Right-Pointing-Pointer A two-step synthesis method was used to prepare the CTAB-Al-MO. Black-Right-Pointing-Pointer The CTAB-Al-MO has the large basal spacing and high specific BET surface area. Black-Right-Pointing-Pointer The thermal stability of the well-ordered CTAB-Al-MO could obviously improve. Black-Right-Pointing-Pointer The CTAB-Al-MO exhibits excellent oxidation and absorption ability to remove organic pollutants.

  10. Normal Cellular Prion Protein Protects against Manganese-induced Oxidative Stress and Apoptotic Cell Death

    PubMed Central

    Choi, Christopher J.; Anantharam, Vellareddy; Saetveit, Nathan J.; Houk, Robert. S.; Kanthasamy, Arthi; Kanthasamy, Anumantha G.

    2012-01-01

    The normal prion protein is abundantly expressed in the CNS, but its biological function remains unclear. The prion protein has octapeptide repeat regions that bind to several divalent metals, suggesting that the prion proteins may alter the toxic effect of environmental neurotoxic metals. In the present study, we systematically examined whether prion protein modifies the neurotoxicity of manganese (Mn) by comparing the effect of Mn on mouse neural cells expressing prion protein (PrPC -cells) and prion-knockout (PrPKO -cells). Exposure to Mn (10 μM-1 mM) for 24 hr produced a dose-dependent cytotoxic response in both PrPC -cells and PrPKO -cells. Interestingly, PrPC -cells (EC50 117.6μM) were more resistant to Mn-induced cytotoxicity, as compared to PrPKO -cells (EC50 59.9μM), suggesting a protective role for PrPC against Mn neurotoxicity. Analysis of intracellular Mn levels showed less Mn accumulation in PrPC -cells as compared to PrPKO -cells. Furthermore, Mn-induced mitochondrial depolarization and ROS generation were significantly attenuated in PrPC -cells as compared to PrPKO -cells. Measurement of antioxidant status revealed similar basal levels of glutathione (GSH) in PrPC -cells and PrPKO -cells; however, Mn treatment caused greater depletion of GSH in PrPKO -cells. Mn-induced mitochondrial depolarization and ROS production were followed by time- and dose-dependent activation of the apoptotic cell death cascade involving caspase-9 and -3. Notably, DNA fragmentation induced by both Mn treatment and oxidative stress-inducer hydrogen peroxide (100μM) was significantly suppressed in PrPC -cells as compared to PrPKO -cells. Together, these results demonstrate that prion protein interferes with divalent metal Mn uptake and protects against Mn-induced oxidative stress and apoptotic cell death. PMID:17483122

  11. Pulsed Laser Deposition of Oxide Thin Films

    NASA Astrophysics Data System (ADS)

    Brodoceanu, D.; Scarisoreanu, N. D.; Filipescu, M. (Morar); Epurescu, G. N.; Matei, D. G.; Verardi, P.; Craciun, F.; Dinescu, M.

    2004-10-01

    Pulsed Laser Deposition (PLD) emerged as an attractive technique for growth of thin films with different properties as metals, semiconductors, ferroelectrics, biocompatibles, polymers, etc., due to its important advantages: (i) the stoichiometric transfer of a complex composition from target to film and film crystallization at lower substrate temperature respect to other techniques (due to the high energy of species in the laser plasma); (ii) single step process, synthesis and deposition; (iii) creation in plasma of species impossible to be obtained by other processes; (iv) possibility of "in situ" heterostructure deposition using a multi-target system, etc. Simple or complex oxides are between the materials widely studied for their applications. PMN is the most known relaxor ferroelectric material: it exhibits a high dielectric constant value around the (diffuse) maximum phase transition temperature, of more than 35 000 in bulk form. Other oxides as lead zirconate titanate, Pb(ZrxTi1-x)O3 simple or La doped exhibit exceptional properties as large remanent polarization, high dielectric permittivity, high piezoelectric coefficient. SrBi2Ta2O9 (SBT) is characterized by a high "fatigue resistance" (constant remanent polarization until 1012 switching cycles), low imprint, and low leakage current. The physical properties of zirconium oxide (or zirconia) -- high strength, stability at high temperatures -- make it useful for applications involving gas sensors, corrosion or heat resistant mechanical parts, high refractive index optical coatings. Of particular interest is its use as an alternative gate dielectric in metal-oxide-semiconductor (MOS) devices or capacitor in dynamic random access memory (DRAM) chips. All these oxides have been deposited by laser ablation in oxygen reactive atmosphere and some of their properties will be presented in this paper.

  12. Revisiting the coordination chemistry for preparing manganese oxide nanocrystals in the presence of oleylamine and oleic acid

    NASA Astrophysics Data System (ADS)

    Zhang, Hongwei; Jing, Lihong; Zeng, Jianfeng; Hou, Yi; Li, Zhen; Gao, Mingyuan

    2014-05-01

    By pyrolyzing manganese(ii) acetate in 1-octadecene in the presence of oleylamine and oleic acid, manganese oxide nanocrystals were prepared. It was observed that both MnO and Mn3O4 nanocrystals were simultaneously formed by quickly heating the reaction mixture up to 250 °C, while a preheating procedure carried out at 100 °C led to uniform MnO nanocubes that developed into eight-arm MnO nanocrystals upon prolonged reaction. To understand the mechanisms for forming these two different kinds of manganese oxide nanocrystals, i.e., Mn3O4 and MnO, the coordination between oleic acid/oleylamine and Mn2+ was investigated. The detailed investigations suggest that Mn2+-oleylamine coordination is kinetically driven and favorable for the formation of Mn3O4 nanocrystals due to the relatively low electronegativity of N from oleylamine, while Mn2+-oleate coordination is thermodynamically driven and can prevent the central metal ion (Mn2+) from being oxidized owing to the relatively high electronegativity of O from the oleate ligand. Following these new insights, by properly balancing the coordination of oleic acid and oleylamine to Mn2+, the selective synthesis of MnO and Mn3O4 nanocrystals with uniform shapes was successfully achieved.By pyrolyzing manganese(ii) acetate in 1-octadecene in the presence of oleylamine and oleic acid, manganese oxide nanocrystals were prepared. It was observed that both MnO and Mn3O4 nanocrystals were simultaneously formed by quickly heating the reaction mixture up to 250 °C, while a preheating procedure carried out at 100 °C led to uniform MnO nanocubes that developed into eight-arm MnO nanocrystals upon prolonged reaction. To understand the mechanisms for forming these two different kinds of manganese oxide nanocrystals, i.e., Mn3O4 and MnO, the coordination between oleic acid/oleylamine and Mn2+ was investigated. The detailed investigations suggest that Mn2+-oleylamine coordination is kinetically driven and favorable for the formation of Mn3

  13. Iron and manganese in oxide minerals and in glasses: preliminary consideration of Eh buffering potential at Yucca Mountain, Nevada

    SciTech Connect

    Caporuscio, F.A.; Vaniman, D.T.

    1985-04-01

    The tuffs of Yucca Mountain at the Nevada Test Site are currently under investigation as a possible deep burial site for high-level radioactive waste disposal. One of the main concerns is the effect of oxidizing groundwater on the transport of radionuclides. Rock components that may affect the oxygen content of groundwater include Fe-Ti oxides, Mn oxides, and glasses that contain ferrous iron. Some phenocryst Fe-Ti oxides at Yucca Mountain are in reduced states, whereas groundmass Fe-Ti oxides have been oxidized to hematite, rutile, and pseudobrookite (Fe{sup 3+}-bearing phases) exclusively. Estimates of Fe{sup 2+}-bearing oxides indicate that less than 0.33 vol% phenocrysts is available to act as solid buffering agents of Eh. Of this percentage, significant amounts of Fe-Ti oxides are isolated from effective interaction with groundwater because they occur in densely welded, devitrified tuffs that have low interstitial permeability. Manganese oxides occur primarily along fractures in the ash-flow tuffs. Because the Mn oxides are concentrated along the same pathways (fractures) where transport has occurred in the past, these small volume percentages could act as buffers. However, the oxidation states of actual Mn-oxide phases are high (Mn{sup 4+}), and these minerals have virtually no potential for reducing groundwater Eh. Manganese oxides may even act as oxidizing agents. However, regardless of their poor capabilities as reducing agents, the Mn oxides could be important as sorbents of heavy metals at Yucca Mountain. The lack of accessible, pristine Fe-Ti oxides and the generally high oxidation states of Mn oxides seem to rule out these oxides as Eh buffers of the Yucca Mountain groundwater system. Reduction of ferrous iron within glassy tuffs may have some effect on Eh, but further study is needed. At present it is prudent to assume that minerals and glasses have little or no capacity for reducing oxygen-rich groundwater at Yucca Mountain. 25 refs., 3 figs., 12

  14. New divalent manganese complex with pyridine carboxylate N-oxide ligand: Synthesis, structure and magnetic properties

    SciTech Connect

    Liu Fuchen; Xue Min; Wang Haichao; Ouyang Jie

    2010-09-15

    Two new manganese complexes, [Mn{sub 3}(L{sup 1}){sub 4}(NO{sub 3}){sub 2}]{sub n} (1, HL{sup 1}=nicotinate N-oxide acid) and [MnL{sup 2}Cl]{sub n} (2, HL{sup 2}=isonicotinate N-oxide acid)], have been hydrothermally synthesized and characterized by elemental analysis, IR and single-crystal X-ray diffraction. In 1, the L{sup 1} ligands take two different coordinated modes bridging four and three Mn{sup II} ions. The nitrate anions take chelating coordination modes, leading one type of the Mn{sup II} ions as a 4-connected node. The whole net can be viewed as a 3, 4, 6-connected 4-nodal net with Schlaefli notation {l_brace}4{sup 3{r_brace}}2{l_brace}4{sup 4}; 6{sup 2{r_brace}}4{l_brace}4{sup 6}; 6{sup 6}; 8{sup 3{r_brace}}. Complex 2 has a honeycomb layer mixed bridged by chlorine, N-oxide and carboxylate. The adjacent layers are linked by the phenyl ring of L{sup 2} ligand, giving a 3D framework with a {l_brace}3{sup 4}; 5{sup 4{r_brace}} {l_brace}3{sup 2};4;5{sup 6};6{sup 6{r_brace}} 4, 6-connect net. Magnetic studies indicate that 1 is an antiferromagnet with low-dimensional characteristic, in which a -J{sub 1}J{sub 1}J{sub 2}- coupled alternating chain is predigested. Fitting the data of 1 gives the best parameters J{sub 1}=-2.77, J{sub 2}=-0.67 cm{sup -1}. The magnetic properties of complex 2 represent the character of the 2D honeycomb layer with the J{sub 1}=-2.05 and J{sub 2}=0.55 cm{sup -1}, which results in a whole antiferromagnetic state. - Graphical abstract: The synthesis, crystal structure and magnetic properties of two new MnII complexes with pyridyl-carboxylate N-oxide ligands are reported.

  15. Biological versus mineralogical chromium reduction: potential for reoxidation by manganese oxide.

    PubMed

    Butler, Elizabeth C; Chen, Lixia; Hansel, Colleen M; Krumholz, Lee R; Elwood Madden, Andrew S; Lan, Ying

    2015-11-01

    Hexavalent chromium (Cr(vi), present predominantly as CrO4(2-) in water at neutral pH) is a common ground water pollutant, and reductive immobilization is a frequent remediation alternative. The Cr(iii) that forms upon microbial or abiotic reduction often co-precipitates with naturally present or added iron (Fe), and the stability of the resulting Fe-Cr precipitate is a function of its mineral properties. In this study, Fe-Cr solids were formed by microbial Cr(vi) reduction using Desulfovibrio vulgaris strain RCH1 in the presence of the Fe-bearing minerals hematite, aluminum substituted goethite (Al-goethite), and nontronite (NAu-2, Clay Minerals Society), or by abiotic Cr(vi) reduction by dithionite reduced NAu-2 or iron sulfide (FeS). The properties of the resulting Fe-Cr solids and their behavior upon exposure to the oxidant manganese (Mn) oxide (birnessite) differed significantly. In microcosms containing strain RCH1 and hematite or Al-goethite, there was significant initial loss of Cr(vi) in a pattern consistent with adsorption, and significant Cr(vi) was found in the resulting solids. The solid formed when Cr(vi) was reduced by FeS contained a high proportion of Cr(iii) and was poorly crystalline. In microcosms with strain RCH1 and hematite, Cr precipitates appeared to be concentrated in organic biofilms. Reaction between birnessite and the abiotically formed Cr(iii) solids led to production of significant dissolved Cr(vi) compared to the no-birnessite controls. This pattern was not observed in the solids generated by microbial Cr(vi) reduction, possibly due to re-reduction of any Cr(vi) generated upon oxidation by birnessite by active bacteria or microbial enzymes. The results of this study suggest that Fe-Cr precipitates formed in groundwater remediation may remain stable only in the presence of active anaerobic microbial reduction. If exposed to environmentally common Mn oxides such as birnessite in the absence of microbial activity, there is the potential

  16. Kinetics of the catalytic oxidation of phenol over manganese oxide in supercritical water

    SciTech Connect

    Oshima, Yoshito; Tomita, Kengo; Koda, Seiichiro

    1999-11-01

    A kinetic analysis was made for the phenol disappearance rate in catalytic oxidation of phenol over MnO{sub 2} in supercritical water at a fixed temperature of 425 C and pressures between 22.7 and 27.2 MPa. The nonsupported MnO{sub 2} catalyst possessed a strong activity for promoting phenol oxidation, though the overall reaction rate was appreciably influenced by internal mass-transfer resistance. From the kinetic analysis on the reaction rate of the phenol disappearance, the global rate expression of the surface reaction was obtained, where the reaction orders with respect to phenol, oxygen, and water were almost unity, 0.7, and {minus}2.0, respectively. A Langmuir-type mechanism, in which phenol and oxygen adsorbed on the catalytic sites and water adsorbed on the same site to inhibit the phenol and oxygen adsorption, was proposed to explain the reaction orders for phenol, oxygen, and water.

  17. Intense photo- and tribo-luminescence of three tetrahedral manganese(II) dihalides with chelating bidentate phosphine oxide ligand.

    PubMed

    Chen, Jun; Zhang, Qing; Zheng, Fa-Kun; Liu, Zhi-Fa; Wang, Shuai-Hua; Wu, A-Qing; Guo, Guo-Cong

    2015-02-21

    Three air-stable tetrahedral manganese(ii) dihalide complexes [MnX2(DPEPO)] (DPEPO = bis[2-(diphenylphosphino)phenyl]ether oxide; X = Cl, Br and I) were prepared. All of the obtained compounds were structurally characterized by single-crystal X-ray diffraction analyses, which reveal that they crystallize in centrosymmetric space groups and feature an isolated mononuclear structure with Mn(2+) in a tetrahedral environment. Interestingly, these complexes show excellent photoluminescent performance in neat solid form, with the highest total quantum yield (Φtotal) of up to 70% recorded for the dibromide complex. Intense green flashes of light could be observed by the naked eye when rubbing the manganese(ii) complexes. PMID:25597698

  18. Detection of different oxidation states of individual manganese porphyrins during their reaction with oxygen at a solid/liquid interface

    NASA Astrophysics Data System (ADS)

    den Boer, Duncan; Li, Min; Habets, Thomas; Iavicoli, Patrizia; Rowan, Alan E.; Nolte, Roeland J. M.; Speller, Sylvia; Amabilino, David B.; de Feyter, Steven; Elemans, Johannes A. A. W.

    2013-07-01

    Manganese porphyrins have been extensively investigated as model systems for the natural enzyme cytochrome P450 and as synthetic oxidation catalysts. Here, we report single-molecule studies of the multistep reaction of manganese porphyrins with molecular oxygen at a solid/liquid interface, using a scanning tunnelling microscope (STM) under environmental control. The high lateral resolution of the STM, in combination with its sensitivity to subtle differences in the electronic properties of molecules, allowed the detection of at least four distinct reaction species. Real-space and real-time imaging of reaction dynamics enabled the observation of active sites, immobile on the experimental timescale. Conversions between the different species could be tuned by the composition of the atmosphere (argon, air or oxygen) and the surface bias voltage. By means of extensive comparison of the results to those obtained by analogous solution-based chemistry, we assigned the observed species to the starting compound, reaction intermediates and products.

  19. Understanding Interactions between Manganese Oxide and Gold That Lead to Enhanced Activity for Electrocatalytic Water Oxidation

    PubMed Central

    2015-01-01

    To develop active nonprecious metal-based electrocatalysts for the oxygen evolution reaction (OER), a limiting reaction in several emerging renewable energy technologies, a deeper understanding of the activity of the first row transition metal oxides is needed. Previous studies of these catalysts have reported conflicting results on the influence of noble metal supports on the OER activity of the transition metal oxides. Our study aims to clarify the interactions between a transition metal oxide catalyst and its metal support in turning over this reaction. To achieve this goal, we examine a catalytic system comprising nanoparticulate Au, a common electrocatalytic support, and nanoparticulate MnOx, a promising OER catalyst. We conclusively demonstrate that adding Au to MnOx significantly enhances OER activity relative to MnOx in the absence of Au, producing an order of magnitude higher turnover frequency (TOF) than the TOF of the best pure MnOx catalysts reported to date. We also provide evidence that it is a local rather than bulk interaction between Au and MnOx that leads to the observed enhancement in the OER activity. Engineering improvements in nonprecious metal-based catalysts by the addition of Au or other noble metals could still represent a scalable catalyst as even trace amounts of Au are shown to lead a significant enhancement in the OER activity of MnOx. PMID:24661269

  20. Understanding interactions between manganese oxide and gold that lead to enhanced activity for electrocatalytic water oxidation.

    PubMed

    Gorlin, Yelena; Chung, Chia-Jung; Benck, Jesse D; Nordlund, Dennis; Seitz, Linsey; Weng, Tsu-Chien; Sokaras, Dimosthenis; Clemens, Bruce M; Jaramillo, Thomas F

    2014-04-01

    To develop active nonprecious metal-based electrocatalysts for the oxygen evolution reaction (OER), a limiting reaction in several emerging renewable energy technologies, a deeper understanding of the activity of the first row transition metal oxides is needed. Previous studies of these catalysts have reported conflicting results on the influence of noble metal supports on the OER activity of the transition metal oxides. Our study aims to clarify the interactions between a transition metal oxide catalyst and its metal support in turning over this reaction. To achieve this goal, we examine a catalytic system comprising nanoparticulate Au, a common electrocatalytic support, and nanoparticulate MnO(x), a promising OER catalyst. We conclusively demonstrate that adding Au to MnO(x) significantly enhances OER activity relative to MnO(x) in the absence of Au, producing an order of magnitude higher turnover frequency (TOF) than the TOF of the best pure MnO(x) catalysts reported to date. We also provide evidence that it is a local rather than bulk interaction between Au and MnO(x) that leads to the observed enhancement in the OER activity. Engineering improvements in nonprecious metal-based catalysts by the addition of Au or other noble metals could still represent a scalable catalyst as even trace amounts of Au are shown to lead a significant enhancement in the OER activity of MnO(x). PMID:24661269

  1. Manganese-Cobalt Mixed Spinel Oxides as Surface Modifiers for Stainless Steel Interconnects of Solid Oxide Fuel Cells

    SciTech Connect

    Xia, Gordon; Yang, Z Gary; Stevenson, Jeffry W.

    2006-11-06

    Ferritic stainless steels are promising candidates for interconnect applications in low- and mid-temperature solid oxide fuel cells (SOFCs). A couple of issues however remain for the particular application, including the chromium poisoning due to chromia evaporation, and long-term surface and electrical stability of the scale grown on these steels. Application of a manganese colbaltite spinel protection layer on the steels appears to be an effective approach to solve the issues. For an optimized performance, Mn{sub 1+x}Co{sub 2-x}O{sub 4} (-1 {le} x {le} 2) spinels were investigated against properties relative for protection coating applications on ferritic SOFC interconnects. Overall it appears that the spinels with x around 0.5 demonstrate a good CTE match to ceramic cell components, a relative high electrical conductivity, and a good thermal stability up to 1,250 C. This was confirmed by a long-term test on the Mn{sub 1.5}Co{sub 1.5}O{sub 4} protection layer that was thermally grown on Crofer22 APU, indicating the spinel protection layer not only significantly decreased the contact resistance between a LSF cathode and the stainless steel interconnects, but also inhibited the sub-scale growth on the stainless steels.

  2. PROGRESS REPORT. TRANSURANIC INTERFACIAL REACTION STUDIES ON MANGANESE OXIDE HYDROXIDE MINERAL SURFACES

    EPA Science Inventory

    Several DOE sites have been contaminated by transuranic radionuclide (TRU) discharges including neptunium and plutonium. Their interaction with the surrounding geological media can affect the transport and remediation of these radionuclides in the environment. Manganese based min...

  3. Investigation of photoelectrochemical-oxidized p-GaSb films

    NASA Astrophysics Data System (ADS)

    Lee, Hsin-Ying; Huang, Hung-Lin; Lee, Ching-Ting; Petrovich Pchelyakov, Oleg; Andreevich Pakhanov, Nikolay

    2012-12-01

    GaSb oxide films were directly formed on the p-GaSb films using the bias-assisted photoelectrochemical (PEC) oxidation method. X-ray photoelectron spectroscopy analysis indicated that the resulting GaSb oxide films consisted of Ga2O3, Sb2O3, and Sb2O5. Different from the non-PEC oxides, the PEC derived oxide contained much more Sb2O5 than Sb2O3. Besides, the interface state density between the PEC oxide and p-GaSb was lower than that of the ordinary oxide/p-GaSb interface. The high quality of the PEC-oxidized GaSb films was attributed to the increase of the stable Sb2O5 content and decrease of the elemental Sb content in the films.

  4. Rapid and highly selective removal of lead from water using graphene oxide-hydrated manganese oxide nanocomposites.

    PubMed

    Wan, Shunli; He, Feng; Wu, Jiayu; Wan, Wubo; Gu, Yawei; Gao, Bin

    2016-08-15

    To overcome the limits of graphene oxide (GO) as a novel sorbent for heavy metal removal (e.g., low sorption selectivity and difficulty in solid-liquid separation), a nanocomposite (HMO@GO) with excellent settling ability (<2min) was fabricated through in situ growing nanosized hydrated manganese oxide (HMO) (10.8±4.1nm) on GO. As a graphene-based adsorbent, HMO@GO exhibited fast sorption kinetics (<20min). Meanwhile, the introduced HMO endowed HMO@GO with outstanding sorption selectivity and capacity toward Pb(II) (>500mgg(-1)) in the presence of high-level competing Ca(II). Cyclic sorption batches showed that 1kg HMO@GO can treat at least 22m(3) Pb(II)-laden synthetic industrial drainage (5mgL(-1) Pb(II)) and 40m(3) drinking water (0.5mgL(-1) Pb(II)) to their corresponding limits (0.1mgL(-1) for wastewater and 10μgL(-1) for drinking water) enforced in China. Additionally, the exhausted HMO@GO can be effectively regenerated using 0.3 M HCl for repeated uses. The eminent performance of HMO@GO was attributed to its specific structure, that is, the abundant oxygen-containing groups on GO mediated the growth of highly dispersed HMO that preferably sequestrated Pb(II) through specific interaction, and the host GO offered the preconcentration of Pb(II) for enhanced sequestration through the Donnan membrane effect. PMID:27107233

  5. Removal and Recovery of Toxic Silver Ion Using Deep-Sea Bacterial Generated Biogenic Manganese Oxides

    PubMed Central

    Pei, Yuanjun; Chen, Xiao; Xiong, Dandan; Liao, Shuijiao; Wang, Gejiao

    2013-01-01

    Products containing silver ion (Ag+) are widely used, leading to a large amount of Ag+-containing waste. The deep-sea manganese-oxidizing bacterium Marinobacter sp. MnI7-9 efficiently oxidizes Mn2+ to generate biogenic Mn oxide (BMO). The potential of BMO for recovering metal ions by adsorption has been investigated for some ions but not for Ag+. The main aim of this study was to develop effective methods for adsorbing and recovering Ag using BMO produced by Marinobacter sp. MnI7-9. In addition, the adsorption mechanism was determined using X-ray photoelectron spectroscopy analysis, specific surface area analysis, adsorption kinetics and thermodynamics. The results showed that BMO had a higher adsorption capacity for Ag+ compared to the chemical synthesized MnO2 (CMO). The isothermal absorption curves of BMO and CMO both fit the Langmuir model well and the maximum adsorption capacities at 28°C were 8.097 mmol/g and 0.787 mmol/g, for BMO and CMO, respectively. The change in enthalpy (ΔHθ) for BMO was 59.69 kJ/mol indicating that it acts primarily by chemical adsorption. The change in free energy (ΔGθ) for BMO was negative, which suggests that the adsorption occurs spontaneously. Ag+ adsorption by BMO was driven by entropy based on the positive ΔSθ values. The Ag+ adsorption kinetics by BMO fit the pseudo-second order model and the apparent activation energy of Ea is 21.72 kJ/mol. X-ray photoelectron spectroscopy analysis showed that 15.29% Ag+ adsorbed by BMO was transferred to Ag(0) and meant that redox reaction had happened during the adsorption. Desorption using nitric acid and Na2S completely recovered the Ag. The results show that BMO produced by strain MnI7-9 has potential for bioremediation and reutilization of Ag+-containing waste. PMID:24312566

  6. Removal and recovery of toxic silver ion using deep-sea bacterial generated biogenic manganese oxides.

    PubMed

    Pei, Yuanjun; Chen, Xiao; Xiong, Dandan; Liao, Shuijiao; Wang, Gejiao

    2013-01-01

    Products containing silver ion (Ag(+)) are widely used, leading to a large amount of Ag(+)-containing waste. The deep-sea manganese-oxidizing bacterium Marinobacter sp. MnI7-9 efficiently oxidizes Mn(2+) to generate biogenic Mn oxide (BMO). The potential of BMO for recovering metal ions by adsorption has been investigated for some ions but not for Ag(+). The main aim of this study was to develop effective methods for adsorbing and recovering Ag using BMO produced by Marinobacter sp. MnI7-9. In addition, the adsorption mechanism was determined using X-ray photoelectron spectroscopy analysis, specific surface area analysis, adsorption kinetics and thermodynamics. The results showed that BMO had a higher adsorption capacity for Ag(+) compared to the chemical synthesized MnO2 (CMO). The isothermal absorption curves of BMO and CMO both fit the Langmuir model well and the maximum adsorption capacities at 28°C were 8.097 mmol/g and 0.787 mmol/g, for BMO and CMO, respectively. The change in enthalpy (ΔH(θ)) for BMO was 59.69 kJ/mol indicating that it acts primarily by chemical adsorption. The change in free energy (ΔG(θ)) for BMO was negative, which suggests that the adsorption occurs spontaneously. Ag(+) adsorption by BMO was driven by entropy based on the positive ΔS(θ) values. The Ag(+) adsorption kinetics by BMO fit the pseudo-second order model and the apparent activation energy of Ea is 21.72 kJ/mol. X-ray photoelectron spectroscopy analysis showed that 15.29% Ag(+) adsorbed by BMO was transferred to Ag(0) and meant that redox reaction had happened during the adsorption. Desorption using nitric acid and Na2S completely recovered the Ag. The results show that BMO produced by strain MnI7-9 has potential for bioremediation and reutilization of Ag(+)-containing waste. PMID:24312566

  7. Effect of the high pressure on the structure and intercalation properties of lithium-nickel-manganese oxides

    SciTech Connect

    Yoncheva, M.; Stoyanova, R.; Zhecheva, E. Alcantara, R.; Ortiz, G.; Tirado, J.L.

    2007-06-15

    Lithium-nickel-manganese oxides (Li{sub 1+} {sub x} (Ni{sub 1/2}Mn{sub 1/2}){sub 1-} {sub x} O{sub 2}, x=0 and 0.2), having different cationic distributions and an oxidation state of Ni varying from 2+ to 3+, were formed under a high-pressure (3 GPa). The structure and cationic distribution in these oxides were examined by powder X-ray diffraction, infrared (IR) and electron paramagnetic resonance (EPR) in X-band (9.23 GHz) and at higher frequencies (95 and 285 GHz). Under a high pressure, a solid-state reaction between NiMnO{sub 3} and Li{sub 2}O yields LiNi{sub 0.5}Mn{sub 0.5}O{sub 2} with a disordered rock-salt type structure. The paramagnetic ions stabilized in this oxide are mainly Ni{sup 2+} and Mn{sup 4+} together with Mn{sup 3+} (about 10%). The replacement of Li{sub 2}O by Li{sub 2}O{sub 2} permits increasing the oxidation state of Ni ions in lithium-nickel-manganese oxides. The higher oxidation state of Ni ions favours the stabilization of the layered modification, where the Ni-to-Mn ratio is preserved: Li(Li{sub 0.2}Ni{sub 0.4}Mn{sub 0.4})O{sub 2}. The paramagnetic ions stabilized in the layered oxide are mainly Ni{sup 3+} and Mn{sup 4+} ions. The disordered and ordered phases display different intercalation properties in respect of lithium. The changes in local Ni,Mn-environment during the electrochemical reaction are discussed on the basis of EPR and IR spectroscopy. - Graphical abstract: Lithium-nickel-manganese oxides (Li{sub 1+} {sub x} (Ni{sub 1/2}Mn{sub 1/2}){sub 1-} {sub x} O{sub 2}, x=0 and 0.2), having different cationic distributions and an oxidation states of Ni varying from 2+ to 3+, were formed under a high-pressure (3 GPa)

  8. One-dimensional manganese-cobalt oxide nanofibres as bi-functional cathode catalysts for rechargeable metal-air batteries

    PubMed Central

    Jung, Kyu-Nam; Hwang, Soo Min; Park, Min-Sik; Kim, Ki Jae; Kim, Jae-Geun; Dou, Shi Xue; Kim, Jung Ho; Lee, Jong-Won

    2015-01-01

    Rechargeable metal-air batteries are considered a promising energy storage solution owing to their high theoretical energy density. The major obstacles to realising this technology include the slow kinetics of oxygen reduction and evolution on the cathode (air electrode) upon battery discharging and charging, respectively. Here, we report non-precious metal oxide catalysts based on spinel-type manganese-cobalt oxide nanofibres fabricated by an electrospinning technique. The spinel oxide nanofibres exhibit high catalytic activity towards both oxygen reduction and evolution in an alkaline electrolyte. When incorporated as cathode catalysts in Zn-air batteries, the fibrous spinel oxides considerably reduce the discharge-charge voltage gaps (improve the round-trip efficiency) in comparison to the catalyst-free cathode. Moreover, the nanofibre catalysts remain stable over the course of repeated discharge-charge cycling; however, carbon corrosion in the catalyst/carbon composite cathode degrades the cycling performance of the batteries. PMID:25563733

  9. One-dimensional manganese-cobalt oxide nanofibres as bi-functional cathode catalysts for rechargeable metal-air batteries.

    PubMed

    Jung, Kyu-Nam; Hwang, Soo Min; Park, Min-Sik; Kim, Ki Jae; Kim, Jae-Geun; Dou, Shi Xue; Kim, Jung Ho; Lee, Jong-Won

    2015-01-01

    Rechargeable metal-air batteries are considered a promising energy storage solution owing to their high theoretical energy density. The major obstacles to realising this technology include the slow kinetics of oxygen reduction and evolution on the cathode (air electrode) upon battery discharging and charging, respectively. Here, we report non-precious metal oxide catalysts based on spinel-type manganese-cobalt oxide nanofibres fabricated by an electrospinning technique. The spinel oxide nanofibres exhibit high catalytic activity towards both oxygen reduction and evolution in an alkaline electrolyte. When incorporated as cathode catalysts in Zn-air batteries, the fibrous spinel oxides considerably reduce the discharge-charge voltage gaps (improve the round-trip efficiency) in comparison to the catalyst-free cathode. Moreover, the nanofibre catalysts remain stable over the course of repeated discharge-charge cycling; however, carbon corrosion in the catalyst/carbon composite cathode degrades the cycling performance of the batteries. PMID:25563733

  10. One-dimensional manganese-cobalt oxide nanofibres as bi-functional cathode catalysts for rechargeable metal-air batteries

    NASA Astrophysics Data System (ADS)

    Jung, Kyu-Nam; Hwang, Soo Min; Park, Min-Sik; Kim, Ki Jae; Kim, Jae-Geun; Dou, Shi Xue; Kim, Jung Ho; Lee, Jong-Won

    2015-01-01

    Rechargeable metal-air batteries are considered a promising energy storage solution owing to their high theoretical energy density. The major obstacles to realising this technology include the slow kinetics of oxygen reduction and evolution on the cathode (air electrode) upon battery discharging and charging, respectively. Here, we report non-precious metal oxide catalysts based on spinel-type manganese-cobalt oxide nanofibres fabricated by an electrospinning technique. The spinel oxide nanofibres exhibit high catalytic activity towards both oxygen reduction and evolution in an alkaline electrolyte. When incorporated as cathode catalysts in Zn-air batteries, the fibrous spinel oxides considerably reduce the discharge-charge voltage gaps (improve the round-trip efficiency) in comparison to the catalyst-free cathode. Moreover, the nanofibre catalysts remain stable over the course of repeated discharge-charge cycling; however, carbon corrosion in the catalyst/carbon composite cathode degrades the cycling performance of the batteries.

  11. Higher-power supercapacitor electrodes based on mesoporous manganese oxide coating on vertically aligned carbon nanofibers

    NASA Astrophysics Data System (ADS)

    Klankowski, Steven A.; Pandey, Gaind P.; Malek, Gary; Thomas, Conor R.; Bernasek, Steven L.; Wu, Judy; Li, Jun

    2015-04-01

    A study on the development of high-power supercapacitor materials based on formation of thick mesoporous MnO2 shells on a highly conductive 3D template using vertically aligned carbon nanofibers (VACNFs). Coaxial manganese shells of 100 to 600 nm nominal thicknesses are sputter-coated on VACNFs and then electrochemically oxidized into rose-petal-like mesoporous MnO2 structure. Such a 3D MnO2/VACNF hybrid architecture provides enhanced ion diffusion throughout the whole MnO2 shell and yields excellent current collection capability through the VACNF electrode. These two effects collectively enable faster electrochemical reactions during charge-discharge of MnO2 in 1 M Na2SO4. Thick MnO2 shells (up to 200 nm in radial thickness) can be employed, giving a specific capacitance up to 437 F g-1. More importantly, supercapacitors employing such a 3D MnO2/VACNF hybrid electrode illustrate more than one order of magnitude higher specific power than the state-of-the-art ones based on other MnO2 structures, reaching ~240 kW kg-1, while maintaining a comparable specific energy in the range of 1 to 10 Wh kg-1. This hybrid approach demonstrates the potential of 3D core-shell architectures for high-power energy storage devices.A study on the development of high-power supercapacitor materials based on formation of thick mesoporous MnO2 shells on a highly conductive 3D template using vertically aligned carbon nanofibers (VACNFs). Coaxial manganese shells of 100 to 600 nm nominal thicknesses are sputter-coated on VACNFs and then electrochemically oxidized into rose-petal-like mesoporous MnO2 structure. Such a 3D MnO2/VACNF hybrid architecture provides enhanced ion diffusion throughout the whole MnO2 shell and yields excellent current collection capability through the VACNF electrode. These two effects collectively enable faster electrochemical reactions during charge-discharge of MnO2 in 1 M Na2SO4. Thick MnO2 shells (up to 200 nm in radial thickness) can be employed, giving a

  12. Characterization of the Fe-Doped Mixed-Valent Tunnel Structure 2 Manganese Oxide KOMS-2

    SciTech Connect

    Hanson J. C.; Shen X.; Morey A.M.; Liu J.; Ding Y.; Cai J.; Durand J.; Wang Q.; Wen W.; Hines W.A.; Bai J.; Frenkel A.I.; Reiff W.; Aindow M.; Suib S.L.

    2011-11-10

    A sol-gel-assisted combustion method was used to prepare Fe-doped manganese oxide octahedral molecular sieve (Fe-KOMS-2) materials with the cryptomelane structure. Characterization of the nanopowder samples over a wide range of Fe-doping levels (0 {le} Fe/Mn {le} 1/2) was carried out using a variety of experimental techniques. For each sample, Cu K{alpha} XRD and ICP-AES were used to index the cryptomelane structure and determine the elemental composition, respectively. A combination of SEM and TEM images revealed that the morphology changes from nanoneedle to nanorod after Fe doping. Furthermore, TGA scans indicated that the thermal stability is also enhanced with the doping. Anomalous XRD demonstrated that the Fe ions replace the Mn ions in the cryptomelane structure, particularly in the (211) planes, and results in a lattice expansion along the c axis, parallel to the tunnels. Reasonable fits to EXAFS data were obtained using a model based on the cryptomelane structure. Moessbauer spectra for selected Fe-KOMS-2 samples indicated that the Fe is present as Fe{sup 3+} in an octahedral environment similar to Mn in the MnO{sub 6} building blocks of KOMS-2. Magnetization measurements detected a small amount of {gamma}-Fe{sub 2}O{sub 3} second phase (e.g., 0.6 wt % for the Fe/Mn = 1/10 sample), the vast majority of the Fe being in the structure as Fe{sup 3+} in the high-spin state.

  13. The dielectric behavior of perovskite-related manganese oxides with stretched bonds or multiferroic properties

    NASA Astrophysics Data System (ADS)

    Denyszyn, Jonathan Charles

    This dissertation presents two investigations into the dielectric behavior of non-d0 perovskite-related manganese oxides: the first investigation probes the unique multiferroic properties of the hexagonal-perovskite series RMn1-xGaxO3 (R = Y, Ho) and the second explores the importance of lattice stress and the effect of the metal-cation d n-character on the dielectric properties of the perovskite series SryCa1-yMn1-xBxO3-delta (B = Ti, Zr). In the hexagonal-perovskite series, doping the Mn-site with Ga increased the c lattice constant and diluted the magnetic interactions in the ab plane. The interplay of these two effects perturbed the ferrielectric, antiferromagnetic, and multiferroic interactions. The change in these interactions demonstrated chemical control of the multiferroic interactions in the hexagonal-perovskite system for the first time and highlighted the structural mechanism behind the multiferroic properties. In the second investigation, the relationship between the tensile stress on the (Mn--O) bond and the ionic dielectric constant of SryCa 1-yMnO3-delta proved difficult to quantify because the small band gap and chemical activity of the Mn4+ cation made samples with y ≥ 0.5 too conducting to measure the dielectric relaxations. To explore the ionic contribution to the dielectric behavior by an alternate path, a doping scheme was devised to decrease the sample conductivity of SrMnO 3-delta at the expense of some of the tensile stress on the (Mn--O) bond. Doping the Mn site with larger 4+ cations (Ti and Zr) reduced the dielectric constant; however, the reduction of the dielectric constant cannot be explained by the effect of the tensile stress on the (Mn--O) bond alone.

  14. Copper oxide thin films for ethanol sensing

    NASA Astrophysics Data System (ADS)

    Lamri Zeggar, M.; Bourfaa, F.; Adjimi, A.; Aida, M. S.; Attaf, N.

    2016-03-01

    The present is a study of a new active layer for ethanol (C2H5OH) vapour sensing devices based on copper oxide (CuO). CuO films were prepared by spray ultrasonic pyrolysis at a substrate temperature of 350 °C. Films microstructure was examined by X-ray diffraction and atomic force microscopy. Vapour-sensing testing was conducted using static vapour-sensing system, at different operating temperatures in the range of 100°C to 175°C for the vapour concentration of 300 ppm. The results show a high response of 45% at relatively low operating temperatures of 150°C towards ethanol vapour.

  15. Thin zinc oxide and cuprous oxide films for photovoltaic applications

    NASA Astrophysics Data System (ADS)

    Jeong, Seongho

    Metal oxide semiconductors and heterojunctions made from thin films of metal oxide semiconductors have broad range of functional properties and high potential in optical, electrical and magnetic devices such as light emitting diodes, spintronic devices and solar cells. Among the oxide semiconductors, zinc oxide (ZnO) and cuprous oxide (Cu2O) are attractive because they are inexpensive, abundant and nontoxic. As synthesized ZnO is usually an intrinsic n - type semiconductor with wide band gap (3.4 eV) and can be used as the transparent conducting window layer in solar cells. As synthesized Cu2O is usually a p - type semiconductor with a band gap of 2.17 eV and has been considered as a potential material for the light absorbing layer in solar cells. I used various techniques including metal organic chemical vapor deposition, magnetron sputtering and atomic layer deposition to grow thin films of ZnO and Cu2O and fabricated Cu2O/ZnO heterojunctions. I specifically investigated the optical and electrical properties of Cu 2O thin films deposited on ZnO by MOCVD and showed that Cu2O thin films grow as single phase with [110] axis aligned perpendicular to the ZnO surface which is (0001) plane and with in-plane rotational alignment due to (220) Cu2O || (0002)ZnO; [001]Cu2O || [12¯10]ZnO epitaxy. Moreover, I fabricated solar cells based on these Cu2O/ZnO heterojunctions and characterized them. Electrical characterization of these solar cells as a function of temperature between 100 K and 300 K under illumination revealed that interface recombination and tunneling at the interface are the factors that limit the solar cell performance. To date solar cells based on Cu2O/ZnO heterojunctions had low open circuit voltages (~ 0.3V) even though the expected value is around 1V. I achieved open circuit voltages approaching 1V at low temperature (~ 100 K) and showed that if interfacial recombination is reduced these cells can achieve their predicted potential.

  16. Oxidation resistance of Pb-Te-Se optical recording film

    NASA Astrophysics Data System (ADS)

    Terao, Motoyasu; Horigome, Shinkichi; Shigematsu, Kazuo; Miyauchi, Yasushi; Nakazawa, Masatoshi

    1987-08-01

    The dependence of oxidation resistance of metal-Te-Se optical recording films on film composition is investigated, as well as the effects of oxidation on laser beam recorded hole shape. The films are deposited by vacuum evaporation on substrates with a glass/UV light curing resin/cellulose nitrate structure. The role of Se in the film is to inhibit the oxidation. With at least 14% Se addition, film oxidation is completely inhibited even at 60 °C, relative humidity 95%. Depth profiles of elements in the recording films are analyzed by Auger electron and x-ray photoelectron spectroscopy to clarify the mechanisms of oxidation inhibition by Se addition. A selenium condensed layer is found at the inner part of an oxidized surface layer. The surface Te oxide layer and the Se-rich layer should inhibit the film inside from oxidizing. The role of the metallic elements In, Pb, Sn, Bi, and Sb in the film is to inhibit cracking and to decrease noise in reproduced signals by decreasing the size of crystal grains. Lead is found to be the best among these metallic elements, because the recorded hole shape is clean even when recorded after 15 days accelerated oxidation at 60 °C, relative humidity 95%. A very long storage life is expected for the Pb-Te-Se optical recording film.

  17. Time-of-flight study of photoinduced dynamics of copper and manganese phthalocyanine thin films on Si(111)

    NASA Astrophysics Data System (ADS)

    Ramonova, A. G.; Butkhuzi, T. G.; Abaeva, V. V.; Tvauri, I. V.; Khubezhov, S. A.; Turiev, A. M.; Tsidaeva, N. I.; Magkoev, T. T.

    2013-11-01

    Photoinduced fragmentation and desorption of species from copper phthalocyanine (CuPc) and manganese phthalocyanine 80 nm thick films deposited on Si(111) have been studied by means of atomic force microscopy and time-of-flight mass spectroscopy in an ultra-high vacuum chamber. The main fragments formed under the effect of low-fluence (1-3 mJ cm-2) nanosecond laser light with photon energies of 2.34 and 1.17 eV are the entire phthalocyanine molecule, molecular fragments, atomic Cu and Mn and a Si-substituted CuPc. The latter is presumably due to migration of the Si atom of the underlying support to the vacancy formed after photoejection of the metallic atom out of the phthalocyanine molecule. The mechanism of photofragmentation and desorption is essentially non-thermal involving the metal atom as a key factor.

  18. Towards an understanding of thallium isotope fractionation during adsorption to manganese oxides

    NASA Astrophysics Data System (ADS)

    Nielsen, Sune G.; Wasylenki, Laura E.; Rehkämper, Mark; Peacock, Caroline L.; Xue, Zichen; Moon, Ellen M.

    2013-09-01

    We have conducted the first study of Tl isotope fractionation during sorption of aqueous Tl(I) onto the manganese oxide hexagonal birnessite. The experiments had different initial Tl concentrations, amounts of birnessite, experimental durations, and temperatures, but all of them exhibit heavy Tl isotope compositions for the sorbed Tl compared with the solution, which is consistent with the direction of isotope fractionation observed between seawater and natural ferromanganese sediments. However, the magnitude of fractionation in all experiments (α ≈ 1.0002-1.0015, where α=205Tl/203Tl/205Tl/203Tl is smaller than observed between seawater and natural sediments (α ≈ 1.0019-1.0021; Rehkämper et al., 2002, Earth. Planet. Sci. Lett. 197, 65-81). The experimental results display a strong correlation between the concentration of Tl in the resulting Tl-sorbed birnessite and the magnitude of fractionation. This correlation is best explained by sorption of Tl to two sites on birnessite, one with large isotope fractionation and one with little or no isotope fractionation. Previous work (Peacock and Moon, 2012, Geochim. Cosmochim. Acta 84, 297-313) indicates that Tl in natural ferromanganese sediments is oxidized to Tl(III) and adsorbed over Mn vacancy sites in the phyllomanganate sheets of birnessite, and we hypothesize that this site is strongly fractionated from Tl in solution due to the change in oxidation state from aqueous Tl(I). In most experiments, which have orders of magnitude more Tl associated with the solid than in nature, these vacancy sites are probably fully saturated, so various amounts of additional Tl are likely sorbed to either edge sites on the birnessite or triclinic birnessite formed through oxidative ripening of the hexagonal starting material, with unknown oxidation state and little or no isotopic fractionation. Thus each experiment displays isotopic fractionation governed by the proportions of Tl in the fractionated and slightly fractionated

  19. Microbially-mediated thiocyanate oxidation and manganese cycling control arsenic mobility in groundwater at an Australian gold mine

    NASA Astrophysics Data System (ADS)

    Horvath, A. S.; Baldisimo, J. G.; Moreau, J. W.

    2010-12-01

    Arsenic contamination of groundwater poses a serious environmental and human health problem in many regions around the world. Historical groundwater chemistry data for a Western-Central Victorian gold mine (Australia) revealed a strong inverse correlation between dissolved thiocyanate and iron(II), supporting the interpretation that oxidation of thiocyanate, a major groundwater contaminant by-product of cyanide-based gold leaching, was coupled to reductive dissolution of iron ox(yhydrox)ides in tailings dam sediments. Microbial growth was observed in this study in a selective medium using SCN- as the sole carbon and nitrogen source. The potential for use of SCN- as a tracer of mining contamination in groundwater was evaluated in the context of biological SCN- oxidation potential in the aquifer. Geochemical data also revealed a high positive correlation between dissolved arsenic and manganese, indicating that sorption on manganese-oxides most likely controls arsenic mobility at this site. Samples of groundwater and sediments along a roughly straight SW-NE traverse away from a large mine tailings storage facility, and parallel to the major groundwater flow direction, were analysed for major ions and trace metals. Groundwater from wells approaching the tailings along this traverse showed a nearly five-fold increase (roughly 25-125 ppb) in dissolved arsenic concentrations relative to aqueous Mn(II) concentrations. Thus, equivalent amounts of dissolved manganese released a five-fold difference in the amount of adsorbed arsenic. The interpretation that reductive dissolution of As-bearing MnO2 at the mine site has been mediated by groundwater (or aquifer) microorganisms is consistent with our recovery of synthetic birnessite-reducing enrichment cultures that were inoculated with As-contaminated groundwaters.

  20. Electrochromism: from oxide thin films to devices

    NASA Astrophysics Data System (ADS)

    Rougier, A.; Danine, A.; Faure, C.; Buffière, S.

    2014-03-01

    In respect of their adaptability and performance, electrochromic devices, ECDs, which are able to change their optical properties under an applied voltage, have received significant attention. Target applications are multifold both in the visible region (automotive sunroofs, smart windows, ophthalmic lenses, and domestic appliances (oven, fridge…)) and in the infrared region (Satellites Thermal Control, IR furtivity). In our group, focusing on oxide thin films grown preferentially at room temperature, optimization of ECDs performances have been achieved by tuning the microstructure, the stoichiometry and the cationic composition of the various layers. Herein, our approach for optimized ECDs is illustrated through the example of WO3 electrochromic layer in the visible and in the IR domain as well as ZnO based transparent conducting oxide layer. Targeting the field of printed electronics, simplification of the device architecture for low power ECDs is also reported.

  1. Transparent Conductive Oxides in Thin Film Photovoltaics

    NASA Astrophysics Data System (ADS)

    Hamelmann, Frank U.

    2014-11-01

    This paper show results from the development of transparent conductive oxides (TCO's) on large areas for the use as front electrode in thin film silicon solar modules. It is focused on two types of zinc oxide, which are cheap to produce and scalable to a substrate size up to 6 m2. Low pressure CVD with temperatures below 200°C can be used for the deposition of boron doped ZnO with a native surface texture for good light scattering, while sputtered aluminum doped ZnO needs a post deposition treatment in an acid bath for a rough surface. The paper presents optical and electrical characterization of large area samples, and also results about long term stability of the ZnO samples with respect to the so called TCO corrosion.

  2. Theoretical technique for predicting the cumulative impact of iron and manganese oxidation in streams receiving discharge from coal mines

    USGS Publications Warehouse

    Bobay, Keith E.

    1986-01-01

    Two U.S. Geological Survey computer programs are modified and linked to predict the cumulative impact of iron and manganese oxidation in coal-mine discharge water on the dissolved chemical quality of a receiving stream. The coupled programs calculate the changes in dissolved iron, dissolved manganese, and dissolved oxygen concentrations; alkalinity; and, pH of surface water downstream from the point of discharge. First, the one-dimensional, stead-state stream, water quality program uses a dissolved oxygen model to calculate the changes in concentration of elements as a function of the chemical reaction rates and time-of-travel. Second, a program (PHREEQE) combining pH, reduction-oxidation potential, and equilibrium equations uses an aqueous-ion association model to determine the saturation indices and to calculate pH; it then mixes the discharge with a receiving stream. The kinetic processes of the first program dominate the system, whereas the equilibrium thermodynamics of the second define the limits of the reactions. A comprehensive test of the technique was not possible because a complete set of data was unavailable. However, the cumulative impact of representative discharges from several coal mines on stream quality in a small watershed in southwestern Indiana was simulated to illustrate the operation of the technique and to determine its sensitivity to changes in physical, chemical, and kinetic parameters. Mine discharges averaged 2 cu ft/sec, with a pH of 6.0, and concentrations of 7.0 mg/L dissolved iron, 4.0 mg/L dissolved manganese, and 8.08 mg/L dissolved oxygen. The receiving stream discharge was 2 cu ft/sec, with a pH of 7.0, and concentrations of 0.1 mg/L dissolved iron, 0.1 mg/L dissolved manganese, and 8.70 mg/L dissolved oxygen. Results of the simulations indicated the following cumulative impact on the receiving stream from five discharges as compared with the effect from one discharge: 0.30 unit decrease in pH, 1.82 mg/L increase in dissolved

  3. Oxidizing annealing effects on VO2 films with different microstructures

    NASA Astrophysics Data System (ADS)

    Dou, Yan-Kun; Li, Jing-Bo; Cao, Mao-Sheng; Su, De-Zhi; Rehman, Fida; Zhang, Jia-Song; Jin, Hai-Bo

    2015-08-01

    Vanadium dioxide (VO2) films have been prepared by direct-current magnetron sputter deposition on m-, a-, and r-plane sapphire substrates. The obtained VO2 films display different microstructures depending on the orientation of sapphire substrates, i.e. mixed microstructure of striped grains and equiaxed grains on m-sapphire, big equiaxed grains on a-sapphire and fine-grained microstructure on r-sapphire. The VO2 films were treated by the processes of oxidation in air. The electric resistance and infrared transmittance of the oxidized films were characterized to examine performance characteristics of VO2 films with different microstructures in oxidation environment. The oxidized VO2 films on m-sapphire exhibit better electrical performance than the other two films. After air oxidization for 600 s at 450 °C, the VO2 films on m-sapphire show a resistance change of 4 orders of magnitude over the semiconductor-to-metal transition. The oxidized VO2 films on a-sapphire have the highest optical modulation efficiency in infrared region compared to other samples. The different performance characteristics of VO2 films are understood in terms of microstructures, i.e. grain size, grain shape, and oxygen vacancies. The findings reveal the correlation of microstructures and performances of VO2 films, and provide useful knowledge for the design of VO2 materials to different applications.

  4. Nitrogen-Enriched Porous Carbon Coating for Manganese Oxide Nanostructures toward High-Performance Lithium-Ion Batteries.

    PubMed

    Wang, Jiangan; Zhang, Cunbao; Kang, Feiyu

    2015-05-01

    Manganese oxides are promising high-capacity anode materials for lithium-ion batteries (LIBs) yet suffer from short cycle life and poor rate capability. Herein, we demonstrate a facile in situ interfacial synthesis of core-shell heterostructures comprising nitrogen-enriched porous carbon (pN-C) nanocoating and manganese oxide (MnOx) nanotubes. When MnOx/pN-C serves as an anode material for LIBs, the pN-C coating plays multiple roles in substantially improving the lithium storage performance. In combination with the nanosized structure and nanotubular architecture, the MnOx/pN-C nanocomposites exhibit an impressive reversible capacity of 1068 mAh g(-1) at 100 mA g(-1), a high-rate delivery of 361 mAh g(-1) at 8 A g(-1), and a stable cycling retention up to 300 cycles. The surface pN-C coating strategy can be extended to design and fabricate various metal oxide nanostructures for high-performance LIBs. PMID:25871883

  5. Possibilities of liquid-phase low-temperature deposition of manganese oxides on NaY synthetic zeolite

    SciTech Connect

    Eremeev, A.P.; Petrusevich, E.F.

    1985-05-20

    This paper studies the possibilities of low-temperature liquid-phase deposition of manganese oxides on NaY synthetic zeolite and compares the results with literature data. The experiments were conducted in accordance with a design matrix that is presented in a table. The coefficients of regression equations are presented which describe the experimental responses against the background of the errors. A summary is given of rounded-off estimates of relative errors of determination of manganese oxides on the three zeolite types studied and the average values of responses of the same type for all the zeolites. It follows that the optimal estimates of the Mn/sub 2/O/sub 3/ and MnO/sub 2/ contents are the same for all the zeolites within the averaged error limits, while the estimates of MnO contents and conversion of Mn (II) from solution on the zeolite surface are not the same for clinoptilolite as for synthetic NaY, confirming that oxidation proceeds more actively on the NaY surface, while conversion is very pronounced in the case of clinoptilolite.

  6. Dysprosium oxide and dysprosium-oxide-doped titanium oxide thin films grown by atomic layer deposition

    SciTech Connect

    Tamm, Aile Kozlova, Jekaterina; Aarik, Lauri; Aarik, Jaan; Kukli, Kaupo; Link, Joosep; Stern, Raivo

    2015-01-15

    Dysprosium oxide and dysprosium-oxide-doped titanium oxide thin films were grown by atomic layer deposition on silicon substrates. For depositing dysprosium and titanium oxides Dy(thd){sub 3}-O{sub 3} and TiCl{sub 4}-O{sub 3} were used as precursors combinations. Appropriate parameters for Dy(thd){sub 3}-O{sub 3} growth process were obtained by using a quartz crystal microbalance system. The Dy{sub 2}O{sub 3} films were deposited on planar substrates and on three-dimensional substrates with aspect ratio 1:20. The Dy/Ti ratio of Dy{sub 2}O{sub 3}-doped TiO{sub 2} films deposited on a planar silicon substrate ranged from 0.04 to 0.06. Magnetometry studies revealed that saturation of magnetization could not be observed in planar Dy{sub 2}O{sub 3} films, but it was observable in Dy{sub 2}O{sub 3} films on 3D substrates and in doped TiO{sub 2} films with a Dy/Ti atomic ratio of 0.06. The latter films exhibited saturation magnetization 10{sup −6} A cm{sup 2} and coercivity 11 kA/m at room temperature.

  7. Synthesis of waste cooking oil based biodiesel via ferric-manganese promoted molybdenum oxide / zirconia nanoparticle solid acid catalyst: influence of ferric and manganese dopants.

    PubMed

    Alhassan, Fatah H; Rashid, Umer; Taufiq-Yap, Yun Hin

    2015-01-01

    The utilization of ferric-manganese promoted molybdenum oxide/zirconia (Fe-Mn- MoO3/ZrO2) (FMMZ) solid acid catalyst for production of biodiesel was demonstrated. FMMZ is produced through impregnation reaction followed by calcination at 600°C for 3 h. The characterization of FMMZ had been done using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), thermal gravimetric analysis (TGA), temperature programmed desorption of NH3 (TPD-NH3), transmission electron microscopy(TEM) and Brunner-Emmett-Teller (BET) surface area measurement. The effect of waste cooking oil methyl esters (WCOME's) yield on the reactions variables such as reaction temperature, catalyst loading, molar ratio of methanol/oil and reusability were also assessed. The catalyst was used to convert the waste cooking oil into corresponding methyl esters (95.6%±0.15) within 5 h at 200℃ reaction temperature, 600 rpm stirring speed, 1:25 molar ratio of oil to alcohol and 4% w/w catalyst loading. The reported catalyst was successfully recycled in six connective experiments without loss in activity. Moreover, the fuel properties of WCOME's were also reported using ASTM D 6751 methods. PMID:25843280

  8. Suppression of oxidative damage by Saccharomyces cerevisiae ATX2, which encodes a manganese-trafficking protein that localizes to Golgi-like vesicles.

    PubMed Central

    Lin, S J; Culotta, V C

    1996-01-01

    Oxygen toxicity in Saccharomyces cerevisiae lacking the copper/zinc superoxide dismutase (SOD1) can be suppressed by overexpression of the S. cerevisiae ATX2 gene. Multiple copies of ATX2 were found to reverse the aerobic auxotrophies of sod1(delta) mutants for lysine and methionine and also to enhance the resistance of these yeast strains to paraquat and atmospheric levels of oxygen. ATX2 encodes a novel 34.4-kDa polypeptide with a number of potential membrane-spanning domains. Our studies indicate that Atx2p localizes to the membrane of a vesicular compartment in yeast cells reminiscent of the Golgi apparatus. With indirect immunofluorescence microscopy, Atx2p exhibited a punctate pattern of staining typical of the Golgi apparatus, and upon subcellular fractionation, Atx2p colocalized with a biochemical marker for the yeast Golgi apparatus. We demonstrate here that this vesicle protein normally functions in the homeostasis of manganese ions and that this role in metal metabolism is necessary for the ATX1 suppression of SOD1 deficiency. First, overexpression of ATX2 caused cells to accumulate increased levels of manganese. Second, a deletion in ATX2 caused a decrease in the apparent available level of intracellular manganese and caused sod1(delta) mutants to become dependent upon exogenous manganese for aerobic growth. Third, ATX2 was incapable of suppressing oxidative damage in cells depleted of manganese ions or lacking the plasma membrane transporter for manganese. The effect of ATX2 overexpression on manganese accumulation and oxygen resistance is similar to what we have previously reported for mutations in PMR1, which encodes a manganese-trafficking protein that also resides in a vesicular compartment. Our studies are consistent with a model in which Atx2p and Pmr1p work in opposite directions to control manganese homeostasis. PMID:8887660

  9. High carrier concentration p-type transparent conducting oxide films

    DOEpatents

    Yan, Yanfa; Zhang, Shengbai

    2005-06-21

    A p-type transparent conducting oxide film is provided which is consisting essentially of, the transparent conducting oxide and a molecular doping source, the oxide and doping source grown under conditions sufficient to deliver the doping source intact onto the oxide.

  10. Arsenite Oxidation by a Poorly-Crystalline Manganese Oxide 2. Results from X-ray Absorption Spectroscopy and X-ray Diffraction

    PubMed Central

    Lafferty, Brandon J.; Ginder-Vogel, Matthew; Zhu, Mengqiang; Livi, Kenneth J. T.; Sparks, Donald L.

    2010-01-01

    Arsenite (AsIII) oxidation by manganese oxides (Mn-oxides) serves to detoxify and, under many conditions, immobilize arsenic (As) by forming arsenate (AsV). AsIII oxidation by MnIV-oxides can be quite complex, involving many simultaneous forward reactions and subsequent back reactions. During AsIII oxidation by Mn-oxides, a reduction in oxidation rate is often observed, which is attributed to Mn-oxide surface passivation. X-ray absorption spectroscopy (XAS) and X-ray diffraction (XRD) data show that MnII sorption on a poorly-crystalline hexagonal birnessite (δ-MnO2) is important in passivation early during reaction with AsIII. Also, it appears that MnIII in the δ-MnO2 structure is formed by conproportionation of sorbed MnII and MnIV in the mineral structure. The content of MnIII within the δ-MnO2 structure appears to increase as the reaction proceeds. Binding of AsV to δ-MnO2 also changes as MnIII becomes more prominent in the δ-MnO2 structure. The data presented indicate that AsIII oxidation and AsV sorption by poorly-crystalline δ-MnO2 is greatly affected by Mn oxidation state in the δ-MnO2 structure. PMID:20977204

  11. The Staphylococcus aureus ABC-Type Manganese Transporter MntABC Is Critical for Reinitiation of Bacterial Replication Following Exposure to Phagocytic Oxidative Burst

    PubMed Central

    Coady, Alison; Xu, Min; Phung, Qui; Cheung, Tommy K.; Bakalarski, Corey; Alexander, Mary Kate; Lehar, Sophie M.; Kim, Janice; Park, Summer; Tan, Man-Wah; Nishiyama, Mireille

    2015-01-01

    Manganese plays a central role in cellular detoxification of reactive oxygen species (ROS). Therefore, manganese acquisition is considered to be important for bacterial pathogenesis by counteracting the oxidative burst of phagocytic cells during host infection. However, detailed analysis of the interplay between bacterial manganese acquisition and phagocytic cells and its impact on bacterial pathogenesis has remained elusive for Staphylococcus aureus, a major human pathogen. Here, we show that a mntC mutant, which lacks the functional manganese transporter MntABC, was more sensitive to killing by human neutrophils but not murine macrophages, unless the mntC mutant was pre-exposed to oxidative stress. Notably, the mntC mutant formed strikingly small colonies when recovered from both type of phagocytic cells. We show that this phenotype is a direct consequence of the inability of the mntC mutant to reinitiate growth after exposure to phagocytic oxidative burst. Transcript and quantitative proteomics analyses revealed that the manganese-dependent ribonucleotide reductase complex NrdEF, which is essential for DNA synthesis and repair, was highly induced in the mntC mutant under oxidative stress conditions including after phagocytosis. Since NrdEF proteins are essential for S. aureus viability we hypothesize that cells lacking MntABC might attempt to compensate for the impaired function of NrdEF by increasing their expression. Our data suggest that besides ROS detoxification, functional manganese acquisition is likely crucial for S. aureus pathogenesis by repairing oxidative damages, thereby ensuring efficient bacterial growth after phagocytic oxidative burst, which is an attribute critical for disseminating and establishing infection in the host. PMID:26379037

  12. Electrical transport properties of manganese containing pyrochlore type semiconducting oxides using impedance analyses

    SciTech Connect

    Sumi, S.; Prabhakar Rao, P.; Mahesh, S.K.; Koshy, Peter

    2012-12-15

    Graphical abstract: DC conductivity variation of CaCe{sub 1−x}Mn{sub x}SnNbO{sub 7−δ} (x = 0, 0.2, 0.4 and 0.6) with inverse of temperature. Variation of conductivity with Mn concentration at 600 °C is shown in the inset. Display Omitted Highlights: ► We have observed that the structural ordering as well as grain size increase with Mn substitution. ► Impedance analysis proved that a correlated barrier hopping type conduction mechanism is involved in the materials. ► Activation energy as well as electrical conductivity increases with increase in Mn substitution. ► Localization of electrons associated with Mn{sup 2+} and structural ordering are the key factors for the increased activation energy with Mn substitution. ► All the materials showed good NTC thermistor properties. -- Abstract: A new series of manganese containing pyrochlore type semiconducting oxides CaCe{sub 1−x}Mn{sub x}SnNbO{sub 7−δ} (x = 0, 0.2, 0.4 and 0.6) have been synthesized to study the effect of Mn substitution on the structure, microstructure and electrical properties of these samples. X-ray diffraction and scanning electron microscopy studies revealed an increase of structural ordering and grain size respectively with increase of Mn substitution. Rietveld analysis and Raman spectroscopy were also employed to corroborate the XRD results. The bulk resistance measurements with temperature exhibit negative temperature coefficient behavior. The impedance analysis of the samples revealed a non-Debye type relaxation existed in the materials. The ac conductivity variation with temperature and frequency indicates a correlated barrier hopping type conduction mechanism in these materials. The barrier height and the intersite separation for hopping influence the electrical conductivity of these samples and are found to be a function of localization of electrons associated with the Mn{sup 2+} ions and the unit cell volume respectively. The Mn substitution increases both electrical

  13. Bio-inspired catechol chemistry for electrophoretic nanotechnology of oxide films.

    PubMed

    Wang, Y; Zhitomirsky, I

    2012-08-15

    Bio-inspired chemical approach has been developed for the surface modification and electrophoretic deposition of manganese dioxide and zirconia nanoparticles, prepared by chemical precipitation methods. Caffeic acid, trans-cinnamic acid, p-coumaric acid, and 2,4-dihydroxycinnamic acid were investigated for the surface modification of the nanoparticles. The influence of the structure of the organic molecules on their adsorption on the oxide nanoparticles has been investigated. The mechanism of caffeic acid adsorption was similar to that of natural catecholic amino acid, L-3,4-dihydroxyphenylalanine. The use of caffeic acid allowed for agglomerate-free synthesis, efficient dispersion, charging, electrophoretic deposition and co-deposition of manganese dioxide and zirconia nanoparticles. The deposition yield data, coupled with the results of thermogravimetric analysis, X-ray diffraction analysis, and Fourier transform infrared spectroscopy, showed that surface chemistry, rather than the crystal structure, determined the adsorption behavior. Electron microscopy and energy dispersive spectroscopy investigations showed the formation of nanostructured oxide films and composites. The deposit composition can be varied. PMID:22652591

  14. Chemical fluxes and origin of a manganese carbonate-oxide-silicate deposit in bedded chert

    USGS Publications Warehouse

    Huebner, J.S.; Flohr, M.J.K.; Grossman, J.N.

    1992-01-01

    Lens-like rhodochrosite-rich bodies within interbedded chert and shale are associated with basalt and/or graywacke in ophiolitic and orogenic zones. The Buckeye manganese mine in the Franciscan Complex of the California Coast Ranges is associated with metagraywacke. Despite blueschist-facies metamorphism, this deposit preserves the compositions and some textural features of its sedimentary protoliths. For this reason, it is a suitable deposit with which to compare more intensely altered deposits, or deposits originating in different paleoenvironments. Six Mn-rich and three Mn-poor minerals form monomineralic layers and mixtures: rhodochrosite, gageite, Mn-oxides (hausmannite, braunite), divalent Mn-silicates (caryopilite, taneyamalite), chlorite, quartz (metachert) and aegirine-augite. The Mn-rich protoliths have high Mn/Fe combined with relatively low concentrations of Ca, Al, Ti, Co, Ni, Cu, Th and REE. REE patterns of various protoliths are distinct. Rhodochrosite and gageite layers are depleted (seawater ?? 5 ?? 104) and flat, whereas patterns of metachert and the Mn-silicate-rich layers mimic the patterns of metashale and metagraywacke (seawater ?? 106). Hausmannite layers have flat patterns (seawater ?? 7 ?? 104) whereas braunite-rich layers are more enriched (seawater ?? 2 ?? 105) and show a distinct positive Ce anomaly. Factor analysis reveals components and fluxes attributed to sub-seafloor fluids (Ni, As, Zn, Sb, W, Mn), seawater (Mg, Au, V, Mo), detritus and veins (Ca, Ba, Sr). Silica is negatively correlated with the sub-seafloor factor. The observed variances indicate that water from the sediment column mixed with seawater, that deposition occurred near the sediment-seawater interface before mixtures of subsurface fluid and seawater homogenized, and that the system was not entirely closed during metamorphism. The variations in REE enrichment can be related to kinetics of deposition: rhodochrosite and gageite were precipitated most rapidly, and

  15. p-type conduction in sputtered indium oxide films

    SciTech Connect

    Stankiewicz, Jolanta; Alcala, Rafael; Villuendas, Francisco

    2010-05-10

    We report p-type conductivity in intrinsic indium oxide (IO) films deposited by magnetron sputtering on fused quartz substrates under oxygen-rich ambient. Highly oriented (111) films were studied by x-ray diffraction, optical absorption, and Hall effect measurements. We fabricated p-n homojunctions on these films.

  16. Polymer-assisted aqueous deposition of metal oxide films

    DOEpatents

    Li, DeQuan; Jia, Quanxi

    2003-07-08

    An organic solvent-free process for deposition of metal oxide thin films is presented. The process includes aqueous solutions of necessary metal precursors and an aqueous solution of a water-soluble polymer. After a coating operation, the resultant coating is fired at high temperatures to yield optical quality metal oxide thin films.

  17. Multi-functional porous mix-valent manganese oxide nano-materials and ruthenium/titanium dioxide for magnetic, electronic, and catalytic applications

    NASA Astrophysics Data System (ADS)

    Shen, Xiongfei

    This thesis contains two parts: (1) development of porous mixed-valent manganese oxide octahedral molecular sieve (OMS) nano-materials with controlled tunnel structures and muilt-functionalities and (2) application of H 2 adsorption for metal particle size evaluation on TiO2 supported Ru Fischer-Tropsch catalysts. Manganese oxide OMS with different nano-scale tunnel sizes may result in various microporosities for different selective catalysis and separation applications. A hydrothermal method was developed to synthesize manganese oxide nano-materials with controlled nano-scale tunnel sizes by hydrothermal treatments of layered structure manganese oxides under different pH conditions. Manganese oxides with increasing tunnel sizes of 2.3 A x 2.3 A (1x1 tunnel structure), 4.6 A x 6.9 A (2x3 tunnel structure), and 4.6 A x 9.2 A (2x4 tunnel structure) were synthesized with increasing pH value from 1.0, 7.0, to 13.0, respectively. Phase transformation mechanism of layered precursors to tunnel structures was obtained by characterization of the materials during synthesis using in situ synchrotron X-ray diffraction. The obtained phase transformation mechanism was used for synthesis of better materials such as new lxl/1x2 tunnel structures and controlled BET surface areas. Most manganese oxide OMS materials show paramagnetism at temperatures from 100 to 350 K. A new method was established to measure the average oxidation state (AOS) of mix-valent manganese in OMS materials by describing their paramagnetic behavior using the Curie-Weiss law. Measurement results show a maximum 7% deviation error compared to the reference titration method for 10 different samples. Magnetism of OMS was further explored by doping Fe into KOMS-2 (a 2x2 tunnel structure manganese oxide) to create high temperature ferromagnetism. The possession of both semiconducting and high temperature ferromagnetism in the Fe-doped KOMS-2 created a highly promising new group of functional materials for

  18. Method of producing solution-derived metal oxide thin films

    DOEpatents

    Boyle, Timothy J.; Ingersoll, David

    2000-01-01

    A method of preparing metal oxide thin films by a solution method. A .beta.-metal .beta.-diketonate or carboxylate compound, where the metal is selected from groups 8, 9, 10, 11, and 12 of the Periodic Table, is solubilized in a strong Lewis base to form a homogeneous solution. This precursor solution forms within minutes and can be deposited on a substrate in a single layer or a multiple layers to form a metal oxide thin film. The substrate with the deposited thin film is heated to change the film from an amorphous phase to a ceramic metal oxide and cooled.

  19. Structural study of biotic and abiotic poorly-crystalline manganese oxides using atomic pair distribution function analysis

    SciTech Connect

    Zhu, Mengqiang; Farrow, Christopher L.; Post, Jeffrey E.; Livi, Kenneth J.T.; Billinge, Simon J.L.; Ginder-Vogel, Matthew; Sparks, Donald L.

    2012-03-15

    Manganese (Mn) oxides are among the most reactive natural minerals and play an important role in elemental cycling in oceanic and terrestrial environments. A large portion of naturally-occurring Mn oxides tend to be poorly-crystalline and/or nanocrystalline, with not fully resolved crystal structures. In this study, the crystal structures of their synthetic analogs including acid birnessite (AcidBir), {delta}-MnO{sub 2}, polymeric MnO{sub 2} (PolyMnO{sub 2}) and a bacteriogenic Mn oxide (BioMnO{sub x}), have been revealed using atomic pair distribution function (PDF) analysis. Results unambiguously verify that these Mn oxides are layered materials. The best models that accurately allow simulation of pair distribution functions (PDFs) belong to the monoclinic C12/m1 space group with a disk-like shape. The single MnO{sub 6} layers in the average structures deviate significantly from hexagonal symmetry, in contrast to the results of previous studies based on X-ray diffraction analysis in reciprocal space. Manganese occupancies in MnO{sub 6} layers are estimated to be 0.936, 0.847, 0.930 and 0.935, for AcidBir, BioMnOx, {delta}-MnO{sub 2} and PolyMnO{sub 2}, respectively; however, occupancies of interlayer cations and water molecules cannot be accurately determined using the models in this study. The coherent scattering domains (CSDs) of PolyMnO{sub 2}, {delta}-MnO{sub 2} and BioMnO{sub x} are at the nanometer scale, comprising one to three MnO{sub 6} layers stacked with a high disorder in the crystallographic c-axis direction. Overall, the results of this study advance our understanding of the mineralogy of Mn oxide minerals in the environment.

  20. Structural Study of Biotic and Abiotic Poorly-crystalline Manganese Oxides Using Atomic Pair Distribution Function Analysis

    SciTech Connect

    Billinge S. J.; Zhu, M.; Farrow, C.L.; Post, J.E.; Livi, K.J.T.; Ginder-Vogel, M.; Sparks, D.L.

    2012-03-15

    Manganese (Mn) oxides are among the most reactive natural minerals and play an important role in elemental cycling in oceanic and terrestrial environments. A large portion of naturally-occurring Mn oxides tend to be poorly-crystalline and/or nanocrystalline, with not fully resolved crystal structures. In this study, the crystal structures of their synthetic analogs including acid birnessite (AcidBir), {delta}-MnO{sub 2}, polymeric MnO{sub 2} (PolyMnO{sub 2}) and a bacteriogenic Mn oxide (BioMnO{sub x}), have been revealed using atomic pair distribution function (PDF) analysis. Results unambiguously verify that these Mn oxides are layered materials. The best models that accurately allow simulation of pair distribution functions (PDFs) belong to the monoclinic C12/m1 space group with a disk-like shape. The single MnO{sub 6} layers in the average structures deviate significantly from hexagonal symmetry, in contrast to the results of previous studies based on X-ray diffraction analysis in reciprocal space. Manganese occupancies in MnO{sub 6} layers are estimated to be 0.936, 0.847, 0.930 and 0.935, for AcidBir, BioMnO{sub x}, {delta}-MnO{sub 2} and PolyMnO{sub 2}, respectively; however, occupancies of interlayer cations and water molecules cannot be accurately determined using the models in this study. The coherent scattering domains (CSDs) of PolyMnO{sub 2}, {delta}-MnO{sub 2} and BioMnO{sub x} are at the nanometer scale, comprising one to three MnO{sub 6} layers stacked with a high disorder in the crystallographic c-axis direction. Overall, the results of this study advance our understanding of the mineralogy of Mn oxide minerals in the environment.

  1. Graphene-Based Hybrids with Manganese Oxide Polymorphs as Tailored Interfaces for Electrochemical Energy Storage: Synthesis, Processing, and Properties

    NASA Astrophysics Data System (ADS)

    Gupta, S.; van Meveren, M. M.; Jasinski, J.

    2015-01-01

    Technological progress is determined to a greater extent by developments of novel materials or new combinations of known materials with different dimensionality and diverse functionality. In this work, we report on the synthesis and characterization of graphene-based hybrid nanomaterials coupled with transition-metal oxide polymorphs (nano/micro-manganese oxides, i.e., β-MnO2 [Mn(IV)] and Mn3O4 [Mn(II, III)]). This lays the groundwork for high-performance electrochemical electrodes for alternative energy devices owing to their higher specific capacitance, wide operational potential window and stability through charge-discharge cycling, environmentally benignity, cost-effectiveness, easy processing, and reproducibility on a larger scale. To accomplish this, we strategically designed these hybrids by direct anchoring or physical adsorption of β-MnO2 and Mn3O4 on variants of graphene, namely graphene oxide and its reduced form, via mixing dispersions of the constituents under mild ultrasonication and drop-casting, resulting in four different combinations. This facile approach affords strong chemical/physical attachment and is expected to result in coupling between the pseudocapacitive transition-metal oxides and supercapacitive nanocarbons showing enhanced activity/reactivity and reasonable areal density of tailored interfaces. We used a range of complementary analytical characterization tools to determine the structure and physical properties, such as scanning electron microscopy combined with energy-dispersive x-ray spectroscopy, atomic force microscopy, x-ray diffraction, resonance Raman spectroscopy combined with elemental Raman mapping, and transmission electron microscopy in conjunction with selected-area electron diffraction. All of these techniques reveal surface morphology, local (lattice dynamical) and average structure, and local charge transfer due to the physically (or chemically) adsorbed manganese oxide of synthesized hybrids that helps to establish

  2. Oxidant Selection for the Treatment of Manganese (II), Iron (II), and Arsenic (III) in Groundwaters

    EPA Science Inventory

    In order to comply with the United States Environmental Protection Agency’s (U.S. EPA’s) arsenic standard and the manganese and iron secondary maximum contaminant levels (MCLs) in water (10µg/L, 50µg/L, and 300µg/L, respectively), many Midwestern water utilities must add a strong...

  3. Effects of oxidative treatments on human hair keratin films.

    PubMed

    Fujii, T; Ito, Y; Watanabe, T; Kawasoe, T

    2012-01-01

    The effects of hydrogen peroxide and commercial bleach on hair and human hair keratin films were examined by protein solubility, scanning electron microscopy (SEM), immunofluorescence microscopy, immunoblotting, and Fourier-transform infrared spectroscopy. Protein solubility in solutions containing urea decreased when the keratin films were treated with hydrogen peroxide or bleach. Oxidative treatments promoted the urea-dependent morphological change by turning films from opaque to transparent in appearance. Immunofluorescence microscopy and immunoblotting showed that the oxidation of amino acids and proteins occurred due to the oxidative treatments, and such occurrence was more evident in the bleach-treated films than in the hydrogen peroxide-treated films. Compared with hair samples, the formation of cysteic acid was more clearly observed in the keratin films after the oxidative treatments. PMID:22487448

  4. Manganese, Metallogenium, and Martian Microfossils

    NASA Technical Reports Server (NTRS)

    Stein, L. Y.; Nealson, K. H.

    1999-01-01

    Manganese could easily be considered an abundant element in the Martian regolith, assuming that the composition of martian meteorites reflects the composition of the planet. Mineralogical analyses of 5 SNC meteorites have revealed an average manganese oxide concentration of 0.48%, relative to the 0.1% concentration of manganese found in the Earth's crust. On the Earth, the accumulation of manganese oxides in oceans, soils, rocks, sedimentary ores, fresh water systems, and hydrothermal vents can be largely attributed to microbial activity. Manganese is also a required trace nutrient for most life forms and participates in many critical enzymatic reactions such as photosynthesis. The wide-spread process of bacterial manganese cycling on Earth suggests that manganese is an important element to both geology and biology. Furthermore, there is evidence that bacteria can be fossilized within manganese ores, implying that manganese beds may be good repositories for preserved biomarkers. A particular genus of bacteria, known historically as Metallogenium, can form star-shaped manganese oxide minerals (called metallogenium) through the action of manganese oxide precipitation along its surface. Fossilized structures that resemble metallogenium have been found in Precambrian sedimentary formations and in Cretaceous-Paleogene cherts. The Cretaceous-Paleogene formations are highly enriched in manganese and have concentrations of trace elements (Fe, Zn, Cu, and Co) similar to modern-day manganese oxide deposits in marine environments. The appearance of metallogenium-like fossils associated with manganese deposits suggests that bacteria may be preserved within the minerals that they form. Additional information is contained in the original extended abstract.

  5. Selective Alkane Oxidation by Manganese Oxide: Site Isolation of MnOx Chains at the Surface of MnWO4 Nanorods.

    PubMed

    Li, Xuan; Lunkenbein, Thomas; Pfeifer, Verena; Jastak, Mateusz; Nielsen, Pia Kjaer; Girgsdies, Frank; Knop-Gericke, Axel; Rosowski, Frank; Schlögl, Robert; Trunschke, Annette

    2016-03-14

    The electronic and structural properties of vanadium-containing phases govern the formation of isolated active sites at the surface of these catalysts for selective alkane oxidation. This concept is not restricted to vanadium oxide. The deliberate use of hydrothermal techniques can turn the typical combustion catalyst manganese oxide into a selective catalyst for oxidative propane dehydrogenation. Nanostructured, crystalline MnWO4 serves as the support that stabilizes a defect-rich MnOx surface phase. Oxygen defects can be reversibly replenished and depleted at the reaction temperature. Terminating MnOx zigzag chains on the (010) crystal planes are suspected to bear structurally site-isolated oxygen defects that account for the unexpectedly good performance of the catalyst in propane activation. PMID:26913704

  6. Adsorption of antimony(V) onto Mn(II)-enriched surfaces of manganese-oxide and FeMn binary oxide.

    PubMed

    Liu, Ruiping; Xu, Wei; He, Zan; Lan, Huachun; Liu, Huijuan; Qu, Jiuhui; Prasai, Tista

    2015-11-01

    Manganese(IV) oxide [Mn(IV)] potentially oxidizes antimony(III) [Sb(III)] to antimony(V) [Sb(V)] and improves Sb removal by FeMn binary oxide (FMBO) through an oxidation-adsorption mechanism. This study focused on the effect of Mn(IV) reductive dissolution by potassium sulfite (K2SO3) on Sb(V) adsorption onto manganese oxide (Mn-oxide) and FMBO. The maximum Sb(V) adsorption (Qmax,Sb(V)) increased from 1.0 to 1.1 mmol g(-1) for FMBO and from 0.4 to 0.6 mmol g(-1) for Mn-oxide after pretreatment with 10 mmol L(-1) K2SO3. The addition of 2.5 mmol L(-1) Mn(2+) also significantly improved Sb(V) adsorption, and the observed Qmax,Sb(V) increased to 1.4 and 1.0 mmol g(-1) for FMBO and Mn-oxide, respectively, with pre-adsorbed Mn(2+). Neither K2SO3 nor Mn(2+) addition had any effect on Sb(V) adsorption onto iron oxide (Fe-oxide). Mn(2+) introduced by either Mn(IV) dissolution or addition tended to form outer-sphere surface complexes with hydroxyl groups on Mn-oxide surfaces (MnOOH). Mn(2+) at 2.5 mmol L(-1) shifted the isoelectric point (pHiep) from 7.5 to 10.2 for FMBO and from 4.8 to 9.2 for Mn-oxide and hence benefited Sb(V) adsorption. The adsorption of Sb(V) onto Mn(2+)-enriched surfaces contributed to the release of Mn(2+), and the X-ray photoelectron spectra also indicated increased binding energy of Mn 2p3/2 after the adsorption of Sb(V) onto K2SO3-pretreated FMBO and Mn-oxide. Sb(V) adsorption involved the formation of inner-sphere complexes and contributed to the release of Mn(2+). In the removal of Sb(III) by Mn-based oxides, the oxidation of Sb(III) to Sb(V) by Mn(IV) oxides had an effect; however, Mn(IV) dissolution and Mn(2+)-enrichment also played an important role. PMID:26218341

  7. Cesium and cobalt adsorption on synthetic nano manganese oxide: A two dimensional infra-red correlation spectroscopic investigation

    NASA Astrophysics Data System (ADS)

    Al Lafi, Abdul G.; Al Abdullah, Jamal

    2015-08-01

    Molecular scale information is of prime importance to understand ions coordination to mineral surfaces and consequently to aid in the design of improved ion exchange materials. This paper reports on the use of two-dimensional correlation infra-red spectroscopy (2D-COS-IR) to investigate the time dependent adsorptions of cesium and cobalt ions onto nano manganese oxide (NMO). The metal ions uptake was driven mainly by inner-sphere complex formation as demonstrated by the production of new absorption bands at 1160, 1100, 585 and 525 cm-1, which were assigned to the O-O bond vibration and the coupled vibrations of M-O and Mn-O bonds. The progressive development of the 3100 cm-1 band, which is attributed to the stretching vibration of the lattice-OH group, indicates an M+/H+ ion-exchange reaction. The new bands at 700 and 755 cm-1 in the case of cobalt ion adsorption and at 800 and 810 cm-1 in the case of cesium ion adsorption, and the splitting of other bands at 1135 and 875 cm-1 indicate the presence of different O-O bond lengths. This suggests different coordination of the two metal ions with oxygen. The infrared spectroscopy combined with 2D-COS provides a powerful tool to investigate the mechanism of interaction between heavy metals and manganese oxide.

  8. Influence of dissolved organic matter and manganese oxides on metal speciation in soil solution: A modelling approach.

    PubMed

    Schneider, Arnaud R; Ponthieu, Marie; Cancès, Benjamin; Conreux, Alexandra; Morvan, Xavier; Gommeaux, Maxime; Marin, Béatrice; Benedetti, Marc F

    2016-06-01

    Trace element (TE) speciation modelling in soil solution is controlled by the assumptions made about the soil solution composition. To evaluate this influence, different assumptions using Visual MINTEQ were tested and compared to measurements of free TE concentrations. The soil column Donnan membrane technique (SC-DMT) was used to estimate the free TE (Cd, Cu, Ni, Pb and Zn) concentrations in six acidic soil solutions. A batch technique using DAX-8 resin was used to fractionate the dissolved organic matter (DOM) into four fractions: humic acids (HA), fulvic acids (FA), hydrophilic acids (Hy) and hydrophobic neutral organic matter (HON). To model TE speciation, particular attention was focused on the hydrous manganese oxides (HMO) and the Hy fraction, ligands not considered in most of the TE speciation modelling studies in soil solution. In this work, the model predictions of free ion activities agree with the experimental results. The knowledge of the FA fraction seems to be very useful, especially in the case of high DOM content, for more accurately representing experimental data. Finally, the role of the manganese oxides and of the Hy fraction on TE speciation was identified and, depending on the physicochemical conditions of the soil solution, should be considered in future studies. PMID:27017138

  9. Electrocatalytic oxidation of 2-mercaptoethanol using modified glassy carbon electrode by MWCNT in combination with unsymmetrical manganese (II) Schiff base complexes

    SciTech Connect

    Mohebbi, Sajjad Eslami, Saadat

    2015-06-15

    Highlights: • High electocatalytic efficiency and stability of modified hybrid electrode GC/MWCNTs/MnSaloph. • Direct reflection of catalytic activity of manganese complexes on electrocatalytic oxidation of 2-ME. • Decreasing overpotential and increasing catalytic peak current toward oxidation of 2-ME. • Deposition of range of novel substituted N{sub 2}O{sub 2} Saloph complexes of manganese(II) on GCE/MWCNT. • Enhancement of electrocatalytic oxidation activity upon electron donating substitutions on the Saloph. - Abstract: The performance of modified hybrid glassy carbon electrode with composite of carbon nanotubes and manganese complexes for the electrocatalytic oxidation of 2-mercaptoethanol is developed. GC electrode was modified using MWCNT and new N{sub 2}O{sub 2} unsymmetrical tetradentate Schiff base complexes of manganese namely Manganese Saloph complexes 1-5, with general formula Mn[(5-x-4-y-Sal)(5-x′-4-y′-Sal) Ph], where x, x′ = H, Br, NO{sub 2} and y, y′ = H, MeO. Direct immobilization of CNT on the surface of GCE is performed by abrasive immobilization, and then modified by manganese(II) complexes via direct deposition method. These novel modified electrodes clearly demonstrate the necessity of modifying bare carbon electrodes to endow them with the desired behavior and were identified by HRTEM. Also complexes were characterized by elemental analyses, MS, UV–vis and IR spectroscopy. Modified hybrid GC/MWCNT/MnSaloph electrode exhibits strong and stable electrocatalytic activity towards the electrooxidation of 2-mercaptoethanol molecules in comparison with bare glassy carbon electrode with advantages of very low over potential and high catalytic current. Such ability promotes the thiol’s electron transfer reaction. Also, electron withdrawing substituent on the Saloph was enhanced electrocatalytic oxidation activity.

  10. Copper doped hollow structured manganese oxide mesocrystals with controlled phase structure and morphology as anode materials for lithium ion battery with improved electrochemical performance.

    PubMed

    Li, Qun; Yin, Longwei; Li, Zhaoqiang; Wang, Xuekun; Qi, Yongxin; Ma, Jingyun

    2013-11-13

    We develop a facile synthesis route to prepare Cu doped hollow structured manganese oxide mesocrystals with controlled phase structure and morphology using manganese carbonate as the reactant template. It is shown that Cu dopant is homogeneously distributed among the hollow manganese oxide microspherical samples, and it is embedded in the lattice of manganese oxide by substituting Mn(3+) in the presence of Cu(2+). The crystal structure of manganese oxide products can be modulated to bixbyite Mn2O3 and tetragonal Mn3O4 in the presence of annealing gas of air and nitrogen, respectively. The incorporation of Cu into Mn2O3 and Mn3O4 induces a great microstructure evolution from core-shell structure for pure Mn2O3 and Mn3O4 samples to hollow porous spherical Cu-doped Mn2O3 and Mn3O4 samples with a larger surface area, respectively. The Cu-doped hollow spherical Mn2O3 sample displays a higher specific capacity of 642 mAhg(-1) at a current density of 100 mA g(-1) after 100 cycles, which is about 1.78 times improvement compared to that of 361 mA h g(-1) for the pure Mn2O3 sample, displaying a Coulombic efficiency of up to 99.5%. The great enhancement of the electrochemical lithium storage performance can be attributed to the improvement of the electronic conductivity and lithium diffusivity of electrodes. The present results have verified the ability of Cu doping to improve electrochemical lithium storage performances of manganese oxides. PMID:24080017

  11. Bioaccumulation of manganese and its toxicity in feral pigeons (Columba livia) exposed to manganese oxide dust (Mn{sub 3}O{sub 4})

    SciTech Connect

    Sierra, P.; Chakrabarti, S.; Tounkara, R.; Loranger, S.; Kennedy, G.; Zayed, J.

    1998-11-01

    Manganese tetroxide (Mn{sub 3}O{sub 4}) is a product from the combustion of methylcyclopentadienyl manganese tricarbonyl. Exposure to high levels of manganese can lead to serious health effects especially to the central nervous and respiratory systems. Very few studies on the effects of long-term low level exposure to Mn{sub 3}O{sub 4} have been reported. The present study was therefore conducted to examine the bioaccumulation and toxicity of manganese in various organs of feral pigeons (Columba kivia) when exposed to low levels of Mn{sub 3}O{sub 4} via inhalation and hence to find any possible relationship between these two parameters. A total of 22 pigeons was exposed to 239 {micro}g/m{sup 3} of manganese for 7 h/day, 5 days/week for 5, 9, and 13 consecutive weeks. Manganese concentrations in various tissues, e.g., brain (mesencephalon), lung, liver, intestine, pancreas, kidney, muscle, bone, and whole blood, were measured by neutron activation analysis. Various biochemical parameters in blood, e.g., hematocrit, total proteins, glucose, uric acid, alinine aminotransferase, total iron, blood urea nitrogen and triglycerides, were also measured.

  12. Chemical oxygen demand analysis of wastewater using trivalent manganese oxidant with chloride removal by sodium bismuthate pretreatment.

    PubMed

    Miller, D G; Brayton, S V; Boyles, W T

    2001-01-01

    Current chemical oxygen demand (COD) analyses generate wastes containing hexavalent and trivalent chromium, mercury, and silver. Waste disposal is difficult, expensive, and poses environmental hazards. A new COD test is proposed that eliminates these metals and shortens analysis time, where trivalent manganese oxidant replaces hexavalent chromium (dichromate). A silver catalyst is not required. Optional pretreatment removes chloride via oxidation to chlorine using sodium bismuthate, eliminating the need for mercury. Sample aqueous and solid components are separated for chloride removal, then recombined for total COD measurement. Soluble and nonsoluble COD can be determined separately. Digestion at 150 degrees C is complete in 1 hour. Results are determined by titration or by spectrophotometric reading. Test wastes contain none of the metals regulated for disposal under the Resource Conservation and Recovery Act. Results are shown for selected organic compounds and various wastewaters. Statistical comparisons are made with dichromate COD and biochemical oxygen demand (BOD5) test values. PMID:11558305

  13. Identifying active surface phases for metal oxide electrocatalysts: a study of manganese oxide bi-functional catalysts for oxygen reduction and water oxidation catalysis.

    PubMed

    Su, Hai-Yan; Gorlin, Yelena; Man, Isabela C; Calle-Vallejo, Federico; Nørskov, Jens K; Jaramillo, Thomas F; Rossmeisl, Jan

    2012-10-28

    Progress in the field of electrocatalysis is often hampered by the difficulty in identifying the active site on an electrode surface. Herein we combine theoretical analysis and electrochemical methods to identify the active surfaces in a manganese oxide bi-functional catalyst for the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER). First, we electrochemically characterize the nanostructured α-Mn(2)O(3) and find that it undergoes oxidation in two potential regions: initially, between 0.5 V and 0.8 V, a potential region relevant to the ORR and, subsequently, between 0.8 V and 1.0 V, a potential region between the ORR and the OER relevant conditions. Next, we perform density function theory (DFT) calculations to understand the changes in the MnO(x) surface as a function of potential and to elucidate reaction mechanisms that lead to high activities observed in the experiments. Using DFT, we construct surface Pourbaix and free energy diagrams of three different MnO(x) surfaces and identify 1/2 ML HO* covered Mn(2)O(3) and O* covered MnO(2), as the active surfaces for the ORR and the OER, respectively. Additionally, we find that the ORR occurs through an associative mechanism and that its overpotential is highly dependent on the stabilization of intermediates through hydrogen bonds with water molecules. We also determine that OER occurs through direct recombination mechanism and that its major source of overpotential is the scaling relationship between HOO* and HO* surface intermediates. Using a previously developed Sabatier model we show that the theoretical predictions of catalytic activities match the experimentally determined onset potentials for the ORR and the OER, both qualitatively and quantitatively. Consequently, the combination of first-principles theoretical analysis and experimental methods offers an understanding of manganese oxide oxygen electrocatalysis at the atomic level, achieving fundamental insight that can potentially be

  14. Electronic structure at transition metal phthalocyanine-transition metal oxide interfaces: Cobalt phthalocyanine on epitaxial MnO films

    SciTech Connect

    Glaser, Mathias; Peisert, Heiko Adler, Hilmar; Aygül, Umut; Ivanovic, Milutin; Chassé, Thomas; Nagel, Peter; Merz, Michael; Schuppler, Stefan

    2015-03-14

    The electronic structure of the interface between cobalt phthalocyanine (CoPc) and epitaxially grown manganese oxide (MnO) thin films is studied by means of photoemission (PES) and X-ray absorption spectroscopy (XAS). Our results reveal a flat-lying adsorption geometry of the molecules on the oxide surface which allows a maximal interaction between the π-system and the substrate. A charge transfer from MnO, in particular, to the central metal atom of CoPc is observed by both PES and XAS. The change of the shape of N-K XAS spectra at the interface points, however, to the involvement of the Pc macrocycle in the charge transfer process. As a consequence of the charge transfer, energetic shifts of MnO related core levels were observed, which are discussed in terms of a Fermi level shift in the semiconducting MnO films due to interface charge redistribution.

  15. Electronic structure at transition metal phthalocyanine-transition metal oxide interfaces: Cobalt phthalocyanine on epitaxial MnO films

    NASA Astrophysics Data System (ADS)

    Glaser, Mathias; Peisert, Heiko; Adler, Hilmar; Aygül, Umut; Ivanovic, Milutin; Nagel, Peter; Merz, Michael; Schuppler, Stefan; Chassé, Thomas

    2015-03-01

    The electronic structure of the interface between cobalt phthalocyanine (CoPc) and epitaxially grown manganese oxide (MnO) thin films is studied by means of photoemission (PES) and X-ray absorption spectroscopy (XAS). Our results reveal a flat-lying adsorption geometry of the molecules on the oxide surface which allows a maximal interaction between the π-system and the substrate. A charge transfer from MnO, in particular, to the central metal atom of CoPc is observed by both PES and XAS. The change of the shape of N-K XAS spectra at the interface points, however, to the involvement of the Pc macrocycle in the charge transfer process. As a consequence of the charge transfer, energetic shifts of MnO related core levels were observed, which are discussed in terms of a Fermi level shift in the semiconducting MnO films due to interface charge redistribution.

  16. Crystalline state and acoustic properties of zinc oxide films

    SciTech Connect

    Kal'naya, G.I.; Pryadko, I.F.; Yarovoi, Yu.A.

    1988-08-01

    We study the effect of the crystalline state of zinc oxide films, prepared by magnetron sputtering, on the efficiency of SAW transducers based on the layered system textured ZnO film-interdigital transducer (IDT)-fused quartz substrate. The crystalline perfection of the ZnO films was studied by the x-ray method using a DRON-2.0 diffractometer. The acoustic properties of the layered system fused quartz substrate-IDT-zinc oxide film were evaluated based on the squared electromechanical coupling constant K/sup 2/ for strip filters. It was found that K/sup 2/ depends on the magnitude of the mechanical stresses. When zinc oxide films are deposited by the method of magnetron deposition on fused quartz substrates, depending on the process conditions limitations can arise on the rate of deposition owing to mechanical stresses, which significantly degrade the efficiency of SAW transducers based on them, in the ZnO films.

  17. Resputtering of zinc oxide films prepared by radical assisted sputtering

    SciTech Connect

    Song Qiuming; Jiang Yousong; Song Yizhou

    2009-02-15

    Sputtering losses of zinc oxide films prepared by radical assisted sputtering were studied. It was found that the sputtering loss can be very severe in oxygenous sputtering processes of zinc oxide films. In general, resputtering caused by negative oxygen ions dominates the sputtering loss, while diffuse deposition plays a minor role. Resputtering is strongly correlated with the sputtering threshold energy of the deposited films and the concentration of O{sup -} in the sputtering zone. The balance between the oxygen concentration in the sputtering zone and the oxidation degree of the growing films depends on the sputtering rate. Our research suggests that a lower oxygen concentration in the sputtering zone and a higher oxidation degree of the growing films are favorable for reducing the resputtering losses. The sputtering loss mechanisms discussed in this work are also helpful for understanding the deposition processes of other magnetron sputtering systems.

  18. Amorphous tin-cadmium oxide films and the production thereof

    DOEpatents

    Li, Xiaonan; Gessert, Timothy A

    2013-10-29

    A tin-cadmium oxide film having an amorphous structure and a ratio of tin atoms to cadmium atoms of between 1:1 and 3:1. The tin-cadmium oxide film may have an optical band gap of between 2.7 eV and 3.35 eV. The film may also have a charge carrier concentration of between 1.times.10.sup.20 cm.sup.-3 and 2.times.10.sup.20 cm.sup.-3. The tin cadmium oxide film may also exhibit a Hall mobility of between 40 cm.sup.2V.sup.-1 s.sup.-1 and 60 cm.sup.2V.sup.-1 s.sup.-1. Also disclosed is a method of producing an amorphous tin-cadmium oxide film as described and devices using same.

  19. Comparisons of the film peeling from the composite oxides of quartz sand filters using ozone, hydrogen peroxide and chlorine dioxide.

    PubMed

    Guo, Yingming; Huang, Tinglin; Wen, Gang; Cao, Xin

    2015-08-01

    To solve the problem of shortened backwashing intervals in groundwater plants, several disinfectants including ozone (O3), hydrogen peroxide (H2O2) and chlorine dioxide (ClO2) were examined to peel off the film from the quartz sand surface in four pilot-scale columns. An optimized oxidant dosage and oxidation time were determined by batch tests. Subsequently, the optimized conditions were tested in the four pilot-scale columns. The results demonstrated that the backwashing intervals increased from 35.17 to 54.33 (H2O2) and to 53.67 hr (ClO2) after the oxidation treatments, and the increase of backwashing interval after treatment by O3 was much less than for the other two treatments. Interestingly, the treatment efficiency of filters was not affected by O3 or H2O2 oxidation; but after oxidation by ClO2, the treatment efficiency was deteriorated, especially the ammonia removal (from 96.96% to 24.95%). The filter sands before and after the oxidation were characterized by scanning electron microscopy and X-ray photoelectron spectroscopy. Compared with the oxidation by O3 and H2O2, the structures on the surface of filter sands were seriously damaged after oxidation by ClO2. The chemical states of manganese on the surfaces of those treated sands were only changed by ClO2. The damage of the structures and the change of the chemical states of manganese might have a negative effect on the ammonia removal. In summary, H2O2 is a suitable agent for film peeling. PMID:26257342

  20. Rapid Deposition of Titanium Oxide and Zinc Oxide Films by Solution Precursor Plasma Spray

    NASA Astrophysics Data System (ADS)

    Ando, Yasutaka

    In order to develop a high rate atmospheric film deposition process for functional films, as a basic study, deposition of titanium oxide film and zinc oxide film by solution precursor plasma spray (SPPS) was conducted in open air. Consequently, in the case of titanium oxide film deposition, anantase film and amorphous film as well as rutile film could be deposited by varying the deposition distance. In the case of anatase dominant film, photo-catalytic properties of the films could be confirmed by wettability test. In addition, the dye sensitized sollar cell (DSC) using the TiO2 film deposited by this SPPS technique as photo voltaic device generates 49mV in OCV. On the other hand, in the case of zinc oxide film deposition, it was proved that well crystallized ZnO films with photo catalytic properties could be deposited. From these results, this process was found to have high potential for high rate functional film deposition process conducted in the air.

  1. Oxidation of aniline and other primary aromatic amines by manganese dioxide

    SciTech Connect

    Laha, S.; Luthy, R.G. )

    1990-03-01

    This investigation evaluated the redox reaction between a manganese dioxide, {sigma}-MnO{sub 2}, and anilines and other aromatic reductants in aqueous suspensions at pH values ranging from 3.7 to 6.5. The reaction with manganese dioxide may represent a pathway for transformation of aniline and other primary aromatic amines in acidic mineralogical and soil/water environments in the absence of oxygen and substantial microbial activity. The reaction rate with aniline is pH-dependent, increasing with decreasing pH, and first order with respect to {sigma}-MnO{sub 2} and organic solute. Aniline and p-toluidine are demonstrated to be 2-equiv reductants, as is believed to be the case for the other aromatic solutes considered in this study, including the substituted anilines, and hydroquinone and catechol and their alkyl substituents. Ring-bound nitrogen-containing aromatic solutes (methylimidazole, quinoline, and 5,5-dimethylhydantion) were unreactive with manganese dioxide at pH 6.4. The order of the reactivity of para-substituted anilines was methoxy >> methyl > chloro > carboxy >> nitro; the relative reactivity of these compounds correlated with the solute's half-wave potential and Hammett constant.

  2. Power generation using spinel manganese-cobalt oxide as a cathode catalyst for microbial fuel cell applications.

    PubMed

    Mahmoud, Mohamed; Gad-Allah, Tarek A; El-Khatib, K M; El-Gohary, Fatma

    2011-11-01

    This study focused on the use of spinel manganese-cobalt (Mn-Co) oxide, prepared by a solid state reaction, as a cathode catalyst to replace platinum in microbial fuel cells (MFCs) applications. Spinel Mn-Co oxides, with an Mn/Co atomic ratios of 0.5, 1, and 2, were prepared and examined in an air cathode MFCs which was fed with a molasses-laden synthetic wastewater and operated in batch mode. Among the three Mn-Co oxide cathodes and after 300 h of operation, the Mn-Co oxide catalyst with Mn/Co atomic ratio of 2 (MnCo-2) exhibited the highest power generation 113 mW/m2 at cell potential of 279 mV, which were lower than those for the Pt catalyst (148 mW/m2 and 325 mV, respectively). This study indicated that using spinel Mn-Co oxide to replace platinum as a cathodic catalyst enhances power generation, increases contaminant removal, and substantially reduces the cost of MFCs. PMID:21944282

  3. Characterization of High-Velocity Solution Precursor Flame-Sprayed Manganese Cobalt Oxide Spinel Coatings for Metallic SOFC Interconnectors

    NASA Astrophysics Data System (ADS)

    Puranen, Jouni; Laakso, Jarmo; Kylmälahti, Mikko; Vuoristo, Petri

    2013-06-01

    A modified high-velocity oxy-fuel spray (HVOF) thermal spray torch equipped with liquid feeding hardware was used to spray manganese-cobalt solutions on ferritic stainless steel grade Crofer 22 APU substrates. The HVOF torch was modified in such a way that the solution could be fed axially into the combustion chamber through 250- and 300-μm-diameter liquid injector nozzles. The solution used in this study was prepared by diluting nitrates of manganese and cobalt, i.e., Mn(NO3)2·4H2O and Co(NO3)2·6H2O, respectively, in deionized water. The as-sprayed coatings were characterized by X-ray diffraction and field-emission scanning electron microscopy operating in secondary electron mode. Chemical analyses were performed on an energy dispersive spectrometer. Coatings with remarkable density could be prepared by the novel high-velocity solution precursor flame spray (HVSPFS) process. Due to finely sized droplet formation in the HVSPFS process and the use of as delivered Crofer 22 APU substrate material having very low substrate roughness ( R a < 0.5 μm), thin and homogeneous coatings, with thicknesses lower than 10 μm could be prepared. The coatings were found to have a crystalline structure equivalent to MnCo2O4 spinel with addition of Co-oxide phases. Crystallographic structure was restored back to single-phase spinel structure by heat treatment.

  4. The development of manganese oxide coated ceramic membranes for combined catalytic ozonation and ultrafiltration of drinking water

    NASA Astrophysics Data System (ADS)

    Corneal, Lindsay Marie

    A novel method for the preparation of hydrated MnO2 by the ozonation of MnCl2 in water is described. The hydrated MnO 2 was used to coat titania water filtration membranes using a layer-by-layer technique. The coated membranes were then sintered in air at 500°C for 45 minutes. Upon sintering, the MnO2 is converted to alpha-Mn 2O3 (as characterized by x-ray and electron diffraction). Atomic force microscopy (AFM) imaging showed no significant change in the roughness or height of the surface features of coated membranes, while scanning electron microscopy (SEM) imaging showed an increase in grain size with increasing number of coating layers. Energy dispersive x-ray spectroscopy (EDS) mapping and line scans revealed manganese present throughout the membrane, indicating that manganese dispersed into the porous membrane during the coating process and diffused into the titania grains during sintering. Selected area diffraction (SAD) of the coated and sintered membrane was used to index the surface layer as alpha-Mn2O3. The surface layer was uneven, although there was a trend of increasing thickness with increasing coating layers. The coating acts as a catalyst for the oxidation of organic matter when coated membranes are used in a hybrid ozonation-membrane filtration system. A trend of decreasing total organic carbon (TOC) in the permeate water was observed with increasing number of coating layers. The catalytic activity also manifests itself as improved recovery of the water flux due to oxidation of foulants on the membrane surface. Ceramic nanoparticle coatings on ceramic water filtration membranes must undergo high temperature sintering. However, this means that the underlying membrane, which has been engineered for a given molecular weight cut-off (MWCO), also undergoes a high temperature heat treatment that serves to increase pore size that have resulted in increases in permeability of titania membranes. Coating the titania membrane with manganese oxide followed

  5. Ferromagnetism in indium manganese arsenide magnetic semiconductor thin films deposited by metalorganic vapor phase epitaxy

    NASA Astrophysics Data System (ADS)

    Blattner, Aaron J.

    The structure-property relationships of (In,Mn)As magnetic semiconductor thin films have been investigated to elucidate the mechanism of ferromagnetism and to assess its viability for use in spintronic device applications. Single phase, epitaxial (In,Mn)As films were deposited for the first time using atmospheric pressure metalorganic vapor phase epitaxy. The microstructure and phase composition of these films were determined using X-ray diffraction, transmission electron microscopy, and extended x-ray absorption fine structure measurements. Magnetic properties of the films were examined using superconducting quantum interference device magnetometery. Room temperature ferromagnetism was observed in single-phase In1-xMn xAs films with x ≤ 0.10. Magnetization measurements indicated that these (In,Mn)As samples had a transition temperature of 298--333 K. The Curie temperature was effectively independent of Mn concentration over the range of 1--10%. The temperature dependent magnetization along with the magnitude of the saturation magnetization and microstructural analysis indicated that the source of the high-temperature ferromagnetism in single-phase films is not attributable to MnAs nanoprecipitates. The Curie temperatures for these films are nearly constant for hole concentrations of 8 x 1017--1.6 x 1018 cm -3. In addition, the hole concentration is at least two orders of magnitude smaller than what is required under the conventional hole-mediated theory of ferromagnetism to obtain room-temperature ferromagnetism. Consequently, this model in its current form is not sufficient to describe the ferromagnetism in (In,Mn)As deposited using MOVPE. A model based upon interacting atomic scale ferromagnetic clusters was developed. The ferromagnetic coupling between these clusters may be a hole-mediated mechanism. This model of interacting ferromagnetic clusters was very successful in describing both the temperature and field dependence of the magnetization. In addition

  6. Films based on oxidized starch and cellulose from barley.

    PubMed

    El Halal, Shanise Lisie Mello; Colussi, Rosana; Deon, Vinícius Gonçalves; Pinto, Vânia Zanella; Villanova, Franciene Almeida; Carreño, Neftali Lenin Villarreal; Dias, Alvaro Renato Guerra; Zavareze, Elessandra da Rosa

    2015-11-20

    Starch and cellulose fibers were isolated from grains and the husk from barley, respectively. Biodegradable films of native starch or oxidized starches and glycerol with different concentrations of cellulose fibers (0%, 10% and 20%) were prepared. The films were characterized by morphological, mechanical, barrier, and thermal properties. Cellulose fibers isolated from the barley husk were obtained with 75% purity and high crystallinity. The morphology of the films of the oxidized starches, regardless of the fiber addition, was more homogeneous as compared to the film of the native starch. The addition of cellulose fibers in the films increased the tensile strength and decreased elongation. The water vapor permeability of the film of oxidized starch with 20% of cellulose fibers was lower than the without fibers. However the films with cellulose fibers had the highest decomposition with the initial temperature and thermal stability. The oxidized starch and cellulose fibers from barley have a good potential for use in packaging. The addition of cellulose fibers in starch films can contribute to the development of films more resistant that can be applied in food systems to maintain its integrity. PMID:26344323

  7. Tunable T1 and T2 contrast abilities of manganese-engineered iron oxide nanoparticles through size control

    NASA Astrophysics Data System (ADS)

    Huang, Guoming; Li, Hui; Chen, Jiahe; Zhao, Zhenghuan; Yang, Lijiao; Chi, Xiaoqin; Chen, Zhong; Wang, Xiaomin; Gao, Jinhao

    2014-08-01

    In this paper, we demonstrate the tunable T1 and T2 contrast abilities of engineered iron oxide nanoparticles with high performance for liver contrast-enhanced magnetic resonance imaging (MRI) in mice. To enhance the diagnostic accuracy of MRI, large numbers of contrast agents with T1 or T2 contrast ability have been widely explored. The comprehensive investigation of high-performance MRI contrast agents with controllable T1 and T2 contrast abilities is of high importance in the field of molecular imaging. In this study, we synthesized uniform manganese-doped iron oxide (MnIO) nanoparticles with controllable size from 5 to 12 nm and comprehensively investigated their MRI contrast abilities. We revealed that the MRI contrast effects of MnIO nanoparticles are highly size-dependent. By controlling the size of MnIO nanoparticles, we can achieve T1-dominated, T2-dominated, and T1-T2 dual-mode MRI contrast agents with much higher contrast enhancement than the corresponding conventional iron oxide nanoparticles.In this paper, we demonstrate the tunable T1 and T2 contrast abilities of engineered iron oxide nanoparticles with high performance for liver contrast-enhanced magnetic resonance imaging (MRI) in mice. To enhance the diagnostic accuracy of MRI, large numbers of contrast agents with T1 or T2 contrast ability have been widely explored. The comprehensive investigation of high-performance MRI contrast agents with controllable T1 and T2 contrast abilities is of high importance in the field of molecular imaging. In this study, we synthesized uniform manganese-doped iron oxide (MnIO) nanoparticles with controllable size from 5 to 12 nm and comprehensively investigated their MRI contrast abilities. We revealed that the MRI contrast effects of MnIO nanoparticles are highly size-dependent. By controlling the size of MnIO nanoparticles, we can achieve T1-dominated, T2-dominated, and T1-T2 dual-mode MRI contrast agents with much higher contrast enhancement than the

  8. Chemical versus Enzymatic Digestion of Contaminated Estuarine Sediment: Relative Importance of Iron and Manganese Oxides in Controlling Trace Metal Bioavailability

    NASA Astrophysics Data System (ADS)

    Turner, A.; Olsen, Y. S.

    2000-12-01

    Chemical and enzymatic reagents have been employed to determine available concentrations of Fe, Mn, Cu and Zn in contaminated estuarine sediment. Gastric and intestinal enzymes (pepsin, pH 2, and trypsin, pH 7·6, respectively) removed significantly more metal than was water-soluble or exchangeable (by seawater or ammonium acetate), while gastro-intestinal fluid of the demersal teleost, Pleuronectes platessa L. (plaice), employed to operationally define a bioavailable fraction of contaminants, generally solubilized more metal than the model enzymes. Manganese was considerably more available than Fe under these conditions and it is suggested that the principal mechanism of contaminant release is via surface complexation and reductive solubilization of Mn oxides, a process which is enhanced under conditions of low pH. Of the chemical reagents tested, acetic acid best represents the fraction of Mn (as well as Cu and Zn) which is available under gastro-intestinal conditions, suggesting that the reducing tendency of acetate is similar to that of the ligands encountered in the natural digestive environment. Although the precise enzymatic and non-enzymatic composition of plaice gastro-intestinal fluid may be different to that encountered in more representative, filter-feeding or burrowing organisms, a general implication of this study is that contaminants associated with Mn oxides are significantly more bioavailable than those associated with Fe oxides, and that contaminant bioavailability may be largely dictated by the oxidic composition of contaminated sediment.

  9. Characterization and stability of thin oxide films on plutonium surfaces

    NASA Astrophysics Data System (ADS)

    Flores, H. G. García; Roussel, P.; Moore, D. P.; Pugmire, D. L.

    2011-02-01

    X-ray photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES) were employed to study oxide films on plutonium metal surfaces. Measurements of the relative concentrations of oxygen and plutonium, as well as the resulting oxidation states of the plutonium (Pu) species in the near-surface region are presented. The oxide product of the auto-reduction (AR) of plutonium dioxide films is evaluated and found to be an oxide species which is reduced further than what is expected. The results of this study show a much greater than anticipated extent of auto-reduction and challenge the commonly held notion of the stoichiometric stability of Pu 2O 3 thin-films. The data indicates that a sub-stoichiometric plutonium oxide (Pu 2O 3 - y ) exists at the metal-oxide interface. The level of sub-stoichiometry is shown to depend, in part, on the carbidic contamination of the metal surface.

  10. Aerosol chemical vapor deposition of metal oxide films

    DOEpatents

    Ott, Kevin C.; Kodas, Toivo T.

    1994-01-01

    A process of preparing a film of a multicomponent metal oxide including: forming an aerosol from a solution comprised of a suitable solvent and at least two precursor compounds capable of volatilizing at temperatures lower than the decomposition temperature of said precursor compounds; passing said aerosol in combination with a suitable oxygen-containing carrier gas into a heated zone, said heated zone having a temperature sufficient to evaporate the solvent and volatilize said precursor compounds; and passing said volatilized precursor compounds against the surface of a substrate, said substrate having a sufficient temperature to decompose said volatilized precursor compounds whereby metal atoms contained within said volatilized precursor compounds are deposited as a metal oxide film upon the substrate is disclosed. In addition, a coated article comprising a multicomponent metal oxide film conforming to the surface of a substrate selected from the group consisting of silicon, magnesium oxide, yttrium-stabilized zirconium oxide, sapphire, or lanthanum gallate, said multicomponent metal oxide film characterized as having a substantially uniform thickness upon said FIELD OF THE INVENTION The present invention relates to the field of film coating deposition techniques, and more particularly to the deposition of multicomponent metal oxide films by aerosol chemical vapor deposition. This invention is the result of a contract with the Department of Energy (Contract No. W-7405-ENG-36).

  11. Preparation of polyacrylnitrile (PAN)/ Manganese oxide based activated carbon nanofibers (ACNFs) for adsorption of Cadmium (II) from aqueous solution

    NASA Astrophysics Data System (ADS)

    Abdullah, N.; Yusof, N.; Jaafar, J.; Ismail, AF; Che Othman, F. E.; Hasbullah, H.; Salleh, W. N. W.; Misdan, N.

    2016-06-01

    In this work, activated carbon nanofibers (ACNFs) from precursor polyacrylnitrile (PAN) and manganese oxide (MnO2) were prepared via electrospinning process. The electrospun PAN/MnO2-based ACNFs were characterised in term of its morphological structure and specific surface area using SEM and BET analysis respectively. The comparative adsorption study of cadmium (II) ions from aqueous solution between the neat ACNFs, composite ACNFs and commercial granular activated carbon was also conducted. SEM analysis illustrated that composite ACNFs have more compact fibers with presence of MnO2 beads with smaller fiber diameter of 437.2 nm as compared to the neat ACNFs which is 575.5 nm. BET analysis elucidated specific surface area of ACNFs/MnO2 to be 67 m2/g. Under adsorption study, it was found out that Cd (II) removal by ACNFs/MnO2 was the highest (97%) followed by neat ACNFs (96%) and GAC (74%).

  12. Graphite coated with manganese oxide/multiwall carbon nanotubes composites as anodes in marine benthic microbial fuel cells

    NASA Astrophysics Data System (ADS)

    Fu, Yubin; Yu, Jian; Zhang, Yelong; Meng, Yao

    2014-10-01

    Improving anode performance is of great significance to scale up benthic microbial fuel cells (BMFCs) for its marine application to drive oceanography instruments. In this study, manganese oxide (MnO2)/multiwall carbon nanotubes (MWCNTs) composites are prepared to be as novel anodes in the BMFCs via a direct redox reaction between permanganate ions (MnO4-) and MWCNTs. The results indicate that the MnO2/MWCNTs anode has a better wettability, greater kinetic activity and higher power density than that of the plain graphite (PG) anode. It is noted that the MnO2 (50% weight percent)/MWCNTs anode shows the highest electrochemical performance among them and will be a promising material for improving bioelectricity production of the BMFCs. Finally, a synergistic mechanism of electron transfer shuttle of Mn ions and their redox reactions in the interface between modified anode and bacteria biofilm are proposed to explain its excellent electrochemical performance.

  13. Ketjenblack carbon supported amorphous manganese oxides nanowires as highly efficient electrocatalyst for oxygen reduction reaction in alkaline solutions.

    PubMed

    Lee, Jang-Soo; Park, Gi Su; Lee, Ho Il; Kim, Sun Tai; Cao, Ruiguo; Liu, Meilin; Cho, Jaephil

    2011-12-14

    A composite air electrode consisting of Ketjenblack carbon (KB) supported amorphous manganese oxide (MnOx) nanowires, synthesized via a polyol method, is highly efficient for the oxygen reduction reaction (ORR) in a Zn-air battery. The low-cost and highly conductive KB in this composite electrode overcomes the limitations due to low electrical conductivity of MnOx while acting as a supporting matrix for the catalyst. The large surface area of the amorphous MnOx nanowires, together with other microscopic features (e.g., high density of surface defects), potentially offers more active sites for oxygen adsorption, thus significantly enhancing ORR activity. In particular, a Zn-air battery based on this composite air electrode exhibits a peak power density of ∼190 mW/cm2, which is far superior to those based on a commercial air cathode with Mn3O4 catalysts. PMID:22050041

  14. Manganese-enhanced biotransformation of atrazine by the white rot fungus Pleurotus pulmonarius and its correlation with oxidation activity.

    PubMed Central

    Masaphy, S; Henis, Y; Levanon, D

    1996-01-01

    Manganese enhanced atrazine transformation by the fungus Pleurotus pulmonarius when added to a liquid culture medium at concentrations of up to 300 microM. Both N-dealkylated and propylhydroxylated metabolites accumulated in the culture medium, with the former accumulating to a greater extent than did the latter. Lipid peroxidation, oxygenase and peroxidase activities, and the cytochrome P-450 concentration increased. In addition, an increase in the spectral interactions between atrazine and components in the cell extract was observed. Antioxidants, mainly nordihydroguaiaretic acid, which inhibits lipoxygenase, peroxidase, and P-450 activities, and piperonyl butoxide, which inhibits P-450 activity, inhibited atrazine transformation by the mycelium. It is suggested that the stimulation of oxidative activity by Mn might be responsible for increasing the biotransformation of atrazine and for nonspecific transformations of other xenobiotic compounds. PMID:8967773

  15. Hybrid nickel manganese oxide nanosheet-3D metallic dendrite percolation network electrodes for high-rate electrochemical energy storage

    NASA Astrophysics Data System (ADS)

    Nguyen, Tuyen; Eugénio, Sónia; Boudard, Michel; Rapenne, Laetitia; Carmezim, M. João; Silva, Teresa M.; Montemor, M. Fátima

    2015-07-01

    This work reports the fabrication, by electrodeposition and post-thermal annealing, of hybrid electrodes for high rate electrochemical energy storage composed of nickel manganese oxide (Ni0.86Mn0.14O) nanosheets over 3D open porous dendritic NiCu foams. The hybrid electrodes are made of two different percolation networks of nanosheets and dendrites, and exhibit a specific capacitance value of 848 F g-1 at 1 A g-1. The electrochemical tests revealed that the electrodes display an excellent rate capability, characterized by capacitance retention of approximately 83% when the applied current density increases from 1 A g-1 to 20 A g-1. The electrodes also evidenced high charge-discharge cycling stability, which attained 103% after 1000 cycles.

  16. Hydrothermal synthesis of Mn(OH)O nanowires and their thermal conversion to (1D)-manganese oxides nanostructures

    NASA Astrophysics Data System (ADS)

    Mohamed Ahmed, Khalid Abdelazez; Abbood, Hayder A.; Huang, Kaixun

    2012-11-01

    Manganite Mn(OH)O nanowires were successfully synthesized using a hydrothermal method based on a mild and direct reaction between potassium permanganate and ethylene glycol. Subsequent heat treatment of Mn(OH)O nanowires in air at 400 °C for 4 h and 900 °C for 2 h, was conducted to prepare pyrolusite MnO2 nanobelts and necklace-like bixbyite-C Mn2O3 nanowires, respectively. A variety of techniques, including X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), selected area electron diffraction (SA-ED), high resolution transmission electron microscopy (HR-TEM) and thermogravimetry-differential thermal analyzer (TG-DTA), were employed to characterize the resulting materials. The ethylene glycol and heating furnace imposed an effect on the morphology evolution of one dimensional (1D) manganese oxides nanocrystals.

  17. Low reflectance sputtered vanadium oxide thin films on silicon

    NASA Astrophysics Data System (ADS)

    Esther, A. Carmel Mary; Dey, Arjun; Rangappa, Dinesh; Sharma, Anand Kumar

    2016-07-01

    Vanadium oxide thin films on silicon (Si) substrate are grown by pulsed radio frequency (RF) magnetron sputtering technique at RF power in the range of 100-700 W at room temperature. Deposited thin films are characterized by field emission scanning electron microscopy (FESEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) techniques to investigate microstructural, phase, electronic structure and oxide state characteristics. The reflectance and transmittance spectra of the films and the Si substrate are recorded at the solar region (200-2300 nm) of the spectral window. Substantial reduction in reflectance and increase in transmittance is observed for the films grown beyond 200 W. Further, optical constants viz. absorption coefficient, refractive index and extinction coefficient of the deposited vanadium oxide films are evaluated.

  18. Evidence of a new structural phase of manganese-iron oxide

    NASA Astrophysics Data System (ADS)

    Kolk, B.; Albers, A.; Hearne, G. R.; Le Roux, H.

    1988-02-01

    Coprecipitation of manganese and iron followed by calcination at temperatures below 500°C results in a new structural phase for the Mn-Fe-O system: a non-stoichiometric spinel with, in every three unit cells, one metal atom missing. About 57% of the iron in this spinel has the composition γMnFeO3 which is paramagnetic at room temperature. The remaining 43% of the iron has the composition MnyFe2-yO3 with y˜0.16 which is magnetic at room temperature.

  19. Method for producing high quality oxide films on substrates

    DOEpatents

    Ruckman, M.W.; Strongin, M.; Gao, Y.L.

    1993-11-23

    A method is described for providing an oxide film of a material on the surface of a substrate using a reactive deposition of the material onto the substrate surface in the presence of a solid or liquid layer of an oxidizing gas. The oxidizing gas is provided on the substrate surface in an amount sufficient to dissipate the latent heat of condensation occurring during deposition as well as creating a favorable oxidizing environment for the material. 4 figures.

  20. Method for producing high quality oxide films on substrates

    DOEpatents

    Ruckman, Mark W.; Strongin, Myron; Gao, Yong L.

    1993-01-01

    A method for providing an oxide film of a material on the surface of a substrate using a reactive deposition of the material onto the substrate surface in the presence of a solid or liquid layer of an oxidizing gas. The oxidizing gas is provided on the substrate surface in an amount sufficient to dissipate the latent heat of condensation occurring during deposition as well as creating a favorable oxidizing environment for the material.