nanoscale manganese oxide: Topics by Science.gov

Sample records for nanoscale manganese oxide

Nanoscale octahedral molecular sieves: Syntheses, characterization, and applications

NASA Astrophysics Data System (ADS)

Liu, Jia

The major part of this research consists of studies on novel synthesis methods, characterization, and catalytic applications of nanoscale manganese oxide octahedral molecular sieves. The second part involves studies of new applications of bulk porous molecular sieve and layered materials (MSLM), zeolites, and inorganic powder materials for diminishing wound bleeding. Manganese oxide octahedral molecular sieves (OMS) are very important microporous materials. They have been used widely as bulk materials in catalysis, separations, chemical sensors, and batteries, due to their unique tunnel structures and useful properties. Novel methods have been developed to synthesize novel nanoscale octahedral molecular sieve manganese oxides (OMS) and metal-substituted OMS materials in order to modify their physical and chemical properties and to improve their catalytic applications. Different synthetic routes were investigated to find better, faster, and cheaper pathways to produce nanoscale or metal-substituted OMS materials. In the synthetic study of nanosize OMS materials, a combination of sol-gel synthesis and hydrothermal reaction was used to prepare pure crystalline nanofibrous todorokite-type (OMS-1) and cryptomelane-typed (OMS-2) manganese oxides using four alkali cations (Li+, K+, Na +, Rb+) and NH4+ cations. In the synthesis study of nanoscale and metal-substituted OMS materials, a combination of sol-gel synthesis and solid-state reaction was used to prepare transition metal-substituted OMS-2 nanorods, nanoneedles, and nanowires. Preparative parameters of syntheses, such as cation templates, heating temperature and time, were investigated in these syntheses of OMS-1 and OMS-2 materials. The catalytic activities of the novel synthetic nanoscale OMS materials has been evaluated on green oxidation of alcohols and toluene and were found to be much higher than their correspondent bulk materials. New applications of bulk manganese oxide molecular sieve and layered materials (MSLM), zeolites, and several inorganic powder materials have also been studied for diminishing bleeding via in vitro tests using horse blood and in vivo tests on rat organs. MSLM, as well as several types of zeolite, and several inorganic compounds, have been found to have excellent ability to clot blood and arrest wound bleeding. Effects of properties of these porous materials on the efficiency of blood coagulation have been discussed.
Redox Deposition of Nanoscale Metal Oxides on Carbon for Next-Generation Electrochemical Capacitors

DTIC Science & Technology

2013-01-01

Nanoscale Metal Oxides Sassin et al. Redox Deposition Approaches to Nanoscale Coatings of Metal Oxides Manganese Oxides. Permanganate (MnO4 ) is a versa...scalability of the permanganate carbon redox reaction for generating MnOx coatings that store charge.21 The initial study per- formed on planar graphite...the carbon surface from the aqueous permanganate solu- tion (pH∼5),29,35 evidenced by a sharp increase in solution pH and a decrease in solution
Thermodynamics of manganese oxides: Sodium, potassium, and calcium birnessite and cryptomelane

PubMed Central

Birkner, Nancy; Navrotsky, Alexandra

2017-01-01

Manganese oxides with layer and tunnel structures occur widely in nature and inspire technological applications. Having variable compositions, these structures often are found as small particles (nanophases). This study explores, using experimental thermochemistry, the role of composition, oxidation state, structure, and surface energy in the their thermodynamic stability. The measured surface energies of cryptomelane, sodium birnessite, potassium birnessite and calcium birnessite are all significantly lower than those of binary manganese oxides (Mn3O4, Mn2O3, and MnO2), consistent with added stabilization of the layer and tunnel structures at the nanoscale. Surface energies generally decrease with decreasing average manganese oxidation state. A stabilizing enthalpy contribution arises from increasing counter-cation content. The formation of cryptomelane from birnessite in contact with aqueous solution is favored by the removal of ions from the layered phase. At large surface area, surface-energy differences make cryptomelane formation thermodynamically less favorable than birnessite formation. In contrast, at small to moderate surface areas, bulk thermodynamics and the energetics of the aqueous phase drive cryptomelane formation from birnessite, perhaps aided by oxidation-state differences. Transformation among birnessite phases of increasing surface area favors compositions with lower surface energy. These quantitative thermodynamic findings explain and support qualitative observations of phase-transformation patterns gathered from natural and synthetic manganese oxides. PMID:28130549
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 spinel Mn3O4) for smaller particle size and in the presence of surface hydration. Chemisorption of water onto anhydrous nanophase Mn2O 3 surfaces promotes rapidly reversible redox phase changes at room temperature as confirmed by calorimetry, X-ray diffraction, and titration for manganese average oxidation state. Water adsorption microcalorimetry (in situ) at room temperature measured the strongly exothermic integral enthalpy of water adsorption (-103.5 kJ/mol) and monitored the energetics of the redox phase transformation. Hydration-driven redox transformation of anhydrous nanophase Mn(III) 2O3, (high surface enthalpy of anhydrous surfaces 1.77 +/- 0.10 J/m2) to Mn(II,III)3O4 (lower surface enthalpy 0.96 +/- 0.08 J/m2) occurred during the first few doses of water vapor. Surface reduction of nanoparticle bixbyite (Mn 2O3) to hausmannite (Mn3O4) occurs under conditions where no such reactions are seen or expected on grounds of bulk thermodynamics in coarse-grained materials. Layered structure manganese oxides contain alkali or alkaline earth cations and water, are generally fine-grained, and have considerable thermodynamic stability. The surface enthalpies (SE) of layered and tunnel structure complex manganese oxides are significantly lower than those of the binary manganese oxide phases. The SE for hydrous surfaces and overall manganese average oxidation state (AOS) (value in parentheses) are: cryptomelane 0.77 +/- 0.10 J/m 2 (3.78), sodium birnessite 0.69 +/- 0.13 J/m2 (3.56), potassium birnessite 0.55 +/- 0.11 J/m2 (3.52), and calcium birnessite 0.41 +/- 0.11 J/m2 (3.50). Surface enthalpies of hydrous surfaces of the calcium manganese oxide nanosheets are: deltaCa 0.39MnO2.3nH2O 0.75 +/- 0.10 J/m2 (3.89) and deltaCa0.43MnO2.3nH2O 0.57 +/- 0.12 J/m2 (3.68). The surface enthalpy of the complex manganese oxides appears to decrease with decreasing manganese average oxidation state, that is, with greater mixed valence manganese (Mn 3+/4+). Low surface energy suggests loose binding of H2O on the internal and external surfaces and may be critical to catalysis in both natural and technological settings.
Probing Interactions at the Nanoscale by Ion Current through Nanopores and Nanovoids

NASA Astrophysics Data System (ADS)

Gamble, Trevor Patrick

Polymer nanopores offer themselves as excellent test beds for study of phenomena that occur on the nano-scale, such as Debye layer formation, surface charge modulation, current saturation, and rectification. Studying ions interactions within the Debye layer, for example, is not possible on the micro-scale, where the pore diameter can be 100 times the size of the zone where interactions of interest occur. However, in our nanopores with an opening diameter less than 10 nm, a slight change of the Debye length can lead to drastic changes of the recorded ion current. Here we present our nanopores' use as a tool to study geometrical and electrochemical properties of porous manganese oxide. There is great value in studying nano-scale properties of this material because of its importance in lithium ion batteries and newly developed nano-architectures within supercapacitors. We electrodeposited manganese oxide wires into our cylindrical nanopores, filling them completely. In this use, nanopores became a template to probe properties of the embedded material such as surface charge, ion selectivity, and porosity. This information was then reported to the Energy Frontier Research Center (EFRC) collaboration, so that other groups can incorporate these recently discovered characteristics into future their nano-architecture design. Additionally, we constructed conical nanopores to study interactions between the surface charges found on the walls and alkali metal ions. In particular we looked at lithium, as it is the electrochemically active ion during charge cycling in EFRC energy storage devices. We attempted to reveal lithium ion's affinity to bind to surface charges. We found this binding led to lowering of the effective surface charge of the pore walls, while also decreasing lithium's ability to move through channels or voids that have charged walls. In connection to manganese oxide, a porous, charged material with voids, information on lithium's interaction with these charges is paramount.
DOE Office of Scientific and Technical Information (OSTI.GOV)

Young, Matthias J.; Schnabel, Hans-Dieter; Holder, Aaron M.

Nanoscale spinel lithium manganese oxide is of interest as a high-rate cathode material for advanced battery technologies among other electrochemical applications. In this work, the synthesis of ultrathin films of spinel lithium manganese oxide (LiMn 2O 4) between 20 and 200 nm in thickness by room-temperature electrochemical conversion of MnO grown by atomic layer deposition (ALD) is demonstrated. The charge storage properties of LiMn 2O 4 thin films in electrolytes containing Li +, Na +, K +, and Mg 2+ are investigated. A unified electrochemical band-diagram (UEB) analysis of LiMn 2O 4 informed by screened hybrid density functional theory calculationsmore » is also employed to expand on existing understanding of the underpinnings of charge storage and stability in LiMn 2O 4. It is shown that the incorporation of Li + or other cations into the host manganese dioxide spinel structure (λ-MnO 2) stabilizes electronic states from the conduction band which align with the known redox potentials of LiMn 2O 4. Furthermore, the cyclic voltammetry experiments demonstrate that up to 30% of the capacity of LiMn 2O 4 arises from bulk electronic charge-switching which does not require compensating cation mass transport. As a result, the hybrid ALD-electrochemical synthesis, UEB analysis, and unique charge storage mechanism described here provide a fundamental framework to guide the development of future nanoscale electrode materials for ion-incorporation charge storage.« less
Band diagram and rate analysis of thin film spinel LiMn 2O 4 formed by electrochemical conversion of ALD-grown MnO

DOE PAGES

Young, Matthias J.; Schnabel, Hans-Dieter; Holder, Aaron M.; ...

2016-09-22

Nanoscale spinel lithium manganese oxide is of interest as a high-rate cathode material for advanced battery technologies among other electrochemical applications. In this work, the synthesis of ultrathin films of spinel lithium manganese oxide (LiMn 2O 4) between 20 and 200 nm in thickness by room-temperature electrochemical conversion of MnO grown by atomic layer deposition (ALD) is demonstrated. The charge storage properties of LiMn 2O 4 thin films in electrolytes containing Li +, Na +, K +, and Mg 2+ are investigated. A unified electrochemical band-diagram (UEB) analysis of LiMn 2O 4 informed by screened hybrid density functional theory calculationsmore » is also employed to expand on existing understanding of the underpinnings of charge storage and stability in LiMn 2O 4. It is shown that the incorporation of Li + or other cations into the host manganese dioxide spinel structure (λ-MnO 2) stabilizes electronic states from the conduction band which align with the known redox potentials of LiMn 2O 4. Furthermore, the cyclic voltammetry experiments demonstrate that up to 30% of the capacity of LiMn 2O 4 arises from bulk electronic charge-switching which does not require compensating cation mass transport. As a result, the hybrid ALD-electrochemical synthesis, UEB analysis, and unique charge storage mechanism described here provide a fundamental framework to guide the development of future nanoscale electrode materials for ion-incorporation charge storage.« less
Synthesis and characterization of porous metal oxides and desulfurization studies of sulfur containing compounds

NASA Astrophysics Data System (ADS)

Garces Trujillo, Hector Fabian

This thesis contains two parts: 1) synthesis and characterization of porous metal oxides that include zinc oxide and a porous mixed-valent manganese oxide with an amorphous structure (AMO) 2) the desulfurization studies for the removal of sulfur compounds. Zinc oxide with different nano-scale morphologies may result in various porosities with different adsorption capabilities. A tunable shape microwave synthesis of ZnO nano-spheres in a co-solvent mixture is presented. The ZnO nano-sphere material is investigated as a desulfurizing sorbent in a fixed bed reactor in the temperature range 200 to 400 °C and compared with ZnO nanorods and platelet-like morphologies. Fresh and sulfided materials were characterized by X-ray diffraction (XRD), BET specific surface area, pore volume, scanning electron microscopy (SEM), X-ray energy dispersive spectroscopy (SEM/EDX), Raman spectroscopy, and thermogravimetric analysis (TGA). The tunable shape microwave synthesis of ZnO presents a high sulfur sorption capacity at temperatures as low as 200 °C which accounts for a three and four fold enhancement over the other preparations presented in this work, and reached 76 % of the theoretical sulfur capacity (TSC) at 300 °C. Another ZnO material with a bimodal micro- and mesopore size distribution investigated as a desulfurizing sorbent presents a sorption capacity that reaches 87% of the theoretical value for desulfurization at 400 °C at breakthrough time. A deactivation model that considers the activity of the solid reactant was used to fit the experimental data. Good agreement between the experimental breakthrough curves and the model predictions are obtained. Manganese oxides are a type of metal oxide materials commonly used in catalytic applications. Little is known about the adsorption capabilities for the removal of sulfur compounds. One of these manganese oxides; amorphous manganese oxide (AMO) is highly promising material for low temperature sorption processes. Amorphous manganese oxide (AMO) has been used in catalytic processes such as for the catalytic oxidation of benzyl alcohol, the preferential oxidation of CO, and for the capture of formate species. This chapter explores the possibility of using AMO in sorption processes for the removal of two contaminants; H 2S and COS in the temperature range 200 - 400 °C.
Synthesis, characterization and application of a nano-manganese-catalyst as an efficient solid catalyst for solvent free selective oxidation of ethylbenzene, cyclohexene, and benzylalcohol

NASA Astrophysics Data System (ADS)

Habibi, Davood; Faraji, Ali Reza

2013-07-01

The object of this study is to synthesize the heterogeneous Mn-nano-catalyst (MNC) which has been covalently anchored on a modified nanoscaleSiO2/Al2O3, and characterized by FT-IR, UV-Vis, CHN elemental analysis, EDS, TEM, and EDX. The method is efficient for the highly selective oxidation of ethylbenzene, cyclohexene, and benzylalcohol without the need to any solvents, using tert-butyl hydroperoxide (TBHP) as an oxidant. Oxidation of ethylbenzene, cyclohexene, and benzylalcohol gave acetophenone, 2-cyclohexene-1-one and benzaldehyde, respectively, as major products. Reaction conditions have been optimized by considering the effect of various factors such as reaction time, amounts of substrates and oxidant, Mn-nano-catalyst and application of various solvents.
Nanoscale surface analysis on second generation advanced high strength steel after hot dip galvanizing.

PubMed

Arndt, M; Duchoslav, J; Preis, K; Samek, L; Stifter, D

2013-09-01

Second generation advanced high strength steel is one promising material of choice for modern automotive structural parts because of its outstanding maximal elongation and tensile strength. Nonetheless there is still a lack of corrosion protection for this material due to the fact that cost efficient hot dip galvanizing cannot be applied. The reason for the insufficient coatability with zinc is found in the segregation of manganese to the surface during annealing and the formation of manganese oxides prior coating. This work analyses the structure and chemical composition of the surface oxides on so called nano-TWIP (twinning induced plasticity) steel on the nanoscopic scale after hot dip galvanizing in a simulator with employed analytical methods comprising scanning Auger electron spectroscopy (SAES), energy dispersive X-ray spectroscopy (EDX), and focused ion beam (FIB) for cross section preparation. By the combination of these methods, it was possible to obtain detailed chemical images serving a better understanding which processes exactly occur on the surface of this novel kind of steel and how to promote in the future for this material system galvanic protection.
Development of a reactive zone technology for simultaneous in situ immobilisation of radium and uranium

NASA Astrophysics Data System (ADS)

Burghardt, D.; Kassahun, A.

2005-12-01

Simultaneous in situ immobilisation of uranium (U) and radium (226Ra) by injectible amounts of grey cast iron (gcFe), nano-scale iron (naFe) and a gcFe/MnO2 mixture (1:1) was studied in batch and column tests. Both 0.5 g/L naFe and gcFe are effective in 226Ra and U removal from mine water, whereas MnO2 addition clearly increased the efficiency of gcFe for 226Ra and U immobilisation. In a column test with 0.6 wt% gcFe/MnO2 mixture (1:1), neither 226Ra nor U was detected in the effluent after replacement of 45 pore volumes. A sequential extraction under flow condition revealed 226Ra to be mostly occluded in manganese oxides. Uranium was mostly sorbed onto poorly crystalline iron hydroxides, but a significant part was found to be occluded in manganese oxides also. The results of this study suggest that MnO2 promotes iron hydroxide formation under slightly reducing environmental conditions resulting in an increased pollutant retention capacity.
Production of Manganese Oxide Nanoparticles by Shewanella Species

PubMed Central

Farooqui, Saad M.; White, Alan R.

2016-01-01

ABSTRACT Several species of the bacterial genus Shewanella are well-known dissimilatory reducers of manganese under anaerobic conditions. In fact, Shewanella oneidensis is one of the most well studied of all metal-reducing bacteria. In the current study, a number of Shewanella strains were tested for manganese-oxidizing capacity under aerobic conditions. All were able to oxidize Mn(II) and to produce solid dark brown manganese oxides. Shewanella loihica strain PV-4 was the strongest oxidizer, producing oxides at a rate of 20.3 mg/liter/day and oxidizing Mn(II) concentrations of up to 9 mM. In contrast, S. oneidensis MR-1 was the weakest oxidizer tested, producing oxides at 4.4 mg/liter/day and oxidizing up to 4 mM Mn(II). Analysis of products from the strongest oxidizers, i.e., S. loihica PV-4 and Shewanella putrefaciens CN-32, revealed finely grained, nanosize, poorly crystalline oxide particles with identical Mn oxidation states of 3.86. The biogenic manganese oxide products could be subsequently reduced within 2 days by all of the Shewanella strains when culture conditions were made anoxic and an appropriate nutrient (lactate) was added. While Shewanella species were detected previously as part of manganese-oxidizing consortia in natural environments, the current study has clearly shown manganese-reducing Shewanella species bacteria that are able to oxidize manganese in aerobic cultures. IMPORTANCE Members of the genus Shewanella are well known as dissimilatory manganese-reducing bacteria. This study shows that a number of species from Shewanella are also capable of manganese oxidation under aerobic conditions. Characterization of the products of the two most efficient oxidizers, S. loihica and S. putrefaciens, revealed finely grained, nanosize oxide particles. With a change in culture conditions, the manganese oxide products could be subsequently reduced by the same bacteria. The ability of Shewanella species both to oxidize and to reduce manganese indicates that the genus plays a significant role in the geochemical cycling of manganese. Due to the high affinity of manganese oxides for binding other metals, these bacteria may also contribute to the immobilization and release of other metals in the environment. PMID:27342559
Iron and manganese oxides modified maize straw to remove tylosin from aqueous solutions.

PubMed

Yin, Yongyuan; Guo, Xuetao; Peng, Dan

2018-08-01

Maize straw modified by iron and manganese oxides was synthesized via a simple and environmentally friendly method. Three maize straw materials, the original maize straw, maize straw modified by manganese oxides and maize straw modified by iron and manganese oxides, were detected by SEM, BET, XPS, XRD and FTIR. The results showed that maize straw was successfully modified and maize straw modified by iron and manganese oxides has a larger surface area than MS. According to the experimental data, the sorption trend could conform to the pseudo-second-order kinetic model well, and the sorption ability of tylosin on sorbents followed the order of original maize straw < maize straw modified by manganese oxides < maize straw modified by iron and manganese oxides. The study indicated that manganese oxides and iron-manganese oxides could significantly enhance the sorption capacity of original maize straw. The sorption isotherm data of tylosin on original maize straw fit a linear model well, while Freundlich models were more suitable for maize straw modified by manganese oxides and maize straw modified by iron and manganese oxides. The pH, ionic strength and temperature can affect the sorption process. The sorption mechanisms of tylosin on iron and manganese oxides modified maize straw were attribute to the surface complexes, electrostatic interactions, H bonding and hydrophobic interactions. Copyright © 2018 Elsevier Ltd. All rights reserved.
Nanoscale morphological and chemical changes of high voltage lithium-manganese rich NMC composite cathodes with cycling.

PubMed

Yang, Feifei; Liu, Yijin; Martha, Surendra K; Wu, Ziyu; Andrews, Joy C; Ice, Gene E; Pianetta, Piero; Nanda, Jagjit

2014-08-13

Understanding the evolution of chemical composition and morphology of battery materials during electrochemical cycling is fundamental to extending battery cycle life and ensuring safety. This is particularly true for the much debated high energy density (high voltage) lithium-manganese rich cathode material of composition Li(1 + x)M(1 - x)O2 (M = Mn, Co, Ni). In this study we combine full-field transmission X-ray microscopy (TXM) with X-ray absorption near edge structure (XANES) to spatially resolve changes in chemical phase, oxidation state, and morphology within a high voltage cathode having nominal composition Li1.2Mn0.525Ni0.175Co0.1O2. Nanoscale microscopy with chemical/elemental sensitivity provides direct quantitative visualization of the cathode, and insights into failure. Single-pixel (∼ 30 nm) TXM XANES revealed changes in Mn chemistry with cycling, possibly to a spinel conformation and likely including some Mn(II), starting at the particle surface and proceeding inward. Morphological analysis of the particles revealed, with high resolution and statistical sampling, that the majority of particles adopted nonspherical shapes after 200 cycles. Multiple-energy tomography showed a more homogeneous association of transition metals in the pristine particle, which segregate significantly with cycling. Depletion of transition metals at the cathode surface occurs after just one cycle, likely driven by electrochemical reactions at the surface.
Nanoscale Morphological and Chemical Changes of High Voltage Lithium–Manganese Rich NMC Composite Cathodes with Cycling

PubMed Central

2015-01-01

Understanding the evolution of chemical composition and morphology of battery materials during electrochemical cycling is fundamental to extending battery cycle life and ensuring safety. This is particularly true for the much debated high energy density (high voltage) lithium–manganese rich cathode material of composition Li1 + xM1 – xO2 (M = Mn, Co, Ni). In this study we combine full-field transmission X-ray microscopy (TXM) with X-ray absorption near edge structure (XANES) to spatially resolve changes in chemical phase, oxidation state, and morphology within a high voltage cathode having nominal composition Li1.2Mn0.525Ni0.175Co0.1O2. Nanoscale microscopy with chemical/elemental sensitivity provides direct quantitative visualization of the cathode, and insights into failure. Single-pixel (∼30 nm) TXM XANES revealed changes in Mn chemistry with cycling, possibly to a spinel conformation and likely including some Mn(II), starting at the particle surface and proceeding inward. Morphological analysis of the particles revealed, with high resolution and statistical sampling, that the majority of particles adopted nonspherical shapes after 200 cycles. Multiple-energy tomography showed a more homogeneous association of transition metals in the pristine particle, which segregate significantly with cycling. Depletion of transition metals at the cathode surface occurs after just one cycle, likely driven by electrochemical reactions at the surface. PMID:25054780
A Generalizable Multigram Synthesis and Mechanistic Investigation of YMnO 3 Nanoplates

DOE PAGES

McBean, Coray L.; Lewis, Crystal S.; Tiano, Amanda L.; ...

2017-05-05

We present that the reproducible gram-scale synthesis of crystalline nanoscale multiferroics is critical for the development of the next generation of commercially relevant electronic devices. Of the subset of multiferroic materials, yttrium manganese oxide (YMnO 3) is highly attractive, because of its large magneto-electric coupling constants and the recent observation of giant polarization under pressure in these types of rare earth manganites. Utilizing a unique synthetic methodology that combines metal–oleate thermal degradation with the use of a molten salt protocol, we were able to reproducibly generate monodisperse distributions of morphologically distinctive yttrium manganese oxides. Specifically, using a molten NaCl flux,more » we were able to synthesize phase-pure, single-crystalline hexagonal YMnO 3 nanoplates, measuring 441 ± 241 nm in diameter and 46 ± 6 nm in height. Moreover, these nanoplates gave rise to multiferroic behavior, which was confirmed by the observation of a ferroelectric phase from a combination of high-resolution TEM (HRTEM) and selected-area electron diffraction (SAED) analysis. Magnetic measurements are consistent with the onset of a spin glass state below 5 K. To highlight the generalizability of the synthetic method we have developed herein, as a demonstration of principle, we have also successfully used the same protocol to produce nanocubes of lanthanum aluminum oxide (LaAlO 3).« less
75 FR 70665 - Proposed Significant New Use Rule for Cobalt Lithium Manganese Nickel Oxide

Federal Register 2010, 2011, 2012, 2013, 2014

2010-11-18

... Proposed Significant New Use Rule for Cobalt Lithium Manganese Nickel Oxide AGENCY: Environmental... as cobalt lithium manganese nickel oxide (CAS No. 182442-95-1) which was the subject of... section 5(a)(2) of TSCA for the chemical substance identified as cobalt lithium manganese nickel oxide...
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 oxide...
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 oxide...
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 oxide...

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

PubMed

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

2013-05-28

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 Mn(3+)/Mn(4+) 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.
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 the...
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 the...
75 FR 70583 - Cobalt Lithium Manganese Nickel Oxide; Withdrawal of Significant New Use Rule

Federal Register 2010, 2011, 2012, 2013, 2014

2010-11-18

... 2070-AB27 Cobalt Lithium Manganese Nickel Oxide; Withdrawal of Significant New Use Rule AGENCY... chemical substance identified as cobalt lithium manganese nickel oxide (CAS No. 182442-95-1), which was the... lithium manganese nickel oxide (PMN P-04-269; CAS No. 182442-95-1) at 40 CFR 721.10201 because the Agency...
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 the...
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 the...
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 the...
Nanostructured manganese oxide thin films as electrode material for supercapacitors

NASA Astrophysics Data System (ADS)

Xia, Hui; Lai, Man On; Lu, Li

2011-01-01

Electrochemical capacitors, also called supercapacitors, are alternative energy storage devices, particularly for applications requiring high power densities. Recently, manganese oxides have been extensively evaluated as electrode materials for supercapacitors due to their low cost, environmental benignity, and promising supercapacitive performance. In order to maximize the utilization of manganese oxides as the electrode material for the supercapacitors and improve their supercapacitive performance, the nanostructured manganese oxides have therefore been developed. This paper reviews the synthesis of the nanostructured manganese oxide thin films by different methods and the supercapacitive performance of different nanostructures.
Crystal engineering in 3D: Converting nanoscale lamellar manganese oxide to cubic spinel while affixed to a carbon architecture

DOE PAGES

Donakowski, Martin D.; Wallace, Jean M.; Sassin, Megan B.; ...

2016-06-17

Here, by applying differential pair distribution function (DPDF) analyses to the energy–storage relevant MnOx/carbon system— but in a 3D architectural rather than powder–composite configuration—we can remove contributions of the carbon nanofoam paper scaffold and quantify the multiphasic oxide speciation as the nanoscale, disordered MnOx grafted to the carbon walls (MnOx@CNF) structurally rearranges in situ from birnessite AMnOx (A = Na +; Li +) to tetragonal Mn 3O 4 to spinel LiMn 2O 4. The first reaction step involves topotactic exchange of interlayer Na + by Li + in solution followed by thermal treatments to crystal engineer the –10–nm–thick 2D layeredmore » oxide throughout the macroscale nanofoam paper into a spinel phase. The oxide remains affixed to the walls of the nanofoam throughout the phase transformations. The DPDF fits are improved by retention of one plane of birnessite–like oxide after conversion to spinel. We support the DPDF–derived assignments by X–ray photoelectron spectroscopy and Raman spectroscopy, the latter of which tracks how crystal engineering the oxide affects the disorder of the carbon substrate. We further benchmark MnOx@CNF with nonaqueous electrochemical measurements versus lithium as the oxide converts from X–ray–amorphous birnessite to interlayer-registered LiMnOx to spinel. The lamellar AMnOx displays pseudocapacitive electrochemical behavior, with a doubling of specific capacitance for the interlayer–registered LiMnOx, while the spinel LiMn 2O 4@CNF displays a faradaic electrochemical response characteristic of Li–ion insertion. Our results highlight the need for holistic understanding when crystal engineering an (atomistic) charge–storing phase within the (architectural) structure of practical electrodes.« less
40 CFR 721.10010 - Barium manganese oxide (BaMnO3).

Code of Federal Regulations, 2011 CFR

2011-07-01

... 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 P-00... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Barium manganese oxide (BaMnO3). 721...
40 CFR 721.10010 - Barium manganese oxide (BaMnO3).

Code of Federal Regulations, 2010 CFR

2010-07-01

... 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 P-00... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Barium manganese oxide (BaMnO3). 721...
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 P-00...
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 P-00...
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 P-00...
QSAR analysis for nano-sized layered manganese-calcium oxide in water oxidation: An application of chemometric methods in artificial photosynthesis.

PubMed

Shahbazy, Mohammad; Kompany-Zareh, Mohsen; Najafpour, Mohammad Mahdi

2015-11-01

Water oxidation is among the most important reactions in artificial photosynthesis, and nano-sized layered manganese-calcium oxides are efficient catalysts toward this reaction. Herein, a quantitative structure-activity relationship (QSAR) model was constructed to predict the catalytic activities of twenty manganese-calcium oxides toward water oxidation using multiple linear regression (MLR) and genetic algorithm (GA) for multivariate calibration and feature selection, respectively. Although there are eight controlled parameters during synthesizing of the desired catalysts including ripening time, temperature, manganese content, calcium content, potassium content, the ratio of calcium:manganese, the average manganese oxidation state and the surface of catalyst, by using GA only three of them (potassium content, the ratio of calcium:manganese and the average manganese oxidation state) were selected as the most effective parameters on catalytic activities of these compounds. The model's accuracy criteria such as R(2)test and Q(2)test in order to predict catalytic rate for external test set experiments; were equal to 0.941 and 0.906, respectively. Therefore, model reveals acceptable capability to anticipate the catalytic activity. Copyright © 2015 Elsevier B.V. All rights reserved.
Photoinduced oxidation of a water-soluble manganese(III) porphyrin

PubMed Central

Maliyackel, Anthony C.; Otvos, John W.; Spreer, Larry O.; Calvin, Melvin

1986-01-01

The photoinduced oxidation of tetra(N-methyl-4-pyridyl)porphyrinmanganese(III) has been achieved in homogeneous solution. The manganese porphyrin was used as an electron donor in a three-component system with tris-(2,2′-bipyridine)ruthenium(II) as the photosensitizer and chloropentaamminecobalt(III) as the electron acceptor. The photooxidized manganese porphyrin is unstable in aqueous solution, reverting to the starting manganese(III) porphyrin. The oxidation of manganese(III) porphyrin and the subsequent reduction of the oxidized porphyrin can be cycled repeatedly. PMID:16593699
Influence of oxalic acid on the dissolution kinetics of manganese oxide

NASA Astrophysics Data System (ADS)

Godunov, E. B.; Artamonova, I. V.; Gorichev, I. G.; Lainer, Yu. A.

2012-11-01

The kinetics and electrochemical processes of the dissolution of manganese oxides with various oxidation states in sulfuric acid solutions containing oxalate ion additives is studied under variable conditions (concentration, pH, temperature). The parameters favoring a higher degree of the dissolution of manganese oxides in acidic media are determined. The optimal conditions are found for the dissolution of manganese oxides in acidic media in the presence of oxalate ions. The mechanism proposed for the dissolution of manganese oxides in sulfuric acid solutions containing oxalic acid is based on the results of kinetic and electrochemical studies. The steps of the dissolution mechanism are discussed.

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

Code of Federal Regulations, 2012 CFR

2012-07-01

... manganese strontium oxide (PMN P-00-1124; CAS No. 359427-90-0) is subject to reporting under this section... 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...
40 CFR 721.10011 - Barium calcium manganese strontium oxide.

Code of Federal Regulations, 2013 CFR

2013-07-01

... manganese strontium oxide (PMN P-00-1124; CAS No. 359427-90-0) is subject to reporting under this section... 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...
40 CFR 721.10011 - Barium calcium manganese strontium oxide.

Code of Federal Regulations, 2014 CFR

2014-07-01

... manganese strontium oxide (PMN P-00-1124; CAS No. 359427-90-0) is subject to reporting under this section... 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...
Manganese Health Research Program (MHRP)

DTIC Science & Technology

2008-01-01

NO3)2 Manganese sulphate or Manganese (II) sulphate – MnSO4 Manganese sulphide or Manganese (II) sulphide – MnS Manganese oxide – MnO Barium... sulphide or Manganese (II) sulphide – MnS 1344-43-0 Manganese oxide – MnO 7787-35-1 Barium manganate - BaMnO4 10294-64-1 Potassium manganate – K2MnO4...Characterization of welding fumes and their potential neurotoxic effects. International Workshop: Neurotoxic Metals- Lead, Mercury , and Manganese
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.
Bioturbation and Manganese Cycling in Hemipelagic Sediments

NASA Astrophysics Data System (ADS)

Aller, R. C.

1990-06-01

The activities of infaunal macrobenthos have major influences on the types, rates and distributions of diagenetic reactions involving manganese in relatively carbon-rich deep-sea and nearshore sediments. In some non-sulphidic hemipelagic deposits of the eastern equatorial Pacific (Panama Basin) biogenic reworking drives internal cycles of manganese, which can apparently account for up to ca. 100% of organic carbon oxidation and reduction of O2 supplied (diffusively) to the sea floor. Heterotrophic (carbon-based) manganese reduction is stimulated by simultaneous mixing of reactive organic matter and manganese oxide into suboxic-anoxic deposits. In sulphidic sediments, biogenic reworking must also enhance a lithotrophic pathway (sulphur-based) pathway of manganese reduction by promoting contact of manganese oxides and iron sulphides. Particle reworking dramatically alters the balance between aerobic and anaerobic decomposition pathways, promoting the utilization of O2 in the reoxidaton of reduced metabolites rather than direct oxidation of carbon. Irrigated burrows create microenvironments, which increase manganese reduction-oxidation and deplete Mn2+ from deeper pore waters. This may increase net Mn2+ production rates by removal of metabolites and potential co-precipitants with Mn2+. The occurrence and geometry of manganese oxide encrusted biogenic structures imply specific adaptations of infauna to manganese based microbial activity in hemipelagic sediments like the Panama Basin.
Reduction in the Band Gap of Manganese-Doped Zinc Oxide: Role of the Oxidation State

NASA Astrophysics Data System (ADS)

Sharma, Sonia; Ramesh, Pranith; Swaminathan, P.

2015-12-01

Manganese-doped zinc oxide powders were synthesized by solid state reaction of the respective oxides. The high-temperature conditions were chosen such that multiple valence states of manganese were doped in the host zinc oxide lattice. Structural characterization was carried out to confirm the doping and to find the maximum amount of manganese that can be incorporated. Diffuse reflectance spectroscopy was used to measure the optical band gap of the doped sample and the lowering with respect to pure ZnO was attributed to the presence of higher oxidation states of manganese. The presence of these oxidation states was confirmed using x-ray photoelectron spectroscopy. The study shows that a solid state reaction is a viable route for synthesizing doped metal oxides with desired optical properties.
76 FR 47996 - Cobalt Lithium Manganese Nickel Oxide; Significant New Use Rule

Federal Register 2010, 2011, 2012, 2013, 2014

2011-08-08

... 2070-AB27 Cobalt Lithium Manganese Nickel Oxide; Significant New Use Rule AGENCY: Environmental... lithium manganese nickel oxide (CAS No. 182442-95-1), which was the subject of premanufacture notice (PMN... 5(a)(2) (15 U.S.C. 2604(a)(2)) for the chemical substance identified as cobalt lithium manganese...
Three manganese oxide-rich marine sediments harbor similar communities of acetate-oxidizing manganese-reducing bacteria

PubMed Central

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

2012-01-01

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 106 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
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.
Efficient determination of average valence of manganese in manganese oxides by reaction headspace gas chromatography.

PubMed

Xie, Wei-Qi; Gong, Yi-Xian; Yu, Kong-Xian

2017-08-18

This work investigates a new reaction headspace gas chromatographic (HS-GC) technique for efficient quantifying average valence of manganese (Mn) in manganese oxides. This method is on the basis of the oxidation reaction between manganese oxides and sodium oxalate under the acidic condition. The carbon dioxide (CO 2 ) formed from the oxidation reaction can be quantitatively analyzed by headspace gas chromatography. The data showed that the reaction in the closed headspace vial can be completed in 20min at 80°C. The relative standard deviation of this reaction HS-GC method in the precision testing was within 1.08%, the relative differences between the new method and the reference method (titration method) were no more than 5.71%. The new HS-GC method is automated, efficient, and can be a reliable tool for the quantitative analysis of average valence of manganese in the manganese oxide related research and applications. Copyright © 2017 Elsevier B.V. All rights reserved.
Structural and surface changes of cobalt modified manganese oxide during activation and ethanol steam reforming reaction

NASA Astrophysics Data System (ADS)

Gac, Wojciech; Greluk, Magdalena; Słowik, Grzegorz; Turczyniak-Surdacka, Sylwia

2018-05-01

Surface and structural changes of unmodified manganese and cobalt-manganese oxide during activation and ethanol steam reforming reaction conditions (ESR) were studied by means of X-ray diffraction, X-ray photoelectron spectroscopy, temperature-programmed reduction/oxidation (TPR/TPO) and transmission electron microscopy. It was shown that synthesis of cobalt manganese oxide by the redox precipitation method led to the formation of strongly dispersed cobalt ionic species within cryptomelane-based manganese oxide structure. Development of large cube-like MnO nanoparticles with spherical cobalt metallic crystallites decorated by manganese oxide on the high oxidation state and potassium species was observed during reduction. Cobalt manganese catalyst showed high initial activity and selectivity to H2 and CO2 in ethanol stem reforming reaction in the range of 390-480 °C. The drop of ethanol conversion and changes of selectivity with the time-on-stream were observed. An increase of reaction temperature led to intensification of deactivation phenomena. TEM studies evidenced coexistence of Co and CoOx nanoparticles formed under ethanol steam reforming conditions, partially covered by filamentous and encapsulating carbonaceous deposits.
DOE Office of Scientific and Technical Information (OSTI.GOV)

Jun, Young -Shin; Kim, Doyoon; Neil, Chelsea W.

Here, mineral nucleation is a phase transformation of aqueous components to solids with an accompanying creation of new surfaces. In this evolutional, yet elusive, process, nuclei often form at environmental interfaces, which provide remarkably reactive sites for heterogeneous nucleation and growth. Naturally occurring nucleation processes significantly contribute to the biogeochemical cycles of important components in the Earth’s crust, such as iron and manganese oxide minerals and calcium carbonate. However, in recent decades, these cycles have been significantly altered by anthropogenic activities, which affect the aqueous chemistry and equilibrium of both surface and subsurface systems. These alterations can trigger the dissolutionmore » of existing minerals and formation of new nanoparticles (i.e., nucleation and growth) and consequently change the porosity and permeability of geomedia in subsurface environments. Newly formed nanoparticles can also actively interact with components in natural and engineered aquatic systems, including those posing a significant hazard such as arsenic. These interactions can bilaterally influence the fate and transport of both newly formed nanoparticles and aqueous components. Due to their importance in natural and engineered processes, heterogeneous nucleation at environmental interfaces has started to receive more attention. However, a lack of time-resolved in situ analyses makes the evaluation of heterogeneous nucleation challenging because the physicochemical properties of both the nuclei and surfaces significantly and dynamically change with time and aqueous chemistry. This Account reviews our in situ kinetic studies of the heterogeneous nucleation and growth behaviors of iron(III) (hydr)oxide, calcium carbonate, and manganese (hydr)oxide minerals in aqueous systems. In particular, we utilized simultaneous small-angle and grazing incidence small-angle X-ray scattering (SAXS/GISAXS) to investigate in situ and in real-time the effects of water chemistry and substrate identity on heterogeneously and homogeneously formed nanoscale precipitate size dimensions and total particle volume. Using this technique, we also provided a new platform for quantitatively comparing between heterogeneous and homogeneous nucleation and growth of nanoparticles and obtaining undiscovered interfacial energies between nuclei and surfaces. In addition, nanoscale surface characterization tools, such as in situ atomic force microscopy (AFM), were utilized to support and complement our findings. With these powerful nanoscale tools, we systematically evaluated the influences of environmentally abundant (oxy)anions and cations and the properties of environmental surfaces, such as surface charge and hydrophobicity. The findings, significantly enhanced by in situ observations, can lead to a more accurate prediction of the behaviors of nanoparticles in the environment and enable better control of the physicochemical properties of nanoparticles in engineered systems, such as catalytic reactions and energy storage.« less
Heterogeneous nucleation and growth of nanoparticles at environmental interfaces

DOE PAGES

Jun, Young -Shin; Kim, Doyoon; Neil, Chelsea W.

2016-08-11

Here, mineral nucleation is a phase transformation of aqueous components to solids with an accompanying creation of new surfaces. In this evolutional, yet elusive, process, nuclei often form at environmental interfaces, which provide remarkably reactive sites for heterogeneous nucleation and growth. Naturally occurring nucleation processes significantly contribute to the biogeochemical cycles of important components in the Earth’s crust, such as iron and manganese oxide minerals and calcium carbonate. However, in recent decades, these cycles have been significantly altered by anthropogenic activities, which affect the aqueous chemistry and equilibrium of both surface and subsurface systems. These alterations can trigger the dissolutionmore » of existing minerals and formation of new nanoparticles (i.e., nucleation and growth) and consequently change the porosity and permeability of geomedia in subsurface environments. Newly formed nanoparticles can also actively interact with components in natural and engineered aquatic systems, including those posing a significant hazard such as arsenic. These interactions can bilaterally influence the fate and transport of both newly formed nanoparticles and aqueous components. Due to their importance in natural and engineered processes, heterogeneous nucleation at environmental interfaces has started to receive more attention. However, a lack of time-resolved in situ analyses makes the evaluation of heterogeneous nucleation challenging because the physicochemical properties of both the nuclei and surfaces significantly and dynamically change with time and aqueous chemistry. This Account reviews our in situ kinetic studies of the heterogeneous nucleation and growth behaviors of iron(III) (hydr)oxide, calcium carbonate, and manganese (hydr)oxide minerals in aqueous systems. In particular, we utilized simultaneous small-angle and grazing incidence small-angle X-ray scattering (SAXS/GISAXS) to investigate in situ and in real-time the effects of water chemistry and substrate identity on heterogeneously and homogeneously formed nanoscale precipitate size dimensions and total particle volume. Using this technique, we also provided a new platform for quantitatively comparing between heterogeneous and homogeneous nucleation and growth of nanoparticles and obtaining undiscovered interfacial energies between nuclei and surfaces. In addition, nanoscale surface characterization tools, such as in situ atomic force microscopy (AFM), were utilized to support and complement our findings. With these powerful nanoscale tools, we systematically evaluated the influences of environmentally abundant (oxy)anions and cations and the properties of environmental surfaces, such as surface charge and hydrophobicity. The findings, significantly enhanced by in situ observations, can lead to a more accurate prediction of the behaviors of nanoparticles in the environment and enable better control of the physicochemical properties of nanoparticles in engineered systems, such as catalytic reactions and energy storage.« less
Heterogeneous Nucleation and Growth of Nanoparticles at Environmental Interfaces.

PubMed

Jun, Young-Shin; Kim, Doyoon; Neil, Chelsea W

2016-09-20

Mineral nucleation is a phase transformation of aqueous components to solids with an accompanying creation of new surfaces. In this evolutional, yet elusive, process, nuclei often form at environmental interfaces, which provide remarkably reactive sites for heterogeneous nucleation and growth. Naturally occurring nucleation processes significantly contribute to the biogeochemical cycles of important components in the Earth's crust, such as iron and manganese oxide minerals and calcium carbonate. However, in recent decades, these cycles have been significantly altered by anthropogenic activities, which affect the aqueous chemistry and equilibrium of both surface and subsurface systems. These alterations can trigger the dissolution of existing minerals and formation of new nanoparticles (i.e., nucleation and growth) and consequently change the porosity and permeability of geomedia in subsurface environments. Newly formed nanoparticles can also actively interact with components in natural and engineered aquatic systems, including those posing a significant hazard such as arsenic. These interactions can bilaterally influence the fate and transport of both newly formed nanoparticles and aqueous components. Due to their importance in natural and engineered processes, heterogeneous nucleation at environmental interfaces has started to receive more attention. However, a lack of time-resolved in situ analyses makes the evaluation of heterogeneous nucleation challenging because the physicochemical properties of both the nuclei and surfaces significantly and dynamically change with time and aqueous chemistry. This Account reviews our in situ kinetic studies of the heterogeneous nucleation and growth behaviors of iron(III) (hydr)oxide, calcium carbonate, and manganese (hydr)oxide minerals in aqueous systems. In particular, we utilized simultaneous small-angle and grazing incidence small-angle X-ray scattering (SAXS/GISAXS) to investigate in situ and in real-time the effects of water chemistry and substrate identity on heterogeneously and homogeneously formed nanoscale precipitate size dimensions and total particle volume. Using this technique, we also provided a new platform for quantitatively comparing between heterogeneous and homogeneous nucleation and growth of nanoparticles and obtaining undiscovered interfacial energies between nuclei and surfaces. In addition, nanoscale surface characterization tools, such as in situ atomic force microscopy (AFM), were utilized to support and complement our findings. With these powerful nanoscale tools, we systematically evaluated the influences of environmentally abundant (oxy)anions and cations and the properties of environmental surfaces, such as surface charge and hydrophobicity. The findings, significantly enhanced by in situ observations, can lead to a more accurate prediction of the behaviors of nanoparticles in the environment and enable better control of the physicochemical properties of nanoparticles in engineered systems, such as catalytic reactions and energy storage.
Controllable Synthesis of Formaldehyde Modified Manganese Oxide Based on Gas-Liquid Interfacial Reaction and Its Application of Electrochemical Sensing.

PubMed

Bai, Wushuang; Sheng, Qinglin; Nie, Fei; Zheng, Jianbin

2015-12-30

Controllable synthesis of manganese oxides was performed via a simple one-step synthetic method. Then obtained manganese oxides which exhibit flower-like, cloud-like, hexagon-like, and rod-like morphologies were modified by formaldehyde based on a simple self-made gas-liquid reaction device respectively and the modified manganese oxides with coral-like, scallop-like and rod-like morphology were synthesized accordingly. The obtained materials were characterized and the formation mechanism was also researched. Then the modified manganese oxides were used to fabricate electrochemical sensors to detect H2O2. Comparison of electrochemical properties between three kinds of modified manganese oxides was investigated and the best one has been successfully employed as H2O2 sensor which shows a low detection limit of 0.01 μM, high sensitivity of 162.69 μA mM(-1) cm(-2), and wide linear range of 0.05 μM-12.78 mM. The study provides a new method for controllable synthesis of metal oxides, and electrochemical application of formaldehyde modified manganese oxides will provides a new strategy for electrochemical sensing with high performance, low cost, and simple fabrication.
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

Recovery of manganese from manganese oxide ores in the EDTA solution

NASA Astrophysics Data System (ADS)

Zhang, Chao; Wang, Shuai; Cao, Zhan-fang; Zhong, Hong

2018-04-01

A new process has been experimentally and theoretically established for the recovery of manganese from manganese oxide ores, mainly including the reductive leaching of manganese by ethylenediaminetetraacetic acid (EDTA), EDTA recovery, and manganese electrolysis. The experimental conditions for this process were investigated. Moderate leaching environment by EDTA with the pH in the range of 5-6 is of benefit to leach manganese from some manganese oxide ores with high-content impurities, such as iron and aluminum. Most of EDTA can be recovered by acidification. A small amount of the residual EDTA in the electrolyte can prevent the generation of anode mud. In addition, trimanganese tetroxide (Mn3O4) can be obtained by the roasting of the EDTA-Mn crystallized product.
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.
Beta-manganese dioxide nanorods for sufficient high-temperature electromagnetic interference shielding in X-band

NASA Astrophysics Data System (ADS)

Song, Wei-Li; Cao, Mao-Sheng; Hou, Zhi-Ling; Lu, Ming-Ming; Wang, Chan-Yuan; Yuan, Jie; Fan, Li-Zhen

2014-09-01

As the development of electronic and communication technology, electromagnetic interference (EMI) shielding and attenuation is an effective strategy to ensure the operation of the electronic devices. Among the materials for high-performance shielding in aerospace industry and related high-temperature working environment, the thermally stable metal oxide semiconductors with narrow band gap are promising candidates. In this work, beta-manganese dioxide ( β-MnO2) nanorods were synthesized by a hydrothermal method. The bulk materials of the β-MnO2 were fabricated to evaluate the EMI shielding performance in the temperature range of 20-500 °C between 8.2 and 12.4 GHz (X-band). To understand the mechanisms of high-temperature EMI shielding, the contribution of reflection and absorption to EMI shielding was discussed based on temperature-dependent electrical properties and complex permittivity. Highly sufficient shielding effectiveness greater than 20 dB was observed over all the investigated range, suggesting β-MnO2 nanorods as promising candidates for high-temperature EMI shielding. The results have also established a platform to develop high-temperature EMI shielding materials based on nanoscale semiconductors.
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 (1
Manganese oxide-based materials as electrochemical supercapacitor electrodes.

PubMed

Wei, Weifeng; Cui, Xinwei; Chen, Weixing; Ivey, Douglas G

2011-03-01

Electrochemical supercapacitors (ECs), characteristic of high power and reasonably high energy densities, have become a versatile solution to various emerging energy applications. This critical review describes some materials science aspects on manganese oxide-based materials for these applications, primarily including the strategic design and fabrication of these electrode materials. Nanostructurization, chemical modification and incorporation with high surface area, conductive nanoarchitectures are the three major strategies in the development of high-performance manganese oxide-based electrodes for EC applications. Numerous works reviewed herein have shown enhanced electrochemical performance in the manganese oxide-based electrode materials. However, many fundamental questions remain unanswered, particularly with respect to characterization and understanding of electron transfer and atomic transport of the electrochemical interface processes within the manganese oxide-based electrodes. In order to fully exploit the potential of manganese oxide-based electrode materials, an unambiguous appreciation of these basic questions and optimization of synthesis parameters and material properties are critical for the further development of EC devices (233 references).
Timing of Neogene Manganese Deposit Formation in the Paleo-Japan Sea, northeast Japan

NASA Astrophysics Data System (ADS)

Ito, T.; Orihashi, Y.; Yanagisawa, Y.; Sakai, S.; Motoyama, I.; Kamikuri, S. I.; Komuro, K.; Suzuki, K.

2017-12-01

The generation ages of the two Neogene manganese deposits in northeast Japan were determined by diatom and radiolarian biostratigraphic analyses and zircon U-Pb dating. The manganese deposits analyzed were from the Kitaichi and Maruyama mines in the Fukaura district, northeast Japan. Manganese oxide layers of 0.5 m (Kitaichi) and 1.5 m (Maruyama) in thickness were predominantly composed of todorokite and occur conformably within volcanogenic sediments, which stratigraphically had correlated to middle Miocene in previous studies. The ages of the manganese oxide layers were 12.4 Ma. There was no time gap between the Kitaichi and the Maruyama manganese oxide layers, between the manganese oxide layer and the underlying tuffaceous sandstone in the Kitaichi mine, or within the manganese oxide layer of ca. 1.5 m thickness in the Maruyama mine. On the other hand, the overlying tuffaceous sandstone was dated at 4.5 Ma. The results suggest that the manganese oxide layers were formed immediately after the deposition of the tuffaceous sandstone at 12.4 Ma and that the restricted supply of volcanogenic and/or other detrital matter had kept for a long time (ca. 7 m.y.). The timing of the manganese deposit generation, 12.4 Ma, is identical to the age of the base of the Onnagawa Stage on the Nishikurosawa Stage in the Neogene stratotype section on the Japan Sea side, northeast Japan. And this is equivalent to the age of the start of diatom blooming. Paleogeographically, the manganese oxide deposition happened in a shallower area on a paleo-hill or a small island surrounded by stagnant mid to deep basins with diatom and organically carbon-rich, laminated, and fine-grained mud. It is highly probable that upwelling of mid to deep water rich in both dissolved manganese and nutrients is the trigger for the manganese deposit generation in shallower areas and the deposition of diatomaceous sediments in mid and deep basins. Eustatic regression might be the reason for the short-term formation of manganese deposits in shallower areas compared to continuous sedimentation ( several million years) of diatomaceous and organic carbon-rich mud in the surrounding mid to deep basins.
Metal Doped Manganese Oxide Thin Films for Supercapacitor Application.

PubMed

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

2015-09-01

Co and Fe doped manganese oxide thin films were prepared by anodic deposition at current density of 50 mA cm(-2) using the electrolyte containing manganese sulfate and either cobalt sulfate or ferrous sulfate. Surface morphology and crystal structure of oxides were studied by scanning electron microscope (SEM) and X-ray diffraction (XRD). Chemical composition of materials was analyzed by X-ray energy dispersive spectroscope (EDS), iodometric titration method and complexometric titration method, respectively. Supercapacitive behavior of Co and Fe doped manganese oxide films were characterized by cyclic voltammetry (CV) and impedance spectroscopy (EIS). The results show that the doped manganese oxides are composed of nano fiber-like structure with radius of 5-20 nm and remain amorphous structure after heat treatment at 100 degrees C for 2 hours. The average valence of manganese increases from +3.808 to +3.867 after doping Co and from +3.808 to +3.846 after doping Fe. The doped manganese oxide film electrodes exhibited preferably ideal pseudo-capacitive behavior. The specific capacitance value of deposited manganese oxide reaches a maximum of 175.3 F/g for doping Co and 244.6 F/g for doping Fe. The thin films retained about 84% of the initial capacity even after 500 cycles of charge-discharge test. Doping Co and Fe decreases diffusion and charge transfer resistance of the films. The electric double layer capacitance and capacitor response frequency are increased after doping.
Tellurium content of marine manganese oxides and other manganese oxides

USGS Publications Warehouse

Lakin, H.W.; Thompson, C.E.; Davidson, D.F.

1963-01-01

Tellurium in amounts ranging from 5 to 125 parts per million was present in all of 12 samples of manganese oxide nodules from the floor of the Pacific and Indian oceans. These samples represent the first recognized points of high tellurium concentration in a sedimentary cycle. The analyses may lend support to the theory that the minor-element content of seafloor manganese nodules is derived from volcanic emanations.
Highly Conductive One-Dimensional Manganese Oxide Wires by Coating with Graphene Oxides

NASA Astrophysics Data System (ADS)

Tojo, Tomohiro; Shinohara, Masaki; Fujisawa, Kazunori; Muramatsu, Hiroyuki; Hayashi, Takuya; Ahm Kim, Yoong; Endo, Morinobu

2012-10-01

Through coating with graphene oxides, we have developed a chemical route to the bulk production of long, thin manganese oxide (MnO2) nanowires that have high electrical conductivity. The average diameter of these hybrid nanowires is about 25 nm, and their average length is about 800 nm. The high electrical conductivity of these nanowires (ca. 189.51+/-4.51 µS) is ascribed to the homogeneous coating with conductive graphene oxides as well as the presence of non-bonding manganese atoms. The growth mechanism of the nanowires is theoretically supported by the initiation of morphological conversion from graphene oxide to wrapped structures through the formation of covalent bonds between manganese and oxygen atoms at the graphene oxide edge.
Electrodeposition of Manganese-Nickel Oxide Films on a Graphite Sheet for Electrochemical Capacitor Applications.

PubMed

Lee, Hae-Min; Lee, Kangtaek; Kim, Chang-Koo

2014-01-09

Manganese-nickel (Mn-Ni) oxide films were electrodeposited on a graphite sheet in a bath consisting of manganese acetate and nickel chloride, and the structural, morphological, and electrochemical properties of these films were investigated. The electrodeposited Mn-Ni oxide films had porous structures covered with nanofibers. The X-ray diffractometer pattern revealed the presence of separate manganese oxide (g-MnO₂) and nickel oxide (NiO) in the films. The electrodeposited Mn-Ni oxide electrode exhibited a specific capacitance of 424 F/g in Na₂SO₄ electrolyte. This electrode maintained 86% of its initial specific capacitance over 2000 cycles of the charge-discharge operation, showing good cycling stability.
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 darkening of water and plugging of pipes in drinking or industrial water systems. Soluble manganese can be removed from water by biological processes involving manganese-oxidizing bacteria, either in situ, or in sand filters after pumping. Various procedures are mentioned.
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...
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.
Sorbent for use in hot gas desulfurization

DOEpatents

Gasper-Galvin, Lee D.; Atimtay, Aysel T.

1993-01-01

A multiple metal oxide sorbent supported on a zeolite of substantially silicon oxide is used for the desulfurization of process gas streams, such as from a coal gasifier, at temperatures in the range of about 1200.degree. to about 1600.degree. F. The sorbent is provided by a mixture of copper oxide and manganese oxide and preferably such a mixture with molybdenum oxide. The manganese oxide and the molybdenum are believed to function as promoters for the reaction of hydrogen sulfide with copper oxide. Also, the manganese oxide inhibits the volatilization of the molybdenum oxide at the higher temperatures.
Corrosion-induced release of the main alloying constituents of manganese-chromium stainless steels in different media.

PubMed

Herting, Gunilla; Wallinder, Inger Odnevall; Leygraf, Christofer

2008-09-01

The main focus of this paper is the assessment of release rates of chromium, nickel, iron and manganese from manganese-chromium stainless steel grades of low nickel content. The manganese content varied between 9.7 and 1.5 wt% and the corresponding nickel content between 1 and 5 wt%. All grades were exposed to artificial rain and two were immersed in a synthetic body fluid of similar pH but of different composition and exposure conditions. Surface compositional studies were performed using X-ray photoelectron spectroscopy (XPS) in parallel to correlate the metal release process with changes in surface oxide properties. All grades, independent of media, revealed a time-dependent metal release process with a preferential low release of iron and manganese compared to nickel and chromium while the chromium content of the surface oxide increased slightly. Manganese was detected in the surface oxide of all grades, except the grade of the lowest manganese bulk content. No nickel was observed in the outermost surface oxide. Stainless steel grades of the lowest chromium content (approximately 16 wt%) and highest manganese content (approximately 7-9 wt%), released the highest quantity of alloy constituents in total, and vice versa. No correlation was observed between the release rate of manganese and the alloy composition. Released main alloy constituents were neither proportional to the bulk alloy composition nor to the surface oxide composition.
Electrosynthesis of Biomimetic Manganese-Calcium Oxides for Water Oxidation Catalysis--Atomic Structure and Functionality.

PubMed

González-Flores, Diego; Zaharieva, Ivelina; Heidkamp, Jonathan; Chernev, Petko; Martínez-Moreno, Elías; Pasquini, Chiara; Mohammadi, Mohammad Reza; Klingan, Katharina; Gernet, Ulrich; Fischer, Anna; Dau, Holger

2016-02-19

Water-oxidizing calcium-manganese oxides, which mimic the inorganic core of the biological catalyst, were synthesized and structurally characterized by X-ray absorption spectroscopy at the manganese and calcium K edges. The amorphous, birnesite-type oxides are obtained through a simple protocol that involves electrodeposition followed by active-site creation through annealing at moderate temperatures. Calcium ions are inessential, but tune the electrocatalytic properties. For increasing calcium/manganese molar ratios, both Tafel slopes and exchange current densities decrease gradually, resulting in optimal catalytic performance at calcium/manganese molar ratios of close to 10 %. Tracking UV/Vis absorption changes during electrochemical operation suggests that inactive oxides reach their highest, all-Mn(IV) oxidation state at comparably low electrode potentials. The ability to undergo redox transitions and the presence of a minor fraction of Mn(III) ions at catalytic potentials is identified as a prerequisite for catalytic activity. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Amorphous manganese-calcium oxides as a possible evolutionary origin for the CaMn₄ cluster in photosystem II.

PubMed

Najafpour, Mohammad Mahdi

2011-06-01

In this paper a few calcium-manganese oxides and calcium-manganese minerals are studied as catalysts for water oxidation. The natural mineral marokite is also studied as a catalyst for water oxidation for the first time. Marokite is made up of edge-sharing Mn(3+) in a distorted octahedral environment and eight-coordinate Ca(2+) centered polyhedral layers. The structure is similar to recent models of the oxygen evolving complex in photosystem II. Thus, the oxygen evolving complex in photosystem II does not have an unusual structure and could be synthesized hydrothermally. Also in this paper, oxygen evolution is studied with marokite (CaMn₂O₄), pyrolusite (MnO₂) and compared with hollandite (Ba(0.2)Ca(0.15)K(0.3)Mn(6.9)Al(0.2)Si(0.3)O(16)), hausmannite (Mn₃O₄), Mn₂O₃.H₂O, Ca Mn₃O₆.H₂O, CaMn₄O₈.H₂O, CaMn₂O₄.H₂O and synthetic marokite (CaMn₂O₄). I propose that the origin of the oxygen evolving complex in photosystem II resulted from absorption of calcium and manganese ions that were precipitated together in the archean oceans by protocyanobacteria because of changing pH from ~5 to ~8-10. As reported in this paper, amorphous calcium-manganese oxides with different ratios of manganese and calcium are effective catalysts for water oxidation. The bond types and lengths of the calcium and manganese ions in the calcium-manganese oxides are directly comparable to those in the OEC. This primitive structure of these amorphous calcium-manganese compounds could be changed and modified by environmental groups (amino acids) to form the oxygen evolving complex in photosystem II.
Solid state microwave synthesis of highly crystalline ordered mesoporous hausmannite Mn 3 O 4 films

DOE PAGES

Xia, Yanfeng; Qiang, Zhe; Lee, Byeongdu; ...

2017-06-23

Microwave calcination of ordered micelle templated manganese carbonate films leads to highly crystalline, ordered mesoporous manganese oxide, while similar temperatures in a furnace lead to disordered, amorphous manganese oxide.
The role of electronic and ionic conductivities in the rate performance of tunnel structured manganese oxides in Li-ion batteries

DOE PAGES

Byles, B. W.; Palapati, N. K. R.; Subramanian, A.; ...

2016-04-29

Single nanowires of two manganese oxide polymorphs (α-MnO 2 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-MnO 2 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-MnO 2, the todorokite manganese oxide exhibited better electrochemical rate performance as a Li-ion battery cathode. The relationship between thismore » 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. 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
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.

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

PubMed

Birkner, Nancy; Navrotsky, Alexandra

2014-04-29

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.
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 +]…
Effect of mass density on surface morphology of electrodeposited manganese oxide films

NASA Astrophysics Data System (ADS)

Singh, Avtar; Kumar, Davinder; Thakur, Anup; Kaur, Raminder

2018-05-01

This work focus on high surface area morphology of manganese oxide films which are currently required for electrochemical capacitor electrode to enhance their performance. Electrodeposition of manganese oxide films was carried out using Chronoamperometry for different deposition time ranging from 30 to 120 sec. Cronoamperomertic I-T integrated data have been used to analyze active mass of all electrodeposited films. Morphological study of the deposited films with different mass was carried out through scanning electron microscopy. Film deposited for 30 sec time show highest porous morphology than others. Manganese oxide films with high porosity are suitable for electrochemical capacitor electrode.
Calcium manganese oxides as oxygen evolution catalysts: O2 formation pathways indicated by 18O-labelling studies.

PubMed

Shevela, Dmitriy; Koroidov, Sergey; Najafpour, M Mahdi; Messinger, Johannes; Kurz, Philipp

2011-05-02

Oxygen evolution catalysed by calcium manganese and manganese-only oxides was studied in (18)O-enriched water. Using membrane-inlet mass spectrometry, we monitored the formation of the different O(2) isotopologues (16)O(2), (16)O(18)O and (18)O(2) in such reactions simultaneously with good time resolution. From the analysis of the data, we conclude that entirely different pathways of dioxygen formation catalysis exist for reactions involving hydrogen peroxide (H(2)O(2)), hydrogen persulfate (HSO(5)(-)) or single-electron oxidants such as Ce(IV) and [Ru(III) (bipy)(3)](3+) . Like the studied oxide catalysts, the active sites of manganese catalase and the oxygen-evolving complex (OEC) of photosystem II (PSII) consist of μ-oxido manganese or μ-oxido calcium manganese sites. The studied processes show very similar (18)O-labelling behaviour to the natural enzymes and are therefore interesting model systems for in vivo oxygen formation by manganese metalloenzymes such as PSII. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Permanganate ion oxidations. IX. Manganese intermediates (complexes) in the oxidation of 2,4(1H,3H)-pyrimidinediones.

PubMed

Freeman, F; Karchefski, E M

1976-10-04

Uniquely stable manganese intermediates (complexes) are formed from the permanganate ion oxidation of the 5,6-carbon-carbon double bond in several 2,4(1H,3H)-pyrimidinediones [uracil, (compound 7), 5-methyluracil (thymine, compound 5), and 6-methyluracil (compound 8)]. These manganese complexes, which represent some of the most stable intermediate manganese species observed thus far in the oxidation of carbon-carbon double bonds, show absorption maxima in the 285-296 nm region (epsilon max approximately 4500). The relative reactivities of 6-methyluracil: uracil: thymine are 1: 23 : 194 and the bimolecular oxidation process is characterized by relatively small deltaH++ values and large negative deltaS++ values.
Manganese oxide nanoparticles, methods and applications

DOEpatents

Abruna, Hector D.; Gao, Jie; Lowe, Michael A.

2017-08-29

Manganese oxide nanoparticles having a chemical composition that includes Mn.sub.3O.sub.4, a sponge like morphology and a particle size from about 65 to about 95 nanometers may be formed by calcining a manganese hydroxide material at a temperature from about 200 to about 400 degrees centigrade for a time period from about 1 to about 20 hours in an oxygen containing environment. The particular manganese oxide nanoparticles with the foregoing physical features may be used within a battery component, and in particular an anode within a lithium battery to provide enhanced performance.
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.
21 CFR 582.80 - Trace minerals added to animal feeds.

Code of Federal Regulations, 2011 CFR

2011-04-01

.... Manganese phosphate (dibasic). Manganese sulfate. Manganous oxide. Zinc Zinc acetate. Zinc carbonate. Zinc chloride. Zinc oxide. Zinc sulfate. ... Cobalt Cobalt acetate. Cobalt carbonate. Cobalt chloride. Cobalt oxide. Cobalt sulfate. Copper Copper...
21 CFR 582.80 - Trace minerals added to animal feeds.

Code of Federal Regulations, 2010 CFR

2010-04-01

.... Manganese phosphate (dibasic). Manganese sulfate. Manganous oxide. Zinc Zinc acetate. Zinc carbonate. Zinc chloride. Zinc oxide. Zinc sulfate. ... Cobalt Cobalt acetate. Cobalt carbonate. Cobalt chloride. Cobalt oxide. Cobalt sulfate. Copper Copper...
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 calcium...
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 calcium...
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
Nano-structured manganese oxide as a cathodic catalyst for enhanced oxygen reduction in a microbial fuel cell fed with a synthetic wastewater.

PubMed

Liu, Xian-Wei; Sun, Xue-Fei; Huang, Yu-Xi; Sheng, Guo-Ping; Zhou, Kang; Zeng, Raymond J; Dong, Fang; Wang, Shu-Guang; Xu, An-Wu; Tong, Zhong-Hua; Yu, Han-Qing

2010-10-01

Microbial fuel cells (MFCs) provide new opportunities for the simultaneous wastewater treatment and electricity generation. Enhanced oxygen reduction capacity of cost-effective metal-based catalysts in an air cathode is essential for the scale-up and commercialization of MFCs in the field of wastewater treatment. We demonstrated that a nano-structured MnO(x) material, prepared by an electrochemically deposition method, could be an effective catalyst for oxygen reduction in an MFC to generate electricity with the maximum power density of 772.8 mW/m(3) and remove organics when the MFC was fed with an acetate-laden synthetic wastewater. The nano-structured MnO(x) with the controllable size and morphology could be readily obtained with the electrochemical deposition method. Both morphology and manganese oxidation state of the nano-scale catalyst were largely dependent on the electrochemical preparation process, and they governed its catalytic activity and the cathodic oxygen reduction performance of the MFC accordingly. Furthermore, cyclic voltammetry (CV) performed on each nano-structured material suggests that the MnO(x) nanorods had an electrochemical activity towards oxygen reduction reaction via a four-electron pathway in a neutral pH solution. This work provides useful information on the facile preparation of cost-effective cathodic catalysts in a controllable way for the single-chamber air-cathode MFC for wastewater treatment. Copyright © 2010 Elsevier Ltd. All rights reserved.
Cross dehydrogenative coupling of N-aryltetrahydroisoquinolines (sp3 C–H) with indoles (sp2 C–H) using a heterogeneous mesoporous manganese oxide catalyst

DOE PAGES

Dutta, B.; Sharma, Vinit K.; Sassu, N.; ...

2017-09-01

We disclose a novel, heterogeneous catalytic approach for selective coupling of C1 of N-aryltetrahydroisoquinolines with C3 of indoles in the presence of mesoporous manganese oxides. Our work involves a detailed mechanistic investigation of the reaction on the catalyst surface, backed by DFT computational studies, to understand the superior catalytic activity of manganese oxides.
Water oxidation catalysed by manganese compounds: from complexes to 'biomimetic rocks'.

PubMed

Wiechen, Mathias; Berends, Hans-Martin; Kurz, Philipp

2012-01-07

One of the most fundamental processes of the natural photosynthetic reaction sequence is the light-driven oxidation of water to molecular oxygen. In vivo, this reaction takes place in the large protein ensemble Photosystem II, where a μ-oxido-Mn(4)Ca- cluster, the oxygen-evolving-complex (OEC), has been identified as the catalytic site for the four-electron/four-proton redox reaction of water oxidation. This Perspective presents recent progress for three strategies which have been followed to prepare functional synthetic analogues of the OEC: (1) the synthesis of dinuclear manganese complexes designed to act as water-oxidation catalysts in homogeneous solution, (2) heterogeneous catalysts in the form of clay hybrids of such Mn(2)-complexes and (3) the preparation of manganese oxide particles of different compositions and morphologies. We discuss the key observations from the studies of such synthetic manganese systems in order to shed light upon the catalytic mechanism of natural water oxidation. Additionally, it is shown how research in this field has recently been motivated more and more by the prospect of finding efficient, robust and affordable catalysts for light-driven water oxidation, a key reaction of artificial photosynthesis. As manganese is an abundant and non-toxic element, manganese compounds are very promising candidates for the extraction of reduction equivalents from water. These electrons could consecutively be fed into the synthesis of "solar fuels" such as hydrogen or methanol.
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.
Permanganate-based synthesis of manganese oxide nanoparticles in ferritin

NASA Astrophysics Data System (ADS)

Olsen, Cameron R.; Smith, Trevor J.; Embley, Jacob S.; Maxfield, Jake H.; Hansen, Kameron R.; Peterson, J. Ryan; Henrichsen, Andrew M.; Erickson, Stephen D.; Buck, David C.; Colton, John S.; Watt, Richard K.

2017-05-01

This paper investigates the comproportionation reaction of MnII with {{{{MnO}}}4}- as a route for manganese oxide nanoparticle synthesis in the protein ferritin. We report that {{{{MnO}}}4}- serves as the electron acceptor and reacts with MnII in the presence of apoferritin to form manganese oxide cores inside the protein shell. Manganese loading into ferritin was studied under acidic, neutral, and basic conditions and the ratios of MnII and permanganate were varied at each pH. The manganese-containing ferritin samples were characterized by transmission electron microscopy, UV/Vis absorption, and by measuring the band gap energies for each sample. Manganese cores were deposited inside ferritin under both the acidic and basic conditions. All resulting manganese ferritin samples were found to be indirect band gap materials with band gap energies ranging from 1.01 to 1.34 eV. An increased UV/Vis absorption around 370 nm was observed for samples formed under acidic conditions, suggestive of MnO2 formation inside ferritin.
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. Copyright © 2014 Elsevier B.V. All rights reserved.
Reagent removal of manganese from ground water

NASA Astrophysics Data System (ADS)

Brayalovsky, G.; Migalaty, E.; Naschetnikova, O.

2017-06-01

The study is aimed at the technology development of treating drinking water from ground waters with high manganese content and oxidizability. Current technologies, physical/chemical mechanisms and factors affecting in ground treatment efficiency are reviewed. Research has been conducted on manganese compound removal from ground waters with high manganese content (5 ppm) and oxidizability. The studies were carried out on granular sorbent industrial ODM-2F filters (0.7-1.5 mm fraction). It was determined that conventional reagent oxidization technologies followed by filtration do not allow us to obtain the manganese content below 0.1 ppm when treating ground waters with high oxidizability. The innovative oxidation-based manganese removal technology with continuous introduction of reaction catalytic agent is suggested. This technology is effective in alkalization up to pH 8.8-9. Potassium permanganate was used as a catalytic agent, sodium hypochlorite was an oxidizer and cauistic soda served an alkalifying agent.

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

PubMed

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

2011-06-03

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.
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
Significant role of Mn(III) sites in e(g)(1) configuration in manganese oxide catalysts for efficient artificial water oxidation.

PubMed

Indra, Arindam; Menezes, Prashanth W; Schuster, Felix; Driess, Matthias

2015-11-01

Development of efficient bio-inspired water oxidation system with transition metal oxide catalyst has been considered as the one of the most challenging task in the recent years. As the oxygen evolving center of photosystem II consists of Mn4CaO5 cluster, most of the water oxidation study was converged to build up manganese oxide based catalysts. Here we report the synthesis of efficient artificial water oxidation catalysts by transferring the inactive manganese monooxide (MnO) under highly oxidizing conditions with ceric ammonium nitrate (CAN) and ozone (O3). MnO was partially oxidized to form mixed-valent manganese oxide (MnOx) with CAN whereas completely oxidized to mineral phase of ε-MnO2 (Akhtenskite) upon treatment of O3 in acidic solution, which we explore first time as a water oxidation catalyst. Chemical water oxidation, as well as the photochemical water oxidation in the presence of sacrificial electron acceptor and photosensitizer with the presented catalysts were carried out that followed the trends: MnOx>MnO2>MnO. Structural and activity correlation reveals that the presence of larger extent of Mn(III) in MnOx is the responsible factor for higher activity compared to MnO2. Mn(III) species in octahedral system with eg(1) configuration furnishes and facilitates the Mn-O and Mn-Mn bond enlargement with required structural flexibility and disorder in the manganese oxide structure which indeed facilitates water oxidation. Copyright © 2014 Elsevier B.V. All rights reserved.
Development of Sediment Quality Values for Puget Sound. Volume 1.

DTIC Science & Technology

1986-09-01

62 cadmium CHROMIUM,63 chromium COPPER ,64 copper IRON ,65 iron LEAD ,66 lead MANGANES ,67 manganese NICKEL ,68 nickel SELENIUM,69 selenium SILVER ,70...BERYLLIU beryllium 67. CADMIUM cadmium 68. CHROMIUM chromium 69. COPPER copper 70. IRON iron 71. LEAD lead 72. MANGANES manganese 73. NICKEL nickel 74...they can also be strongly influenced by iron and manganese oxide and hydrous oxide surfaces (these phases can scavenge metals under oxidizing
Durable rechargeable zinc-air batteries with neutral electrolyte and manganese oxide catalyst

NASA Astrophysics Data System (ADS)

Sumboja, Afriyanti; Ge, Xiaoming; Zheng, Guangyuan; Goh, F. W. Thomas; Hor, T. S. Andy; Zong, Yun; Liu, Zhaolin

2016-11-01

Neutral chloride-based electrolyte and directly grown manganese oxide on carbon paper are used as the electrolyte and air cathode respectively for rechargeable Zn-air batteries. Oxygen reduction and oxygen evolution reactions on manganese oxide show dependence of activities on the pH of the electrolyte. Zn-air batteries with chloride-based electrolyte and manganese oxide catalyst exhibit satisfactory voltage profile (discharge and charge voltage of 1 and 2 V at 1 mA cm-2) and excellent cycling stability (≈90 days of continuous cycle test), which is attributed to the reduced carbon corrosion on the air cathode and decreased carbonation in neutral electrolyte. This work describes a robust electrolyte system that improves the cycle life of rechargeable Zn-air batteries.
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.
Sulfur dioxide leaching of spent zinc-carbon-battery scrap

NASA Astrophysics Data System (ADS)

Avraamides, J.; Senanayake, G.; Clegg, R.

Zinc-carbon batteries, which contain around 20% zinc, 35% manganese oxides and 10% steel, are currently disposed after use as land fill or reprocessed to recover metals or oxides. Crushed material is subjected to magnetic separation followed by hydrometallurgical treatment of the non-magnetic material to recover zinc metal and manganese oxides. The leaching with 2 M sulfuric acid in the presence of hydrogen peroxide recovers 93% Zn and 82% Mn at 25 °C. Alkaline leaching with 6 M NaOH recovers 80% zinc. The present study shows that over 90% zinc and manganese can be leached in 20-30 min at 30 °C using 0.1-1.0 M sulfuric acid in the presence of sulfur dioxide. The iron extraction is sensitive to both acid concentration and sulfur dioxide flow rate. The effect of reagent concentration and particle size on the extraction of zinc, manganese and iron are reported. It is shown that the iron and manganese leaching follow a shrinking core kinetic model due to the formation of insoluble metal salts/oxides on the solid surface. This is supported by (i) the decrease in iron and manganese extraction from synthetic Fe(III)-Mn(IV)-Zn(II) oxide mixtures with increase in acid concentration from 1 M to 2 M, and (ii) the low iron dissolution and re-precipitation of dissolved manganese and zinc during prolonged leaching of battery scrap with low sulfur dioxide.
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.
Oxidation of organic contaminants by manganese oxide geomedia for passive urban stormwater treatment systems.

PubMed

Grebel, Janel E; Charbonnet, Joseph A; Sedlak, David L

2016-01-01

To advance cost-effective strategies for removing trace organic contaminants from urban runoff, the feasibility of using manganese oxides as a geomedia amendment in engineered stormwater infiltration systems to oxidize organic contaminants was evaluated. Ten representative organic chemicals that have previously been detected in urban stormwater were evaluated for reactivity in batch experiments with birnessite. With respect to reactivity, contaminants could be classified as: highly reactive (e.g., bisphenol A), moderately reactive (e.g., diuron) and unreactive (e.g., tris(2-chloro-1-propyl)phosphate). Bisphenol A and diuron reacted with birnessite to produce a suite of products, including ring-cleavage products for bisphenol A and partially dechlorinated products for diuron. Columns packed with manganese oxide-coated sand were used evaluate design parameters for an engineered infiltration system, including necessary contact times for effective treatment, as well as the impacts of stormwater matrix variables, such as solution pH, concentration of natural organic matter and major anions and cations. The manganese oxide geomedia exhibited decreased reactivity when organic contaminants were oxidized, especially in the presence of divalent cations, bicarbonate, and natural organic matter. Under typical conditions, the manganese oxides are expected to retain their reactivity for 25 years. Copyright © 2015 Elsevier Ltd. All rights reserved.
Immobilization of iron- and manganese-oxidizing bacteria with a biofilm-forming bacterium for the effective removal of iron and manganese from groundwater.

PubMed

Li, Chunyan; Wang, Shuting; Du, Xiaopeng; Cheng, Xiaosong; Fu, Meng; Hou, Ning; Li, Dapeng

2016-11-01

In this study, three bacteria with high Fe- and Mn-oxidizing capabilities were isolated from groundwater well sludge and identified as Acinetobacter sp., Bacillus megaterium and Sphingobacterium sp. The maximum removal ratios of Fe and Mn (99.75% and 96.69%) were obtained by an optimal combination of the bacteria at a temperature of 20.15°C, pH 7.09 and an inoculum size of 2.08%. Four lab-scale biofilters were tested in parallel for the removal of iron and manganese ions from groundwater. The results indicated that the Fe/Mn removal ratios of biofilter R4, which was inoculated with iron- and manganese-oxidizing bacteria and a biofilm-forming bacterium, were approximately 95% for each metal during continuous operation and were better than the other biofilters. This study demonstrated that the biofilm-forming bacterium could promote the immobilization of the iron- and manganese-oxidizing bacteria on the biofilters and enhance the removal efficiency of iron and manganese ions from groundwater. Copyright © 2016 Elsevier Ltd. All rights reserved.
The simple preparation of birnessite-type manganese oxide with flower-like microsphere morphology and its remarkable capacity retention

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

Zhu, Gang; Deng, Lingjuan; Wang, Jianfang

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 °Cmore » 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.« less
Structural Characterization of Biogenic Manganese Oxides Produced in Sea Water

NASA Astrophysics Data System (ADS)

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

2003-12-01

Manganese oxides have been coined as the "scavengers of the sea" and play important roles in both marine and freshwater systems. Natural manganese oxide nanoparticles and grain coatings are ubiquitous in the environment and profoundly impact the quality of sediments via their ability to degrade and sequester contaminants. These oxides are believed to form dominantly via oxidation of Mn(II) by marine and freshwater bacteria and have extremely high sorptive capacities for heavy metals. We have used XANES, EXAFS, and synchrotron (SR)-XRD techniques to study biogenic manganese oxides produced by spores of the marine Bacillus sp., strain SG-1 in seawater as a function of reaction time under fully in-situ conditions. The primary biogenic solid-phase Mn oxide product is a hexagonal layered phyollomanganate with an oxidation state similar to that in delta-MnO2. XRD data show the biooxides to have a phyllomanganate 10 basal plane spacing, suggesting the interlayer is hydrated and contains calcium. As the experiment continues, the initial biooxide changes to show triclinic symmetry. Fits to these EXAFS spectra suggest the octahedral layers have low Mn octahedral site vacancies in the lattice and the latyers bend to accommodate Jahn-Teller distortions creating the change in symmetry. The oxides observed in this study as models of Mn(II) bio-oxidation may be representative of the most abundant manganese oxide phase suspended in the oxic and sub-oxic zones of the oceanic water column.
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.
A multicopper oxidase is essential for manganese oxidation and laccase-like activity in Pedomicrobium sp. ACM 3067.

PubMed

Ridge, Justin P; Lin, Marianne; Larsen, Eloise I; Fegan, Mark; McEwan, Alastair G; Sly, Lindsay I

2007-04-01

Pedomicrobium sp. ACM 3067 is a budding-hyphal bacterium belonging to the alpha-Proteobacteria which is able to oxidize soluble Mn2+ to insoluble manganese oxide. A cosmid, from a whole-genome library, containing the putative genes responsible for manganese oxidation was identified and a primer-walking approach yielded 4350 bp of novel sequence. Analysis of this sequence showed the presence of a predicted three-gene operon, moxCBA. The moxA gene product showed homology to multicopper oxidases (MCOs) and contained the characteristic four copper-binding motifs (A, B, C and D) common to MCOs. An insertion mutation of moxA showed that this gene was essential for both manganese oxidation and laccase-like activity. The moxB gene product showed homology to a family of outer membrane proteins which are essential for Type I secretion in Gram-negative bacteria. moxBA has not been observed in other manganese-oxidizing bacteria but homologues were identified in the genomes of several bacteria including Sinorhizobium meliloti 1021 and Agrobacterium tumefaciens C58. These results suggest that moxBA and its homologues constitute a family of genes encoding an MCO and a predicted component of the Type I secretion system.
Dustiness of Fine and Nanoscale Powders

PubMed Central

Evans, Douglas E.; Baron, Paul A.

2013-01-01

Dustiness may be defined as the propensity of a powder to form airborne dust by a prescribed mechanical stimulus; dustiness testing is typically intended to replicate mechanisms of dust generation encountered in workplaces. A novel dustiness testing device, developed for pharmaceutical application, was evaluated in the dustiness investigation of 27 fine and nanoscale powders. The device efficiently dispersed small (mg) quantities of a wide variety of fine and nanoscale powders, into a small sampling chamber. Measurements consisted of gravimetrically determined total and respirable dustiness. The following materials were studied: single and multiwalled carbon nanotubes, carbon nanofibers, and carbon blacks; fumed oxides of titanium, aluminum, silicon, and cerium; metallic nanoparticles (nickel, cobalt, manganese, and silver) silicon carbide, Arizona road dust; nanoclays; and lithium titanate. Both the total and respirable dustiness spanned two orders of magnitude (0.3–37.9% and 0.1–31.8% of the predispersed test powders, respectively). For many powders, a significant respirable dustiness was observed. For most powders studied, the respirable dustiness accounted for approximately one-third of the total dustiness. It is believed that this relationship holds for many fine and nanoscale test powders (i.e. those primarily selected for this study), but may not hold for coarse powders. Neither total nor respirable dustiness was found to be correlated with BET surface area, therefore dustiness is not determined by primary particle size. For a subset of test powders, aerodynamic particle size distributions by number were measured (with an electrical low-pressure impactor and an aerodynamic particle sizer). Particle size modes ranged from approximately 300nm to several micrometers, but no modes below 100nm, were observed. It is therefore unlikely that these materials would exhibit a substantial sub-100nm particle contribution in a workplace. PMID:23065675
Use of manganese oxide and activated carbon fibers for removing a particle, volatile organic compound or ozone from a gas

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

Sidheswaran, Meera A.; Destaillats, Hugo; Fisk, William J.

The present invention provides for a device for reducing a volatile organic compound (VOC) content of a gas comprising a manganese oxide (MnO.sub.x) catalyst. The manganese oxide (MnO.sub.x) catalyst is capable of catalyzing formaldehyde at room temperature, with complete conversion, to CO.sub.2 and water vapor. The manganese oxide (MnO.sub.x) catalyst itself is not consumed by the reaction of formaldehyde into CO.sub.2 and water vapor. The present invention also provides for a device for reducing or removing a particle, a VOC and/or ozone from a gas comprising an activated carbon filter (ACF) on a media that is capable of being periodicallymore » regenerated.« less
Calcium manganese(IV) oxides: biomimetic and efficient catalysts for water oxidation.

PubMed

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

2012-04-28

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

PubMed

Xin, Baoping; Chen, Bing; Duan, Ning; Zhou, Changbo

2011-01-01

Extraction of manganese from electrolytic manganese residues using bioleaching was investigated in this paper. The maximum extraction efficiency of Mn was 93% by sulfur-oxidizing bacteria at 4.0 g/l sulfur after bioleaching of 9days, while the maximum extraction efficiency of Mn was 81% by pyrite-leaching bacteria at 4.0 g/l pyrite. The series bioleaching first by sulfur-oxidizing bacteria and followed by pyrite-leaching bacteria evidently promoted the extraction of manganese, witnessing the maximum extraction efficiency of 98.1%. In the case of sulfur-oxidizing bacteria, the strong dissolution of bio-generated sulfuric acid resulted in extraction of soluble Mn2+, while both the Fe2+ catalyzed reduction of Mn4+ and weak acidic dissolution of Mn2+ accounted for the extraction of manganese with pyrite-leaching bacteria. The chemical simulation of bioleaching process further confirmed that the acid dissolution of Mn2+ and Fe2+ catalyzed reduction of Mn4+ were the bioleaching mechanisms involved for Mn extraction from electrolytic manganese residues. Copyright Â© 2010 Elsevier Ltd. All rights reserved.
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.
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.

Physicochemical properties of manganese oxides obtained via the sol-gel method: The reduction of potassium permanganate by polyvinyl alcohol

NASA Astrophysics Data System (ADS)

Ivanets, A. I.; Prozorovich, V. G.; Krivoshapkina, E. F.; Kuznetsova, T. F.; Krivoshapkin, P. V.; Katsoshvili, L. L.

2017-08-01

Experimental data on the sol-gel synthesis of manganese oxides formed during the reduction of potassium permanganate by polyvinyl alcohol in an aqueous medium are presented. The physicochemical properties of the obtained manganese oxide systems that depend on the conditions of the synthesis are studied by means of DTA, XRD, SEM, and the low temperature adsorption-desorption of nitrogen. It is found that the obtained samples have a mesoporous structure and predominantly consist of double potassium-manganese oxide K2Mn4O8 with a tunnel structure and impurities of oxides such as α-MnO2, MnO, α-Mn2O3, and Mn5O8. It is shown that the proposed method of synthesis allows us to regulate the size and volume of mesopores and, to a lesser extent, the texture of the obtained oxides, which can be considered promising sorbents for the selective extraction of strontium and cesium ions from multicomponent aqueous solutions.
The laccase-like reactivity of manganese oxide nanomaterials for pollutant conversion: rate analysis and cyclic voltammetry.

PubMed

Wang, Xinghao; Liu, Jiaoqin; Qu, Ruijuan; Wang, Zunyao; Huang, Qingguo

2017-08-10

Nanostructured manganese oxides, e.g. MnO 2 , have shown laccase-like catalytic activities, and are thus promising for pollutant oxidation in wastewater treatment. We have systematically compared the laccase-like reactivity of manganese oxide nanomaterials of different crystallinity, including α-, β-, γ-, δ-, and ɛ-MnO 2 , and Mn 3 O 4 , with 2,2'-azinobis-(3-ethylbenzthiazoline-6-sulfonate) (ABTS) and 17β-estradiol (E2) as the probing substrates. The reaction rate behaviors were examined with regard to substrate oxidation and oxygen reduction to evaluate the laccase-like catalysis of the materials, among which γ-MnO 2 exhibits the best performance. Cyclic voltammetry (CV) was employed to assess the six MnO x nanomaterials, and the results correlate well with their laccase-like catalytic activities. The findings help understand the mechanisms of and the factors controlling the laccase-like reactivity of different manganese oxides nanomaterials, and provide a basis for future design and application of MnO x -based catalysts.
Study of interaction and adsorption of aromatic amines by manganese oxides and their role in chemical evolution

NASA Astrophysics Data System (ADS)

Bhushan, Brij; Nayak, Arunima; Kamaluddin

2017-04-01

The role of manganese oxides in concentrating organic moieties and offering catalytic activity for prebiotic reactions is investigated by studying their interaction with different aromatic amines such as aniline, p-chloroaniline, p-toluidine and p-anisidine. For all amines, metal oxides showed highest adsorption at neutral pH. The order of their adsorption capacity and affinity as revealed by the Langmuir constants was found to be manganosite (MnO) > bixbyite (Mn2O3) > hausmannite (Mn3O4) > and pyrolusite (MnO2). At alkaline pH, these manganese oxides offered their surfaces for oxidation of amines to form coloured oligomers. Analysis of the oxidation products by gas chromatography-mass spectrometry showed the formation of a dimer from p-anisidine and p-chloroaniline, while a trimer and tetramer is formed from p-toluidine and aniline, respectively. A reaction mechanism is proposed for the formation of the oligomers. While field-emission scanning electron microscopic studies confirm the binding phenomenon, the Fourier transform infrared spectroscopy analysis suggests that the mechanism of binding of amines on the manganese oxides was primarily electrostatic. The adsorption behaviour of the studied aromatic amines followed the order: p-anisidine > p-toluidine > aniline > p-chloroaniline, which is related to the basicities and structure of the amines. Our studies confirmed the significance of the role of manganese oxides in prebiotic chemistry.
An engineered polypeptide around nano-sized manganese-calcium oxide: copying plants for water oxidation.

PubMed

Najafpour, Mohammad Mahdi; Ghobadi, Mohadeseh Zarei; Sarvi, Bahram; Haghighi, Behzad

2015-09-14

Synthesis of new efficient catalysts inspired by Nature is a key goal in the production of clean fuel. Different compounds based on manganese oxide have been investigated in order to find their water-oxidation activity. Herein, we introduce a novel engineered polypeptide containing tyrosine around nano-sized manganese-calcium oxide, which was shown to be a highly active catalyst toward water oxidation at low overpotential (240 mV), with high turnover frequency of 1.5 × 10(-2) s(-1) at pH = 6.3 in the Mn(III)/Mn(IV) oxidation range. The compound is a novel structural and efficient functional model for the water-oxidizing complex in Photosystem II. A new proposed clever strategy used by Nature in water oxidation is also discussed. The new model of the water-oxidizing complex opens a new perspective for synthesis of efficient water-oxidation catalysts.
Persulfate activation by subsurface minerals.

PubMed

Ahmad, Mushtaque; Teel, Amy L; Watts, Richard J

2010-06-25

Persulfate dynamics in the presence of subsurface minerals was investigated as a basis for understanding persulfate activation for in situ chemical oxidation (ISCO). The mineral-mediated decomposition of persulfate and generation of oxidants and reductants was investigated with four iron and manganese oxides and two clay minerals at both low pH (<7) and high pH (>12). The manganese oxide birnessite was the most effective initiator of persulfate for degrading the oxidant probe nitrobenzene, indicating that oxidants are generated at both low and high pH regimes. The iron oxide goethite was the most effective mineral for degrading the reductant probe hexachloroethane. A natural soil and two soil fractions were used to confirm persulfate activation by synthetic minerals. The soil and soil fractions did not effectively promote the generation of oxidants or reductants. However, soil organic matter was found to promote reductant generation at high pH. The results of this research demonstrate that synthetic iron and manganese oxides can activate persulfate to generate reductants and oxidants; however, iron and manganese oxides in the natural soil studied do not show the same reactivity, most likely due to the lower masses of the metal oxides in the soil relative to the masses studied in isolated mineral systems. 2010. Published by Elsevier B.V.
The key role of biogenic manganese oxides in enhanced removal of highly recalcitrant 1,2,4-triazole from bio-treated chemical industrial wastewater.

PubMed

Wu, Ruiqin; Wu, Haobo; Jiang, Xinbai; Shen, Jinyou; Faheem, Muhammad; Sun, Xiuyun; Li, Jiansheng; Han, Weiqing; Wang, Lianjun; Liu, Xiaodong

2017-04-01

The secondary effluent from biological treatment process in chemical industrial plant often contains refractory organic matter, which deserves to be further treated in order to meet the increasingly stringent environmental regulations. In this study, the key role of biogenic manganese oxides (BioMnOx) in enhanced removal of highly recalcitrant 1,2,4-triazole from bio-treated chemical industrial wastewater was investigated. BioMnOx production by acclimated manganese-oxidizing bacterium (MOB) consortium was confirmed through scanning electronic microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and X-ray diffraction (XRD) analysis. Pseudomonas and Bacillus were found to be the most predominant species in acclimated MOB consortium. Mn 2+ could be oxidized optimally at neutral pH and initial Mn 2+ concentration below 33 mg L -1 . However, 1,2,4-triazole removal by BioMnOx produced occurred optimally at slightly acidic pH. High dosage of both Mn 2+ and 1,2,4-triazole resulted in decreased 1,2,4-triazole removal. In a biological aerated filter (BAF) coupled with manganese oxidation, 1,2,4-triazole and total organic carbon removal could be significantly enhanced compared to the control system without the participation of manganese oxidation, confirming the key role of BioMnOx in the removal of highly recalcitrant 1,2,4-triazole. This study demonstrated that the biosystem coupled with manganese oxidation had a potential for the removal of various recalcitrant contaminants from bio-treated chemical industrial wastewater.
Electrocatalytic oxidation of 2-mercaptoethanol using modified glassy carbon electrode by MWCNT in combination with unsymmetrical manganese (II) Schiff base complexes

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

Mohebbi, Sajjad, E-mail: smohebbi@uok.ac.ir; 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 andmore » 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.« less
Biogeochemical cycling of manganese in Oneida Lake, New York: whole lake studies of manganese

NASA Technical Reports Server (NTRS)

Aguilar, C.; Nealson, K. H.

1998-01-01

Oneida Lake, New York is a eutrophic freshwater lake known for its abundant manganese nodules and a dynamic manganese cycle. Temporal and spatial distribution of soluble and particulate manganese in the water column of the lake were analyzed over a 3-year period and correlated with other variables such as oxygen, pH, and temperature. Only data from 1988 are shown. Manganese is removed from the water column in the spring via conversion to particulate form and deposited in the bottom sediments. This removal is due to biological factors, as the lake Eh/pH conditions alone can not account for the oxidation of the soluble manganese Mn(II). During the summer months the manganese from microbial reduction moves from the sediments to the water column. In periods of stratification the soluble Mn(II) builds up to concentrations of 20 micromoles or more in the bottom waters. When mixing occurs, the soluble Mn(II) is rapidly removed via oxidation. This cycle occurs more than once during the summer, with each manganese atom probably being used several times for the oxidation of organic carbon. At the end of the fall, whole lake concentrations of manganese stabilize, and remain at about 1 micromole until the following summer, when the cycle begins again. Inputs and outflows from the lake indicate that the active Mn cycle is primarily internal, with a small accumulation each year into ferromanganese nodules located in the oxic zones of the lake.
Manganese Oxide Nanoarray-Based Monolithic Catalysts: Tunable Morphology and High Efficiency for CO Oxidation

DOE PAGES

Chen, Sheng-Yu; Song, Wenqiao; Lin, Hui-Jan; ...

2016-03-08

In this work, 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., K 2Cr 2O 7, KClO 3, and K 2S 2O 8, 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 reactivitymore » of carbon monoxide (CO) oxidation. K 2Cr 2O 7 and KClO 3 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. Finally, the straightforward synthetic process showed a scalable, low-cost, and template-free method to fabricate manganese oxide nanoarray monolithic catalysts for exhaust treatment.« less
Manganese oxide octahedral molecular sieves: Synthesis, self-assembly, control over morphologies and tunnel structure

NASA Astrophysics Data System (ADS)

Yuan, Jikang

Direct architecture of complex nanostructures is desirable and still remains a challenge in areas of materials science. Due to their size-, shape-dependent electronic and optical properties, much effort has been made to control morphologies of transition metal oxide nanoparticles and to organize them into complicated 3D structures using templates. In particular, manganese oxides have attracted much attention because they have extensive applications in many chemical processes due to their porous structures, acidity, ionexchange, separation, catalysis, and energy storage in secondary batteries. Using organic templates such as trimethylamine (TMA), manganese oxides have been successfully organized into macroscopic rings and helices via sol-gel processes. However, the methods mentioned above all need further purification, so impurities will be avoided. Subsequent procedures are needed to obtain pure products. Thus facile and template-free methods are highly desired for synthesis of manganese oxide nanaoparticles with complex 3D structures. Manganese oxide octahedral molecular sieves (OMS) are a class of microporous transition metallic oxides with various kinds of tunnel structures that can be synthesized via controlling synthetic conditions such as temperature, concentration, pH, and cations. Manganese oxide molecular sieves are semiconducting mixed-valence catalysts that utilize electron transport to catalyze reactions such as selective oxidation of alcohols. OMS has distinct advantages over aluminosilicate molecular sieve materials for applications in catalysis due to the mixed valence character. The synthesis of manganese oxide OMS materials will be much more complicated than those of main group metallic oxides because of different coordination numbers and oxidation states. OMS-type materials with desirable morphologies formed under mild synthetic conditions are highly desirable. Herein, we report a template-free, low temperature preparation of porous cryptomelane-type manganese oxide (OMS-2) 3D nanostructures. The objectives of this research include exploration of new methods to oxidize Mn2+ in aqueous solution either under low-temperature reflux or hydrothermal conditions. Various oxidants were used with precisely controlled synthetic parameters such as temperature, concentrations of starting materials, pH, and kinds of templates. A variety of techniques including powder X-ray diffraction and transmission electron microscopy (TEM) scanning electron microscopy are used to investigate the structures of synthesized materials. Atomic force microscopy (AFM) and scanning electron microscopy are utilized to studying the morphology and topography. The surface areas of the materials is measured by the BET method. Inductively coupled argon plasma atomic emission spectrometer (ICP-AES) are utilized to investigate the chemical composition of the materials. Thermal-stability of the materials is investigated by thermal gravimetric analysis (TGA). The objectives of this research includes exploring new synthetic approach such as oxidation of Mn2+ in aqueous solution by selecting suitable oxidants so as to control redox potential, varying pH of reaction systems, and controlling tunnel structures using hard templates (cations) under hydrothermal conditions.
Quantifying manganese and nitrogen cycle coupling in manganese-rich, organic carbon-starved marine sediments: Examples from the Clarion-Clipperton fracture zone

NASA Astrophysics Data System (ADS)

Mogollón, José M.; Mewes, Konstantin; Kasten, Sabine

2016-07-01

Extensive deep-sea sedimentary areas are characterized by low organic carbon contents and thus harbor suboxic sedimentary environments where secondary (autotrophic) redox cycling becomes important for microbial metabolic processes. Simulation results for three stations in the Eastern Equatorial Pacific with low organic carbon content (<0.5 dry wt %) and low sedimentation rates (10-1-100 mm ky-1) show that ammonium generated during organic matter degradation may act as a reducing agent for manganese oxides below the oxic zone. Likewise, at these sedimentary depths, dissolved reduced manganese may act as a reducing agent for oxidized nitrogen species. These manganese-coupled transformations provide a suboxic conversion pathway of ammonium and nitrate to dinitrogen. These manganese-nitrogen interactions further explain the presence and production of dissolved reduced manganese (up to tens of μM concentration) in sediments with high nitrate (>20 μM) concentrations.
High manganese concentrations in rocks at Gale crater, Mars

USGS Publications Warehouse

Lanza, Nina L.; Fischer, Woodward W.; Wiens, Roger C.; Grotzinger, John P.; Ollila, Ann M.; Anderson, Ryan B.; Clark, Benton C.; Gellert, Ralf; Mangold, Nicolas; Maurice, Sylvestre; Le Mouélic, Stéphane; Nachon, Marion; Schmidt, Mariek E.; Berger, Jeffrey; Clegg, Samuel M.; Forni, Olivier; Hardgrove, Craig; Melikechi, Noureddine; Newsom, Horton E.; Sautter, Violaine

2014-01-01

The surface of Mars has long been considered a relatively oxidizing environment, an idea supported by the abundance of ferric iron phases observed there. However, compared to iron, manganese is sensitive only to high redox potential oxidants, and when concentrated in rocks, it provides a more specific redox indicator of aqueous environments. Observations from the ChemCam instrument on the Curiosity rover indicate abundances of manganese in and on some rock targets that are 1–2 orders of magnitude higher than previously observed on Mars, suggesting the presence of an as-yet unidentified manganese-rich phase. These results show that the Martian surface has at some point in time hosted much more highly oxidizing conditions than has previously been recognized.
Epoxidation of alkenes and oxidation of alcohols with hydrogen peroxide catalyzed by a manganese(V) nitrido complex.

PubMed

Kwong, Hoi-Ki; Lo, Po-Kam; Lau, Kai-Chung; Lau, Tai-Chu

2011-04-14

The manganese(V) nitrido complex (PPh(4))(2)[Mn(N)(CN)(4)] is an active catalyst for alkene epoxidation and alcohol oxidation using H(2)O(2) as an oxidant. The catalytic oxidation is greatly enhanced by the addition of just one equivalent of acetic acid. The oxidation of ethene by this system has been studied computationally by the DFT method.
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 Ag_xMnO_y, 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 Ag_xMnO_yelectrodes by decomposition of a permanganate salt, such as AgMnO₄, or by the decomposition of KMnO₄or LiMnO₄in the presence of a silver salt.
Synthesis, characterization and photocatalytic activity of porous manganese oxide doped titania for toluene decomposition.

PubMed

Jothiramalingam, R; Wang, M K

2007-08-17

The present study describes the photocatalytic degradation of toluene in gas phase on different porous manganese oxide doped titanium dioxide. As synthesized birnessite and cryptomelane type porous manganese oxide were doped with titania and tested for photocatalytic decomposition of toluene in gas phase. The effects of the inlet concentration of toluene, flow rate (retention time) were examined and the relative humidity was maintained constantly. Thermal and textural characterization of manganese oxide doped titania materials were characterized by X-ray diffraction (XRD), thermogravemetry (TG), BET and TEM-EDAX studies. The aim of the present study is to synthesize the porous manganese oxide doped titania and to study its photocatalytic activity for toluene degradation in gas phase. Cryptomelane doped titania catalyst prepared in water medium [K-OMS-2 (W)] is shown the good toluene degradation with lower catalysts loading compared to commercial bulk titania in annular type photo reactor. The higher photocatalytic activity due to various factors such as catalyst preparation method, experimental conditions, catalyst loading, surface area, etc. In the present study manganese oxide OMS doped titania materials prepared by both aqueous and non-aqueous medium, aqueous medium prepared catalyst shows the good efficiency due to the presence of OH bonded groups on the surface of catalyst. The linear forms of different kinetic equations were applied to the adsorption data and their goodness of fit was evaluated based on the R2 and standard error. The goodness to the linear fit was observed for Elovich model with high R2 (>or=0.9477) value.
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.
Effect of composition on the structure of lithium- and manganese-rich transition metal oxides

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

Shukla, Alpesh Khushalchand; Ramasse, Quentin M.; Ophus, Colin

In this work, we establish a definitive structural model for lithium- and manganese-rich transition metal oxides and demonstrate the effect of composition on their bulk as well as the surface structure.
Effect of composition on the structure of lithium- and manganese-rich transition metal oxides

DOE PAGES

Shukla, Alpesh Khushalchand; Ramasse, Quentin M.; Ophus, Colin; ...

2018-01-01

In this work, we establish a definitive structural model for lithium- and manganese-rich transition metal oxides and demonstrate the effect of composition on their bulk as well as the surface structure.
Enhancing Photocatalytic Activity on (MnO@TNTAs):Mn2+ with a Hierarchical Sandwich-Like Nanostructure via a Two-Step Procedure

NASA Astrophysics Data System (ADS)

Kong, Junhan; Zhang, Wei; Zhang, Yubo; Xia, Minghao; Wu, Xiuling; Wang, Yongqian

2018-02-01

Several semiconductor nanomaterial devices are increasingly being applied in a variety of fields, especially in the treating of environmental pollutants. We have fabricated (MnO@TNTAs):Mn2+ with sandwich-like nanostructures composed of TiO2 nanotube arrays (TNTAs), Mn-doped TNTAs and MnO. The experimental procedure was a two-step synthesis: first, using anodic oxidation methods and then hydrothermal methods. We carried out many characterizations of the "sandwiches" in the nanoscale. From the field emission scanning electron microscopy images we found nanofibers lying on the highly-ordered nanotube arrays. The diameter of the nanotubes was about 50 nm but the size of the nanofibers varied. Energy dispersive spectroscopy demonstrated that the nanofibers contained a manganese element and x-ray diffraction patterns showed the peak of the manganosite phase. From ultraviolet-visible light spectra, it was found that the nanostructures had strong absorption activities under both ultraviolet and visible light radiation, while pure TNTAs had absorption only under ultraviolet light. The photodegradation experiments proved that the sandwich-like nanostructures had an excellent photocatalytic activity (92.5% after 240 min), which was a great improvement compared with pure TNTAs. In this way, the structures as a device at the nanoscale have a huge potential in controlling environmental pollution.
Early stage sustainability evaluation of new, nanoscale cathode materials for Li-ion batteries.

PubMed

Hischier, Roland; Kwon, Nam Hee; Brog, Jean-Pierre; Fromm, Katharina M

2018-05-07

We present results of early stage sustainability evaluation of two development strategies for new, nano-scale cathode materials for Li-ion batteries: (i) a new production pathway of existing material (LiCoO2), and (ii) a new nanomaterial (LiMnPO4). Nano-LiCoO2 was synthesized via a single source precursor route at lower temperature with a shorter reaction time, resulting in a smaller grain size and, thereby, a better diffusivity for Li-ions. Nano-LiMnPO4 was synthesized via a wet chemical method. The sustainability potential of these materials has then been investigated (at the laboratory and pilot production scales). The results show that the environmental impact of nano-LiMnPO4 is lower compared to the other examined nanomaterial by several factors, and this regardless of the indicator for the comparison. In contrast to commercial cathode materials, this new material shows, particularly on an energy and capacity basis, results in the same order of magnitude as those of lithium manganese oxide (LiMn2O4), and only slightly higher values than those for lithium iron phosphate (LiFePO4); values that are clearly lower than those for high-temperature LiCoO2. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis and catalytic activity of Birnessite-Type Manganese Oxide synthesized by solvent-free method

NASA Astrophysics Data System (ADS)

Siregar, S. S.; Awaluddin, A.

2018-04-01

Redox reaction between KMnO4 and glucose usingsolvent-free method produces the octahedral layer birnessite-type manganese oxide. The effects of mole ratios, temperatures, and calcinations time on the structures and crystallinity of the oxides were studied throughthe X-ray powder diffraction analysis. The mole ratio of KMnO4/glucose (1:3) produces the purebirnessite with low crystallinity, whereas the mole ratio of KMnO4/glucose (3:1) yields high crystalline birnessite with minor components of hausmannite-type manganese oxide.The increasing of the temperature and calcinations times (300-700 °C and 3-7 h, respectively) willimprove the crystallinity and the purity of the as-synthesized oxide. Further experiments also showed that the as-syntesized octahedral layer birnessite-type manganese oxides have catalytic activity on the degradation of methylene blue (MB) dye with H2O2 as oxidant. The results revealed that the effective degradation could be achieved only in the presence of both the birnessite and H2O2, whereas without the addition of catalyst (H2O2only) or addition of H2O2 (catalyst only), the 3.5% and 15.5% of MB removal were obtained, respectively.
A Comparative Study of the Adsorption of Methylene Blue onto Synthesized Nanoscale Zero-Valent Iron-Bamboo and Manganese-Bamboo Composites

PubMed Central

Shaibu, Solomon E.; Adekola, Folahan A.; Adegoke, Halimat I.; Ayanda, Olushola S.

2014-01-01

In this study, bamboo impregnated with nanoscale zero-valent iron (nZVI) and nanoscale manganese (nMn) were prepared by the aqueous phase borohydride reduction method and characterized using scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR) and PIXE analysis. The synthesized nMn-bamboo and nZVI-bamboo composites were subsequently applied to the sorption of methylene blue (MB) dye from aqueous solution. The adsorption of MB dye was investigated under various experimental conditions such as pH, contact time, initial concentration of MB dye and adsorbent dosage. The results showed that the synthesized nZVI-bamboo composite was more effective than nMn-bamboo composite in terms of higher MB dye adsorption capacity of 322.5 mg/g compared to 263.5 mg/g of nMn-bamboo composite. At a concentration of 140 mg/L MB dye, 0.02 g of nZVI-bamboo and nMn-bamboo composites resulted in 79.6% and 78.3% removal, respectively, at 165 rpm, contact time of 120 min and at a solution pH of 7.6. The equilibrium data was best represented by Freundlich isotherm model and the pseudo-second order kinetic model better explained the kinetic data for both nZVI-bamboo and nMn-bamboo composites. PMID:28788688
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. Copyright © 2016 Elsevier Inc. All rights reserved.
Manganese complex-catalyzed oxidation and oxidative kinetic resolution of secondary alcohols by hydrogen peroxide.

PubMed

Miao, Chengxia; Li, Xiao-Xi; Lee, Yong-Min; Xia, Chungu; Wang, Yong; Nam, Wonwoo; Sun, Wei

2017-11-01

The highly efficient catalytic oxidation and oxidative kinetic resolution (OKR) of secondary alcohols has been achieved using a synthetic manganese catalyst with low loading and hydrogen peroxide as an environmentally benign oxidant in the presence of a small amount of sulfuric acid as an additive. The product yields were high (up to 93%) for alcohol oxidation and the enantioselectivity was excellent (>90% ee) for the OKR of secondary alcohols. Mechanistic studies revealed that alcohol oxidation occurs via hydrogen atom (H-atom) abstraction from an α-CH bond of the alcohol substrate and a two-electron process by an electrophilic Mn-oxo species. Density functional theory calculations revealed the difference in reaction energy barriers for H-atom abstraction from the α-CH bonds of R - and S -enantiomers by a chiral high-valent manganese-oxo complex, supporting the experimental result from the OKR of secondary alcohols.
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-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. Electronic supplementary information (ESI) available: Chemical structures of functional groups on cellulose fibers, the surface water wettability of rice paper, CV curves of supercapacitors at different scan rates, galvanostatic charge-discharge curves of supercapacitors at different current densities, TGA profiles of the SWCNT-MnO2-paper composites synthesized at different temperatures, TEM images of MnO2 particles deposited on rice paper at different temperatures, photographs of supercapacitors under different bending test conditions, and a video of bending and folding the SWCNT-MnO2-paper composites. See DOI: 10.1039/c3nr03010e
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.
Controllable cyanation of carbon-hydrogen bonds by zeolite crystals over manganese oxide catalyst

PubMed Central

Wang, Liang; Wang, Guoxiong; Zhang, Jian; Bian, Chaoqun; Meng, Xiangju; Xiao, Feng-Shou

2017-01-01

The synthesis of organic nitriles without using toxic cyanides is in great demand but challenging to make. Here we report an environmentally benign and cost-efficient synthesis of nitriles from the direct oxidative cyanation of primary carbon-hydrogen bonds with easily available molecular oxygen and urea. The key to this success is to design and synthesize manganese oxide catalysts fixed inside zeolite crystals, forming a manganese oxide catalyst with zeolite sheath (MnOx@S-1), which exhibits high selectivity for producing nitriles by efficiently facilitating the oxidative cyanation reaction and hindering the side hydration reaction. The work delineates a sustainable strategy for synthesizing nitriles while avoiding conventional toxic cyanide, which might open a new avenue for selective transformation of carbon-hydrogen bonds. PMID:28504259
Preparation and performance of manganese-oxide-coated zeolite for the removal of manganese-contamination in groundwater.

PubMed

Lyu, Cong; Yang, Xuejiao; Zhang, Shengyu; Zhang, Qihui; Su, Xiaosi

2017-12-29

A promising and easily prepared catalytic filler media, manganese-oxide-coated zeolite (MOCZ), for the removal of Mn (II) contamination in groundwater was studied. The optimal condition for MOCZ preparation was given as follows: acid activation of zeolite with 5% HCl mass percent for 12 h, then soaking of acid-activated zeolite with 7% KMnO 4 mass percent for 8 h, and finally calcination at 300°C for 5 h. Acid activation significantly enlarged the specific surface area of the zeolite (>79 m 2 g -1 ), subsequently enhancing the coating of manganese oxides onto the surface of the zeolite. This was further supported by the manganese-to-zeolite ratio (γ Mn ) and Energy dispersive analysis-mapping. The γ Mn was over 12.26 mg Mn g -1 zeolite, representing more active sites for the adsorption and catalytic-oxidation of Mn (II). As such, great performance of Mn (II) removal by MOCZ was obtained in the filter experiment. An estimated 98-100% removal efficiency of Mn (II) was achieved in a greatly short startup time (only 2 h). During the filtration process, newborn flocculent manganese oxides with a mixed-valence of manganese (Mn (II) and Mn (IV)) were generated on the MOCZ surface, further facilitating the adsorption and catalytic-oxidation of Mn (II). The filter with MOCZ as adsorbent had a great performance on the Mn (II) removal in a wide range of hydraulic retention time (HRT) (4-40 min), particularly in a short HRT. Besides, the filter prolonged the filtration period (60 days), which would significantly reduce the frequency of backwash. Thus, it could be concluded that MOCZ prepared in this study showed a good performance in terms of Mn (II) removal in waterworks, especially small waterworks in the villages/towns.
Manganese-cerium oxide catalysts prepared by non-thermal plasma for NO oxidation: Effect of O2 in discharge atmosphere

NASA Astrophysics Data System (ADS)

Liu, Lu; Zheng, Chenghang; Wu, Shenghao; Gao, Xiang; Ni, Mingjiang; Cen, Kefa

2017-09-01

Non-thermal plasma with different O2 concentration in discharge atmosphere was applied to synthesize manganese and cerium mixed-oxides catalysts, which were compared in NO oxidation activity. Discharge atmosphere displayed a crucial influence on the performance of the catalysts prepared by plasma. Relatively low O2 concentration in discharge atmosphere allows synthesizing manganese-cerium oxides catalysts in a moderate environment and therefore is favorable for better physicochemical properties which lead to superior catalytic behavior. The best catalyst was obtained by treatment with 10% O2/N2 plasma and presented over 80% NO conversion in the temperature range of 275-325 °C, whereas catalyst prepared in pure O2 discharge atmosphere had the same activity with a catalyst prepared by calcinations. A correlation between the surface properties of the plasma prepared catalysts and its catalytic activity in NO oxidation is proposed. The amount of the surface adsorbed oxygen has an obvious linear correlation with the amount of Ce3+, the H2 consumption at low temperatures and the catalytic performance. The superior catalytic performance is mainly attributed to the stronger interaction between manganese oxides and ceria, and the formation of poorly crystallized Mn-O-Ce phase in the catalyst which resulted from the slow decomposition of nitrates and organics during plasma treatment. Catalysts prepared in relatively low O2 concentration have large specific surface area and is abundant in Ce3+ species and active oxygen species. The study suggests that plasma treatment with proper discharge gas components is a promising method to prepare effective manganese- cerium oxides catalyst for NO oxidation.
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.
Photogeochemical reactions of manganese under anoxic conditions

NASA Astrophysics Data System (ADS)

Liu, W.; Yee, N.; Piotrowiak, P.; Falkowski, P. G.

2017-12-01

Photogeochemistry describes reactions involving light and naturally occurring chemical species. These reactions often involve a photo-induced electron transfer that does not occur in the absence of light. Although photogeochemical reactions have been known for decades, they are often ignored in geochemical models. In particular, reactions caused by UV radiation during an ozone free early Earth could have influenced the available oxidation states of manganese. Manganese is one of the most abundant transition metals in the crust and is important in both biology and geology. For example, the presence of manganese (VI) oxides in the geologic record has been used as a proxy for oxygenic photosynthesis; however, we suggest that the high oxidation state of Mn can be produced abiotically by photochemical reactions. Aqueous solutions of manganese (II) as well as suspensions of rhodochrosite (MnCO3) were irradiated under anoxic condition using a 450 W mercury lamp and custom built quartz reaction vessels. The photoreaction of the homogeneous solution of Mn(II) produced H2 gas and akhtenskite (ɛ-MnO2) as the solid product . This product is different than the previously identified birnessite. The irradiation of rhodochrosite suspensions also produced H2 gas and resulted in both a spectral shift as well as morphology changes of the mineral particles in the SEM images. These reactions offer alternative, abiotic pathways for the formation of manganese oxides.
Facile N...N coupling of manganese(V) imido species.

PubMed

Yiu, Shek-Man; Lam, William W Y; Ho, Chi-Ming; Lau, Tai-Chu

2007-01-31

(Salen)manganese(V) nitrido species are activated by electrophiles such as trifluoroacetic anhydride (TFAA) or trifluoroacetic acid (TFA) to produce N2. Mechanistic studies suggest that the manganese(V) nitrido species first react with TFAA or TFA to produce an imido species, which then undergoes N...N coupling. It is proposed that the resulting manganese(III) mu-diazene species decomposes via internal redox to give N2 and manganese(II). The manganese(II) species is then rapidly oxidized by manganese(V) imide to give manganese(III) and CF3CONH2 (for TFAA) or NH3 (for TFA).
Iron and manganese in anaerobic respiration: environmental significance, physiology, and regulation

NASA Technical Reports Server (NTRS)

Nealson, K. H.; Saffarini, D.

1994-01-01

Dissimilatory iron and/or manganese reduction is known to occur in several organisms, including anaerobic sulfur-reducing organisms such as Geobacter metallireducens or Desulfuromonas acetoxidans, and facultative aerobes such as Shewanella putrefaciens. These bacteria couple both carbon oxidation and growth to the reduction of these metals, and inhibitor and competition experiments suggest that Mn(IV) and Fe(III) are efficient electron acceptors similar to nitrate in redox abilities and capable of out-competing electron acceptors of lower potential, such as sulfate (sulfate reduction) or CO2 (methanogenesis). Field studies of iron and/or manganese reduction suggest that organisms with such metabolic abilities play important roles in coupling the oxidation of organic carbon to metal reduction under anaerobic conditions. Because both iron and manganese oxides are solids or colloids, they tend to settle downward in aquatic environments, providing a physical mechanism for the movement of oxidizing potential into anoxic zones. The resulting biogeochemical metal cycles have a strong impact on many other elements including carbon, sulfur, phosphorous, and trace metals.
Negative cerium anomalies in manganese (hydr)oxide precipitates due to cerium oxidation in the presence of dissolved siderophores

NASA Astrophysics Data System (ADS)

Kraemer, Dennis; Tepe, Nathalie; Pourret, Olivier; Bau, Michael

2017-01-01

We present experimental results on the sorption behavior of rare earth elements and yttrium (REY) on precipitating manganese (hydr)oxide in the presence of the biogenic siderophore desferrioxamine B (DFOB). In marked contrast to inorganic systems, where preferential adsorption of HREY and depletion of LREY is commonly observed in manganese (hydr)oxide precipitates, sorption of REY in presence of the DFOB siderophore leads to HREY-depleted and LREY-enriched patterns in the precipitates. Moreover, our data indicate that surface oxidation of Ce(III) to Ce(IV) during sorption onto manganese (hydr)oxides and the resulting development of a positive Ce anomaly, which are commonly observed in inorganic experiments, are prevented in the presence of DFOB. Instead, Ce(III) is oxidized to Ce(IV) but associated with the dissolved desferrioxamine B which forms complexes with Ce(IV), that are at least twenty orders of magnitude more stable than those with Ce(III) and REY(III). The overall result is the formation of a positive Ce anomaly in the solution and a negative Ce anomaly in the Mn (hydr)oxides. The distribution of the strictly trivalent REY and Eu(III) between the manganese (hydr)oxide phase and the remaining ambient solution mimics the distribution of published stability constants for complexes of REY(III) with DFOB, i.e. the heavy REY form more stable complexes with the ligand and hence are better shielded from sorption than the LREY. Surface complexation modeling corroborates our experimental results. Negative Ce anomalies in Mn precipitates have been described from biogenic Mn oxides. Our results provide experimental evidence for the development of negative Ce anomalies in abiogenic Mn (hydr)oxide precipitates and show that the presence of the widespread siderophore desferrioxamine B during mineral precipitation results in HREY-depleted Mn (hydr)oxides with negative Ce anomalies.
Manganese Oxidizing Bacteria in Guaymas Basin Hydrothermal Fluids, Sediments, and Plumes

NASA Astrophysics Data System (ADS)

Dick, G. J.; Tebo, B. M.

2002-12-01

The active seafloor hydrothermal system at Guaymas Basin in the Gulf of California is unique in that spreading centers are covered with thick sediments, and hydrothermal fluids are injected into a semi-enclosed basin. This hydrothermal activity is the source of a large input of dissolved manganese [Mn(II)] into Guaymas Basin, and the presence of a large standing stock of particulate manganese in this basin has been taken as evidence for a short residence time of dissolved Mn(II) with respect to oxidation, suggestive of bacterial catalysis. During a recent Atlantis/Alvin expedition (R/V Atlantis Cruise #7, Leg 11, Jim Cowen Chief Scientist), large amounts of particulate manganese oxides were again observed in Guaymas Basin hydrothermal plumes. The goal of the work presented here was to identify bacteria involved in the oxidation of Mn(II) in Guaymas Basin, and to determine what molecular mechanisms drive this process. Culture-based methods were employed to isolate Mn(II)-oxidizing bacteria from Guaymas Basin hydrothermal fluids, sediments, and plumes, and numerous Mn(II)-oxidizing bacteria were identified based on the formation of orange, brown, or black manganese oxides on bacterial colonies on agar plates. The Mn(II)-oxidizing bacteria were able to grow at temperatures from 12 to 50°C, and a selection of the isolates were chosen for phylogenetic (16S rRNA genes) and microscopic characterization. Endospore-forming Bacillus species accounted for many of the Mn(II)-oxidizing isolates obtained from both hydrothermal sediments and plumes, while members of the alpha- and gamma-proteobacteria were also found. Mn(II)-oxidizing enzymes from previously characterized Bacillus spores are known to be active at temperatures greater than 50°C. The presence of Mn(II)-oxidizing spores - some of which are capable of growing at elevated temperatures - in hydrothermal fluids and sediments at Guaymas Basin suggests that Mn(II) oxidation may be occurring immediately or very soon after hydrothermal fluids emerge from the seafloor.
Low-temperature nitridation of manganese and iron oxides using NaNH2 molten salt.

PubMed

Miura, Akira; Takei, Takahiro; Kumada, Nobuhiro

2013-10-21

Manganese and iron nitrides are important functional materials, but their synthesis processes from oxides often require high temperatures. Herein, we show a novel meta-synthesis method for manganese and iron nitrides by low-temperature nitridation of their oxides using NaNH2 molten salt as the nitrogen source in an autoclave at 240 °C. With this method, nitridation of micrometer-sized oxide particles kept their initial morphologies, but the size of the primary particles decreased. The thermodynamic driving force is considered to be the conversion of oxides to sodium hydroxide, and the kinetic of nitridation is improved by the decrease of particle size and the low melting point of NaNH2. This technique as developed here has the advantages of low reaction temperature, reduced consumption of ammonia, employing nonspecialized equipment, and providing facile control of the reactions for producing nitrides from oxides.
Catalytic oxidation of toluene: comparative study over powder and monolithic manganese-nickel mixed oxide catalysts.

PubMed

Duplančić, Marina; Tomašić, Vesna; Gomzi, Zoran

2017-07-05

This paper is focused on development of the metal monolithic structure for total oxidation of toluene at low temperature. The well-adhered catalyst, based on the mixed oxides of manganese and nickel, is washcoated on the Al/Al 2 O 3 plates as metallic support. For the comparison purposes, results observed for the manganese-nickel mixed oxide supported on the metallic monolith are compared with those obtained using powder type of the same catalyst. Prepared manganese-nickel mixed oxides in both configurations show remarkable low-temperature activity for the toluene oxidation. The reaction temperature T 50 corresponding to 50% of the toluene conversion is observed at temperatures of ca. 400-430 K for the powder catalyst and at ca. 450-490 K for the monolith configuration. The appropriate mathematical models, such as one-dimensional (1D) pseudo-homogeneous model of the fixed bed reactor and the 1D heterogeneous model of the metal monolith reactor, are applied to describe and compare catalytic performances of both reactors. Validation of the applied models is performed by comparing experimental data with theoretical predictions. The obtained results confirmed that the reaction over the monolithic structure is kinetically controlled, while in the case of the powder catalyst the reaction rate is influenced by the intraphase diffusion.
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...
The possibility of multi-layer nanofabrication via atomic force microscope-based pulse electrochemical nanopatterning

NASA Astrophysics Data System (ADS)

Kim, Uk Su; Morita, Noboru; Lee, Deug Woo; Jun, Martin; Park, Jeong Woo

2017-05-01

Pulse electrochemical nanopatterning, a non-contact scanning probe lithography process using ultrashort voltage pulses, is based primarily on an electrochemical machining process using localized electrochemical oxidation between a sharp tool tip and the sample surface. In this study, nanoscale oxide patterns were formed on silicon Si (100) wafer surfaces via electrochemical surface nanopatterning, by supplying external pulsed currents through non-contact atomic force microscopy. Nanoscale oxide width and height were controlled by modulating the applied pulse duration. Additionally, protruding nanoscale oxides were removed completely by simple chemical etching, showing a depressed pattern on the sample substrate surface. Nanoscale two-dimensional oxides, prepared by a localized electrochemical reaction, can be defined easily by controlling physical and electrical variables, before proceeding further to a layer-by-layer nanofabrication process.
Adsorption of NO on alumina-supported oxides and oxide-hydroxides of manganese.

PubMed

Spasova, I; Nikolov, P; Mehandjiev, D

2005-10-15

The adsorption capacity for NO of alumina-supported oxides and oxide-hydroxides of manganese have been studied. Two series of samples have been prepared by precipitation on gamma-alumina and appropriate thermal treatment. The samples have been characterized by adsorption methods, magnetic methods, electronic paramagnetic resonance (EPR), transient response technique, and temperature-programmed desorption (TPD). The influence of the concentration of the initial manganese-containing solution has been investigated. The sample, prepared with a solution with Mn concentration of 4 g/100 ml, has been shown to be the best adsorbent for NO under the conditions of the experiment. It has been found that the presence mainly of Mn3+ ions on the surface of the support is probably responsible for the enhanced adsorption capacity.

Potential Role of Epigenetic Mechanism in Manganese Induced Neurotoxicity

PubMed Central

Tarale, Prashant; Chakrabarti, Tapan; Sivanesan, Saravanadevi; Naoghare, Pravin; Bafana, Amit; Krishnamurthi, Kannan

2016-01-01

Manganese is a vital nutrient and is maintained at an optimal level (2.5–5 mg/day) in human body. Chronic exposure to manganese is associated with neurotoxicity and correlated with the development of various neurological disorders such as Parkinson's disease. Oxidative stress mediated apoptotic cell death has been well established mechanism in manganese induced toxicity. Oxidative stress has a potential to alter the epigenetic mechanism of gene regulation. Epigenetic insight of manganese neurotoxicity in context of its correlation with the development of parkinsonism is poorly understood. Parkinson's disease is characterized by the α-synuclein aggregation in the form of Lewy bodies in neuronal cells. Recent findings illustrate that manganese can cause overexpression of α-synuclein. α-Synuclein acts epigenetically via interaction with histone proteins in regulating apoptosis. α-Synuclein also causes global DNA hypomethylation through sequestration of DNA methyltransferase in cytoplasm. An individual genetic difference may also have an influence on epigenetic susceptibility to manganese neurotoxicity and the development of Parkinson's disease. This review presents the current state of findings in relation to role of epigenetic mechanism in manganese induced neurotoxicity, with a special emphasis on the development of Parkinson's disease. PMID:27314012
Electrode structures and surfaces for Li batteries

DOEpatents

Thackeray, Michael M.; Kang, Sun-Ho; Balasubramanian, Mahalingam; Croy, Jason

2017-03-14

This invention relates to methods of preparing positive electrode materials for electrochemical cells and batteries. It relates, in particular, to a method for fabricating lithium-metal-oxide electrode materials for lithium cells and batteries. The method comprises contacting a hydrogen-lithium-manganese-oxide material with one or more metal ions, preferably in an acidic solution, to insert the one or more metal ions into the hydrogen-lithium-manganese-oxide material; heat-treating the resulting product to form a powdered metal oxide composition; and forming an electrode from the powdered metal oxide composition.
Absorption of Thermal Neutrons in Uranium

DOE R&D Accomplishments Database

Creutz, E. C.; Wilson, R. R.; Wigner, E. P.

1941-09-26

A knowledge of the absorption processes for neutrons in uranium is important for planning a chain reaction experiment. The absorption of thermal neutrons in uranium and uranium oxide has been studied. Neutrons from the cyclotron were slowed down by passage through a graphite block. A uranium or uranium oxide sphere was placed at various positions in the block. The neutron intensity at different points in the sphere and in the graphite was measured by observing the activity induced in detectors or uranium oxide or manganese. It was found that both the fission activity in the uranium oxide and the activity induced in manganese was affected by non-thermal neutrons. An experimental correction for such effects was made by making measurements with the detectors surrounded by cadmium. After such corrections the results from three methods of procedure with the uranium oxide detectors and from the manganese detectors were consistent to within a few per cent.
Electrocatalytic Water Oxidation Promoted by 3 D Nanoarchitectured Turbostratic δ-MnOx on Carbon Nanotubes.

PubMed

Zhang, Biaobiao; Li, Yuanyuan; Valvo, Mario; Fan, Lizhou; Daniel, Quentin; Zhang, Peili; Wang, Linqin; Sun, Licheng

2017-11-23

The development of manganese-based water oxidation electrocatalysts is desirable for the production of solar fuels, as manganese is earth-abundant, inexpensive, non-toxic, and has been employed by the Photosystem II in nature for a billion years. Herein, we directly constructed a 3 D nanoarchitectured turbostratic δ-MnO x on carbon nanotube-modified nickel foam (MnO x /CNT/NF) by electrodeposition and a subsequent annealing process. The MnO x /CNT/NF electrode gives a benchmark catalytic current density (10 mA cm -2 ) at an overpotential (η) of 270 mV under alkaline conditions. A steady current density of 19 mA cm -2 is obtained during electrolysis at 1.53 V for 1.0 h. To the best of our knowledge, this work represents the most efficient manganese-oxide-based water oxidation electrode and demonstrates that manganese oxides, as a structural and functional model of oxygen-evolving complex (OEC) in Photosystem II, can also become comparable to those of most Ni- and Co-based catalysts. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
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.
Exposure, Health and Ecological Effects Review of Engineered Nanoscale Cerium and Cerium Oxide Associated with its Use as a Fuel Additive

EPA Science Inventory

Advances of nanoscale science have produced nanomaterials with unique physical and chemical properties at commercial levels which are now incorporated into over 1000 products. Nanoscale cerium (di) oxide (CeO(2)) has recently gained a wide range of applications which includes coa...
Manganese oxide particles as cytoprotective, oxygen generating agents.

PubMed

Tootoonchi, Mohammad Hossein; Hashempour, Mazdak; Blackwelder, Patricia L; Fraker, Christopher A

2017-09-01

Cell culture and cellular transplant therapies are adversely affected by oxidative species and radicals. Herein, we present the production of bioactive manganese oxide nanoparticles for the purpose of radical scavenging and cytoprotection. Manganese comprises the core active structure of somatic enzymes that perform the same function, in vivo. Formulated nanoparticles were characterized structurally and surveyed for maximal activity (superoxide scavenging, hydrogen peroxide scavenging with resultant oxygen generation) and minimal cytotoxicity (48-h direct exposure to titrated manganese oxide concentrations). Cytoprotective capacity was tested using cell exposure to hydrogen peroxide in the presence or absence of the nanoparticles. Several ideal compounds were manufactured and utilized that showed complete disproportionation of superoxide produced by the xanthine/xanthine oxidase reaction. Further, the nanoparticles showed catalase-like activity by completely converting hydrogen peroxide into the corresponding concentration of oxygen. Finally, the particles protected cells (murine β-cell insulinoma) against insult from hydrogen peroxide exposure. Based on these observed properties, these particles could be utilized to combat oxidative stress and inflammatory response in a variety of cell therapy applications. Maintaining viability once cells have been removed from their physiological niche, e.g. culture and transplant, demands proper control of critical variables such as oxygenation and removal of harmful substances e.g. reactive oxygen species. Limited catalysts can transform reactive oxygen species into molecular oxygen and, thereby, have the potential to maintain cell viability and function. Among these are manganese oxide particles which are the subject of this study. Copyright © 2017 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
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 by Basic Science Research Program through the National Research Foundation of Korea(NRF) funded by the Ministry of Education(NRF-2013R1A1A2004898)"
ADSORPTION OF LEAD FROM A CONTAMINATED SOIL TREATED WITH PHOSPHORUS AND MANGANESE OXIDES BY APRAGUE-DAWLEY RATS

EPA Science Inventory

In addition to the formation of insoluble lead (Pb) compounds as a mean of reducing Pb bioavalability, adsorption is another potentially important process controlling the bioavailability of Pb in soils. Less attention has been given to manganese (Mn) oxides, even though they are ...
ChemCam Update – Manganese Oxides on Mars

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

Lanza, Nina

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.
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. Copyright © 2016 Elsevier Ltd. All rights reserved.
Laser-driven coating of vertically aligned carbon nanotubes with manganese oxide from metal organic precursors for energy storage.

PubMed

Pérez Del Pino, A; György, E; Alshaikh, I; Pantoja-Suárez, F; Andújar, J L; Pascual, E; Amade, R; Bertran-Serra, E

2017-09-29

Carbon nanotubes-transition metal oxide systems are intensively studied due to their excellent properties for electrochemical applications. In this work, an innovative procedure is developed for the synthesis of vertically aligned multi-walled carbon nanotubes (VACNTs) coated with transition metal oxide nanostructures. VACNTs are grown by plasma enhanced chemical vapor deposition and coated with a manganese-based metal organic precursor (MOP) film based on manganese acetate solution. Subsequent UV pulsed laser irradiation induces the effective heating-decomposition of the MOP leading to the crystallization of manganese oxide nanostructures on the VACNT surface. The study of the morphology, structure and composition of the synthesized materials shows the formation of randomly oriented MnO 2 crystals, with few nanometers in size, and to their alignment in hundreds of nm long filament-like structures, parallel to the CNT's long axis. Electrochemical measurements reveal a significant increase of the specific capacitance of the MnO 2 -VACNT system (100 F g -1 ) as compared to the initial VACNT one (21 F g -1 ).
Laser-driven coating of vertically aligned carbon nanotubes with manganese oxide from metal organic precursors for energy storage

NASA Astrophysics Data System (ADS)

Pérez del Pino, A.; György, E.; Alshaikh, I.; Pantoja-Suárez, F.; Andújar, J. L.; Pascual, E.; Amade, R.; Bertran-Serra, E.

2017-09-01

Carbon nanotubes-transition metal oxide systems are intensively studied due to their excellent properties for electrochemical applications. In this work, an innovative procedure is developed for the synthesis of vertically aligned multi-walled carbon nanotubes (VACNTs) coated with transition metal oxide nanostructures. VACNTs are grown by plasma enhanced chemical vapor deposition and coated with a manganese-based metal organic precursor (MOP) film based on manganese acetate solution. Subsequent UV pulsed laser irradiation induces the effective heating-decomposition of the MOP leading to the crystallization of manganese oxide nanostructures on the VACNT surface. The study of the morphology, structure and composition of the synthesized materials shows the formation of randomly oriented MnO2 crystals, with few nanometers in size, and to their alignment in hundreds of nm long filament-like structures, parallel to the CNT’s long axis. Electrochemical measurements reveal a significant increase of the specific capacitance of the MnO2-VACNT system (100 F g-1) as compared to the initial VACNT one (21 F g-1).
Water oxidation chemistry of photosystem II.

PubMed Central

Vrettos, John S; Brudvig, Gary W

2002-01-01

The O(2)-evolving complex of photosystem II catalyses the light-driven four-electron oxidation of water to dioxygen in photosynthesis. In this article, the steps leading to photosynthetic O(2) evolution are discussed. Emphasis is given to the proton-coupled electron-transfer steps involved in oxidation of the manganese cluster by oxidized tyrosine Z (Y(*)(Z)), the function of Ca(2+) and the mechanism by which water is activated for formation of an O-O bond. Based on a consideration of the biophysical studies of photosystem II and inorganic manganese model chemistry, a mechanism for photosynthetic O(2) evolution is presented in which the O-O bond-forming step occurs via nucleophilic attack on an electron-deficient Mn(V)=O species by a calcium-bound water molecule. The proposed mechanism includes specific roles for the tetranuclear manganese cluster, calcium, chloride, Y(Z) and His190 of the D1 polypeptide. Recent studies of the ion selectivity of the calcium site in the O(2)-evolving complex and of a functional inorganic manganese model system that test key aspects of this mechanism are also discussed. PMID:12437878
Distribution and genetic diversity of the microorganisms in the biofilter for the simultaneous removal of arsenic, iron and manganese from simulated groundwater.

PubMed

Yang, Liu; Li, Xiangkun; Chu, Zhaorui; Ren, Yuhui; Zhang, Jie

2014-03-01

A biofilter was developed in this study, which showed an excellent performance with the simultaneous removal of AsIII from 150 to 10mg L(-1) during biological iron and manganese oxidation. The distribution and genetic diversity of the microorganisms along the depth of the biofilter have been investigated using DGGE. Results suggested that Iron oxidizing bacteria (IOB, such as Gallionella, Leptothrix), Manganese oxidizing bacteria (MnOB, such as Leptothrix, Pseudomonas, Hyphomicrobium, Arthrobacter) and AsIII-oxidizing bacteria (AsOB, such as Alcaligenes, Pseudomonas) are dominant in the biofilter. The spatial distribution of IOB, MnOB and AsOB at different depths of the biofilter determined the removal zone of FeII, MnII and AsIII, which site at the depths of 20, 60 and 60cm, respectively, and the corresponding removal efficiencies were 86%, 84% and 87%, respectively. This process shows great potential to the treatment of groundwater contaminated with iron, manganese and arsenic due to its stable performance and significant cost-savings. Copyright © 2014 Elsevier Ltd. All rights reserved.
Calcium-manganese oxides as structural and functional models for active site in oxygen evolving complex in photosystem II: lessons from simple models.

PubMed

Najafpour, Mohammad Mahdi

2011-01-01

The oxygen evolving complex in photosystem II which induces the oxidation of water to dioxygen in plants, algae and certain bacteria contains a cluster of one calcium and four manganese ions. It serves as a model to split water by sunlight. Reports on the mechanism and structure of photosystem II provide a more detailed architecture of the oxygen evolving complex and the surrounding amino acids. One challenge in this field is the development of artificial model compounds to study oxygen evolution reaction outside the complicated environment of the enzyme. Calcium-manganese oxides as structural and functional models for the active site of photosystem II are explained and reviewed in this paper. Because of related structures of these calcium-manganese oxides and the catalytic centers of active site of the oxygen evolving complex of photosystem II, the study may help to understand more about mechanism of oxygen evolution by the oxygen evolving complex of photosystem II. Copyright © 2010 Elsevier B.V. All rights reserved.
Microstructural characterization of the cycling behavior of electrodeposited manganese oxide supercapacitors using 3D electron tomography

NASA Astrophysics Data System (ADS)

Dalili, N.; Clark, M. P.; Davari, E.; Ivey, D. G.

2016-10-01

Manganese oxide has been investigated extensively as an electrochemical capacitor or supercapacitor electrode material. Manganese oxide is inexpensive to fabricate and exhibits relatively high capacitance values, i.e., in excess of 200 F g-1 in many cases; the actual value depends very much on the fabrication method and test conditions. The cycling behavior of Mn oxide, fabricated using anodic electrodeposition, is investigated using slice and view techniques, via a dual scanning electron microscope (SEM) and focused ion beam (FIB) instrument to generate three-dimensional (3D) images, coupled with electrochemical characterization. The initial as-fabricated electrode has a rod-like appearance, with a fine-scale, sheet-like morphology within the rods. The rod-like structure remains after cycling, but there are significant morphological changes. These include partial dissolution of Mn oxide followed by redeposition of Mn oxide in regions close to the substrate. The redeposited material has a finer morphology than the original as-fabricated Mn oxide. The Mn oxide coverage is also better near the substrate. These effects result in an increase in the specific capacitance.
Reactivity of biogenic manganese oxide for metal sequestration and photochemistry: Computational solid state physics study (in Korean)

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

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.
Manganese enhances peroxynitrite and leukotriene E4 formation in bovine aortic endothelial cells exposed to arsenic.

PubMed

Bunderson, Melisa; Pereira, Flavia; Schneider, Mark C; Shaw, Pamela K; Coffin, J Douglas; Beall, Howard D

2006-01-01

Long-term exposure to arsenic in drinking water has been linked to cancer and other health effects, including cardiovascular disease. Arsenic in the environment is found in combination with a range of metals that could influence its toxicity. Manganese, in particular, is a metal that is typically found in conjunction with arsenic in contaminated groundwater. Peroxynitrite is a powerful oxidant formed from the reaction between nitric oxide and superoxide anion. Arsenic has been shown to increase the formation of peroxynitrite in bovine aortic endothelial cells (BAECs) and promote the formation of 3-nitrotyrosine (3-NY) in the atherosclerotic plaque of ApoE-/-/LDLr-/- mice. Arsenic exposure also increases leukotriene E4 (LTE4) formation in both the mice and BAECs, an effect that is partially reversed by the addition of Nomega-nitro-L-arginine methyl ester (L-NAME), a nitric oxide synthase (NOS) inhibitor. In the present study, we investigated the effect of adding nontoxic concentrations of manganese along with arsenic to BAEC cultures. Manganese increased arsenic toxicity and enhanced peroxynitrite, 3-NY, and LTE4 formation in BAECs. Addition of LNAME reduced 3-NY formation induced by arsenic/manganese mixtures, but in contrast to its effect on arsenic alone, L-NAME actually increased LTE4 synthesis in BAECs treated with the arsenic/manganese combination. Overall, these data suggest that manganese may exacerbate the toxic effects of arsenic on the vascular system.
Matrix effects on the determination of manganese in geological materials by atomic-absorption spectrophotometry under different flame conditions

USGS Publications Warehouse

Sanzolone, R.F.; Chao, T.T.

1978-01-01

Suppression caused by five of the seven matrix elements studied (Si, Al, Fe, Ca and Mg) was observed in the atomic-absorption determination of manganese in geological materials, when synthetic solutions and the recommended oxidizing air-acetylene flame were used. The magnitude of the suppression effects depends on (1) the kind and concentration of the interfering elements, (2) the type of acid medium, and (3) the concentration of manganese to be determined. All interferences noted are removed or alleviated by using a reducing nitrous oxide-acetylene flame. The atomic-absorption method using this flame can be applied to the determination of total and extractable manganese in a wide range of geological materials without interferences. Analyses of six U.S. Geological Survey rock standards for manganese gave results in agreement with the reported values. ?? 1978.

Simple Methods for Production of Nanoscale Metal Oxide Films from Household Sources

ERIC Educational Resources Information Center

Campbell, Dean J.; Baliss, Michelle S.; Hinman, Jordan J.; Ziegenhorn, John W.; Andrews, Mark J.; Stevenson, Keith J.

2013-01-01

Production of thin metal oxide films was recently explored as part of an outreach program with a goal of producing nanoscale structures with household items. Household items coated with various metals or titanium compounds can be heated to produce colorful films with nanoscale thicknesses. As part of a materials chemistry laboratory experiment…
Electrochemical oxidation of sulfites by DWCNTs, MWCNTs, higher fullerenes and manganese

NASA Astrophysics Data System (ADS)

Uzun, Dzhamal; Pchelarov, George; Dimitrov, Ognian; Vassilev, Sasho; Obretenov, Willi; Petrov, Konstantin

2018-03-01

Different electrocatalysts were tested for oxidation of sulfites to sulfates, namely, manganese thin films deposited on fullerenes and carbon nanotubes. The results presented clearly show that electrodes containing HFs (higher fullerenes), DWCNTs (double-wall carbon nanotubes) and manganese acetate are effective catalysts in S/O2 fuel cells. HFs and DWCNTs have high catalytic activity and can be employed as standalone catalysts. Manganese was deposited on DWCNTs, HFs and fullerenes C60/C70 by a thermal process. The electrocatalysts were characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD). The electrochemical testing was carried out by plotting the E/V polarization curve. The polarization curves of the electrodes composed of pristine DWCNTs showed the lowest overpotentials.
Bacterially mediated diagenetic origin for chert-hosted manganese deposits in the Franciscan Complex, California Coast Ranges

NASA Astrophysics Data System (ADS)

Hein, James R.; Koski, Randolph A.

1987-08-01

Numerous manganese deposits in the Franciscan Complex, California, occur as conformable lenses within bedded radiolarian chert-argillite sequences that are, in turn, intercalated within thicker sections of sandstone and shale. The field relations, composition, and petro-graphic and isotopic characteristics indicate that the manganese was concentrated by diagenetic reconstitution of siliceous and hemipelagic sediment during burial. The ore lenses are Mn-rich and Fe-poor assemblages consisting largely of rhodochrosite, manganese silicates, opal-CT (disordered cristobalite-tridymite), and quartz. Highly negative δ13C values for the carbonate carbon in rhodochrosite indicate that CO2 likely originated from oxidation of methane; less negative values result from mixing of methanogenic carbon and CO2 derived from bacterial degradation of organic matter. The δ18O values for the carbonate of rhodochrosite indicate temperatures of formation between 12 and 100 °C. The oxidation of methane prior to carbonate precipitation may have used the minor (0.4% 0.5%) Mn and Fe oxyhydroxides and oxides deposited with the sediment. The mobilization of manganese from biogenic and terrigenous sources in the sediment column into discrete horizons and the fractioriation of manganese from iron reflect the presence of oxidation-reduction boundaries and gradients in the sediment column. Fluids derived from compaction and silica-dehydration reactions in the transformation of opal-A (X-ray amorphous biogenic silica) to quartz were involved in transportation of principal components. Sedimentary and geochemical attributes suggest that the deposits formed in a deep-water environment in a zone of oceanic upwelling near a continental margin.
ChemCam Update â Manganese Oxides on Mars

ScienceCinema

Lanza, Nina

2018-01-16

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.
Microbiologically Influenced Corrosion

DTIC Science & Technology

2009-01-01

related directly to the biomineralized deposits on the surface. Ennoble- ment in marine waters has been attributed to depolarization of the oxygen... abiotic ally oxi- dized metal precipitates, and still others that derive energy by oxidizing metals. Manganese. Manganese oxidation is coupled to cell...circumstances, pitting involves the conventional features of differential aeration, a large cathode: anode surface area, and the development of
Biological water-oxidizing complex: a nano-sized manganese-calcium oxide in a protein environment.

PubMed

Najafpour, Mohammad Mahdi; Moghaddam, Atefeh Nemati; Yang, Young Nam; Aro, Eva-Mari; Carpentier, Robert; Eaton-Rye, Julian J; Lee, Choon-Hwan; Allakhverdiev, Suleyman I

2012-10-01

The resolution of Photosystem II (PS II) crystals has been improved using isolated PS II from the thermophilic cyanobacterium Thermosynechococcus vulcanus. The new 1.9 Å resolution data have provided detailed information on the structure of the water-oxidizing complex (Umena et al. Nature 473: 55-61, 2011). The atomic level structure of the manganese-calcium cluster is important for understanding the mechanism of water oxidation and to design an efficient catalyst for water oxidation in artificial photosynthetic systems. Here, we have briefly reviewed our knowledge of the structure and function of the cluster.
Laser Flash Photolysis Generation of High-Valent Transition Metal-Oxo Species: Insights from Kinetic Studies in Real Time

PubMed Central

Zhang, Rui; Newcomb, Martin

2010-01-01

Conspectus High-valent transition metal-oxo species are active oxidizing species in many metal-catalyzed oxidation reactions in both Nature and the laboratory. In homogeneous catalytic oxidations, a transition metal catalyst is oxidized to a metal-oxo species by a sacrificial oxidant, and the activated transition metal-oxo intermediate oxidizes substrates. Mechanistic studies of these oxidizing species can provide insights for understanding commercially important catalytic oxidations and the oxidants in cytochrome P450 enzymes. In many cases, however, the transition metal oxidants are so reactive that they do not accumulate to detectable levels in mixing experiments, which have millisecond mixing times, and successful generation and direct spectroscopic characterization of these highly reactive transients remain a considerable challenge. Our strategy for understanding homogeneous catalysis intermediates employs photochemical generation of the transients with spectroscopic detection on time-scales as short as nanoseconds and direct kinetic studies of their reactions with substrates by laser flash photolysis (LFP) methods. This Account describes studies of high-valent manganese- and iron-oxo intermediates. Irradiation of porphyrin-manganese(III) nitrates and chlorates or corrole-manganese(IV) chlorates resulted in homolytic cleavage of the O-X bonds in the ligands, whereas irradiation of porphyrin-manganese(III) perchlorates resulted in heterolytic cleavage of O-Cl bonds to give porphyrin-manganese(V)-oxo cations. Similar reactions of corrole- and porphyrin-iron(IV) complexes gave highly reactive transients that were tentatively identified as macrocyclic ligand-iron(V)-oxo species. Kinetic studies demonstrated high reactivity of the manganese(V)-oxo species, and even higher reactivities of the putative iron(V)-oxo transients. For example, second-order rate constants for oxidations of cis-cyclooctene at room temperature were 6 × 103 M−1 s−1 for a corrole-iron(V)-oxo species and 1.6 × 106 M−1 s−1 for the putative tetramesitylporphyrin-iron(V)-oxo perchlorate species. The latter rate constant is 25,000 times larger than that for oxidation of cis-cyclooctene by iron(IV)-oxo perchlorate tetramesitylporphyrin radical cation, which is the thermodynamically favored electronic isomer of the putative iron(V)-oxo species. The LFP-determined rate constants can be used to implicate the transient oxidants in catalytic reactions under turnover conditions where high-valent species are not observable. Similarly, the observed reactivities of the putative porphyrin-iron(V)-oxo species might explain the unusually high reactivity of oxidants produced in the cytochrome P450 enzymes, heme-thiolate enzymes that are capable of oxidizing unactivated carbon-hydrogen bonds in substrates so rapidly that iron-oxo intermediates have not been detected under physiological conditions. PMID:18278877
Laser flash photolysis generation of high-valent transition metal-oxo species: insights from kinetic studies in real time.

PubMed

Zhang, Rui; Newcomb, Martin

2008-03-01

High-valenttransition metal-oxo species are active oxidizing species in many metal-catalyzed oxidation reactions in both Nature and the laboratory. In homogeneous catalytic oxidations, a transition metal catalyst is oxidized to a metal-oxo species by a sacrificial oxidant, and the activated transition metal-oxo intermediate oxidizes substrates. Mechanistic studies of these oxidizing species can provide insights for understanding commercially important catalytic oxidations and the oxidants in cytochrome P450 enzymes. In many cases, however, the transition metal oxidants are so reactive that they do not accumulate to detectable levels in mixing experiments, which have millisecond mixing times, and successful generation and direct spectroscopic characterization of these highly reactive transients remain a considerable challenge. Our strategy for understanding homogeneous catalysis intermediates employs photochemical generation of the transients with spectroscopic detection on time scales as short as nanoseconds and direct kinetic studies of their reactions with substrates by laser flash photolysis (LFP) methods. This Account describes studies of high-valent manganese- and iron-oxo intermediates. Irradiation of porphyrin-manganese(III) nitrates and chlorates or corrole-manganese(IV) chlorates resulted in homolytic cleavage of the O-X bonds in the ligands, whereas irradiation of porphyrin-manganese(III) perchlorates resulted in heterolytic cleavage of O-Cl bonds to give porphyrin-manganese(V)-oxo cations. Similar reactions of corrole- and porphyrin-iron(IV) complexes gave highly reactive transients that were tentatively identified as macrocyclic ligand-iron(V)-oxo species. Kinetic studies demonstrated high reactivity of the manganese(V)-oxo species, and even higher reactivities of the putative iron(V)-oxo transients. For example, second-order rate constants for oxidations of cis-cyclooctene at room temperature were 6 x 10(3) M(-1) s(-1) for a corrole-iron(V)-oxo species and 1.6 x 10(6) M(-1) s(-1) for the putative tetramesitylporphyrin-iron(V)-oxo perchlorate species. The latter rate constant is 25,000 times larger than that for oxidation of cis-cyclooctene by iron(IV)-oxo perchlorate tetramesitylporphyrin radical cation, which is the thermodynamically favored electronic isomer of the putative iron(V)-oxo species. The LFP-determined rate constants can be used to implicate the transient oxidants in catalytic reactions under turnover conditions where high-valent species are not observable. Similarly, the observed reactivities of the putative porphyrin-iron(V)-oxo species might explain the unusually high reactivity of oxidants produced in the cytochrome P450 enzymes, heme-thiolate enzymes that are capable of oxidizing unactivated carbon-hydrogen bonds in substrates so rapidly that iron-oxo intermediates have not been detected under physiological conditions.
Suppressing Manganese Dissolution from Lithium Manganese Oxide Spinel Cathodes with Single-Layer Graphene

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

Jaber-Ansari, Laila; Puntambekar, Kanan P.; Kim, Soo

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, transmissionmore » 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.« less
Catalytic wet oxidation of ammonia solution: activity of the nanoscale platinum-palladium-rhodium composite oxide catalyst.

PubMed

Hung, Chang-Mao

2009-04-15

Aqueous solutions of 400-1000 mg/L of ammonia were oxidized in a trickle-bed reactor (TBR) in this study of nanoscale platinum-palladium-rhodium composite oxide catalysts, which were prepared by the co-precipitation of H(2)PtCl(6), Pd(NO(3))(3) and Rh(NO(3))(3). Hardly any of the dissolved ammonia was removed by wet oxidation in the absence of any catalyst, whereas about 99% of the ammonia was reduced during wet oxidation over nanoscale platinum-palladium-rhodium composite oxide catalysts at 503 K in an oxygen partial pressure of 2.0 MPa. A synergistic effect exists in the nanoscale platinum-palladium-rhodium composite structure, which is the material with the highest ammonia reduction activity. The nanometer-sized particles were characterized by TEM, XRD and FTIR. The effect of the initial concentration and reaction temperature on the removal of ammonia from the effluent streams was also studied at a liquid hourly space velocity of under 9 h(-1) in the wet catalytic processes.
Oxidation of dimethylselenide by δMnO2: oxidation product and factors affecting oxidation rate

USGS Publications Warehouse

Wang, Bronwen; Burau, Richard G.

1995-01-01

Volatile dimethylselenide (DMSe) was transformed to a nonvolatile Se compound in a ??-MnO2 suspension. The nonvolatile product was a single compound identified as dimethylselenoxide based on its mass spectra pattern. After 24 h, 100% of the DMSe added to a ??-MnO2 suspension was converted to nonpurgable Se as opposed to 20%, 18%, and 4% conversion for chromate, permanganate, and the filtrate from the suspension, respectively. Manganese was found in solution after reaction. These results imply that the reaction between manganese oxide and DMSe was a heterogeneous redox reaction involving solid phase ??-MnO2 and solution phase DMSe. Oxidation of DMSe to dimethylselenoxide [OSe(CH3)2] by a ??-MnO2 suspension appears to be first order with respect to ??-MnO2, to DMSe, and to hydrogen ion with an overall rate law of d[OSe(CH3)2 ]/dt = 95 M-2 min-1 [MnO2]1[DMSe]1[H+]1 for the MnO2 concentration range of 0.89 ?? 10-3 - 2.46 ?? 10-3 M, the DMSe concentration range of 3.9 ?? 10-7 - 15.5 ?? 10-7 M Se, and a hydrogen ion concentation range of 7.4 ?? 10-6 -9.5 ?? 10-8 M. A general surface site adsorption model is consistent with this rate equation if the uncharged |OMnOH is the surface adsorption site. DMSe acts as a Lewis base, and the manganese oxide surface acts as a Lewis acid. DMSe adsorption to |OMnOH can be viewed as a Lewis acid/ base complex between the largely p orbitals of the DMSe lone pair and the unoccupied eg orbitals on manganese oxide. For such a complex, frontier molecular orbital theory predicts electron transfer to occur via an inner-sphere complex between the DMSe and the manganese oxide. ?? 1995 American Chemical Society.
Low power loss and field-insensitive permeability of Fe-6.5%Si powder cores with manganese oxide-coated particles

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

Li, Junnan, E-mail: junnanli1991@163.com, E-mail: rzhgong@hust.edu.cn; Wang, Xian; Xu, Xiaojun

Fe-6.5%Si alloy powders coated with manganese oxides using an innovative in situ process were investigated. The in-situ coating of the insulating oxides was realized with a KMnO{sub 4} solution by a chemical process. The insulating manganese oxides with mixed valance state were verified by X-ray photoelectron spectroscopy analysis. The thickness of the insulating layer on alloy particles was determined to be in a range of 20–210 nm, depending upon the KMnO{sub 4} concentration. The powder core loss and the change in permeability under a DC-bias field were measured at frequencies ranging from 50 to 100 kHz. The experiments indicated that themore » Fe-6.5%Si powder cores with a 210 nm-thick manganese oxide layer not only showed a low core loss of 459 mW/cm{sup 3} at 100 kHz but also showed a small reduction in permeability (μ(H)/μ(0) = 85% for μ = 42) at a DC-bias field of 80 Oe. This work has defined a novel pathway to realizing low core loss and field-insensitive permeability for Fe-Si powder cores.« less
Preliminary reconnaissance survey for thorium, uranium, and rare-earth oxides, Bear Lodge Mountains, Crook County, Wyoming

USGS Publications Warehouse

Wilmarth, V.R.; Johnson, D.H.

1953-01-01

An area about 6 miles north of Sundance, in the Bear Lodge Mountains, in Crook County, Wyo., was examined during August 1950 for thorium, uranium, and rare-earth oxides and samples were collected. Uranium is known to occur in fluorite veins and iron-manganese veins and in the igneous rocks of Tertiary age that compose the core of the Bear Lodge Mountains. The uranium content of the samples ranges from 0.001 to 0.015 percent in those from the fluorite veins, from 0.005 to 0.018 percent in those from the iron-manganese veins, and from 0.001 to 0.017 percent in those from the igneous rocks. The radioactivity of the samples is more than that expected from the uranium content. Thorium accounts for most of this discrepancy. The thorium oxide content of samples ranges from 0.07 to 0.25 percent in those from the iron-manganese veins and from 0.07 to 0.39 percent in those from the sedimentary rocks, and from0.04 to 0.30 in those from the igneous rocks. Rare-earth oxides occur in iron-manganese veins and in zones of altered igneous rocks. The veins contain from 0.16 to 12.99 percent rare-earth oxides, and the igneous rocks, except for two localities, contain from 0.01 to 0.42 percent rare-earth oxides. Inclusions of metamorphosed sedimentary rocks in the intrusive rocks contain from 0.07 to 2.01 percent rare-earth oxides.
A kinetic study of the enhancement of solution chemiluminescence of glyoxylic acid oxidation by manganese species.

PubMed

Otamonga, Jean-Paul; Abdel-Mageed, Amal; Agater, Irena B; Jewsbury, Roger A

2015-08-01

In order to study the mechanism of the enhancement of solution chemiluminescence, the kinetics of the decay of the oxidant and the chemiluminescence emission were followed for oxidations by permanganate, manganese dioxide sol and Mn(3+) (aq) of glyoxylic acid, using stopped-flow spectrophotometry. Results are reported for the glyoxylic acid oxidized under pseudo first-order conditions and in an acidic medium at 25 °C. For permanganate under these conditions, the decay is sigmoidal, consistent with autocatalysis, and for manganese dioxide sol and Mn(3+) it is pseudo first order. The effects of the presence of aqueous formaldehyde and Mn(2+) were observed and a fit to a simple mechanism is discussed. It is concluded that chemiluminescent enhancement in these systems is best explained by reaction kinetics. Copyright © 2014 John Wiley & Sons, Ltd.
Effect of trace metals and sulfite oxidation of adipic acid degradation in FGD systems. Final report Dec 81-May 82

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

Jarvis, J.B.; Terry, J.C.; Schubert, S.A.

The report gives results of the measurement of the adipic acid degradation rate in a bench-scale flue gas desulfurization (FGD) system, designed to simulate many of the important aspects of full-scale FGD systems. Results show that the adipic acid degradation rate depends on the sulfite oxidation rate, the adipic acid concentration, the presence of manganese in solution, and temperature. The degradation rate is also affected by pH, but only when manganese is present. Adipic acid degradation products identified in the liquid phase include valeric, butyric, propionic, succinic, and glutaric acids. When manganese was present, the predominant degradation products were succinicmore » and glutaric acids. Analysis of solids from the bench scale tests shows large concentrations of coprecipitated adipic acid in low oxidation sulfite solids. By contrast, low quantities of coprecipitated adipic acid were found in high oxidation gypsum solids.« less
Influence of cobalt and manganese content on the dehydrogenation capacity and kinetics of air-exposed LaNi 5+ x-type alloys in solid gas and electrochemical reactions

NASA Astrophysics Data System (ADS)

Raekelboom, E.; Cuevas, F.; Knosp, B.; Percheron-Guégan, A.

The effect of cobalt and manganese content on the dehydrogenation properties of air-exposed MmB 5+ x-type (Mm = mischmetal; B = Ni, Al, Co and Mn) alloys was investigated both in solid gas and electrochemical reactions. The cobalt and manganese content were varied separately while keeping constant the plateau pressure of the hydrides. The increase of the cobalt content leads to a decrease of the hydrogen capacity whereas the manganese content has no much effect. In solid gas reactions, the kinetics were found to be limited by the hydrogen diffusion through the surface oxidation layer. As for the electrochemistry, the kinetics are limited by a corrosion layer formed in alkaline medium. The desorption rates for both processes increase as the cobalt or manganese content decreases. This is thought to be due to an enhancement of the hydrogen diffusivity through the oxidation layer. As a result, a low cobalt or manganese content in MmB 5+ x alloys is found to be beneficial for the hydrogen desorption kinetics in both processes.
Synthesis and Characterization of Mixed Iron-Manganese Oxide Nanoparticles and Their Application for Efficient Nickel Ion Removal from Aqueous Samples

PubMed Central

Serra, Antonio; Monteduro, Anna Grazia; Padmanabhan, Sanosh Kunjalukkal; Licciulli, Antonio; Bonfrate, Valentina; Salvatore, Luca; Calcagnile, Lucio

2017-01-01

Mixed iron-manganese oxide nanoparticles, synthesized by a simple procedure, were used to remove nickel ion from aqueous solutions. Nanostructures, prepared by using different weight percents of manganese, were characterized by transmission electron microscopy, selected area diffraction, X-ray diffraction, Raman spectroscopy, and vibrating sample magnetometry. Adsorption/desorption isotherm curves demonstrated that manganese inclusions enhance the specific surface area three times and the pores volume ten times. This feature was crucial to decontaminate both aqueous samples and food extracts from nickel ion. Efficient removal of Ni2+ was highlighted by the well-known dimethylglyoxime test and by ICP-MS analysis and the possibility of regenerating the nanostructure was obtained by a washing treatment in disodium ethylenediaminetetraacetate solution. PMID:28804670
Isolation of iron bacteria from terrestrial and aquatic environments

NASA Astrophysics Data System (ADS)

Schmidt, Bertram; Szewzyk, Ulrich

2010-05-01

Bacteria, which are capable of iron oxidation or at least iron deposition are widely distributed in environments where zones of dissolved ferrous iron and oxygen gradients are overlapping [1]. They take part in the biological cycling of iron and influence other cycles of elements for example carbon [2]. Manganese can be used for similar metabolic purposes as iron, because it can be biologically oxidized by chemolithotrophs or can be reduced by respirating bacteria as well [3, 4]. Bacterial activity is responsible for the accumulation of ferric iron compounds in their surroundings. The formation of bog ore is a well known example for a soil horizon, with an extreme enrichment of biogenic ferric iron [5]. We focused on the isolation of neutrophilic iron bacteria and bacteria capable of manganese oxidation. We used samples from Tierra del Fuego (Argentina) the National Park "Unteres Odertal" (Germany) and Berlin ground water wells. Microscopic examination of the samples revealed a considerable diversity of iron encrusted structures of bacterial origin. Most of these morphologic types are already well known. The taxonomic classification of many of these organisms is based on morphologic features and is not reliable compared to recent methods of molecular biology. That is mainly due to the fact, that most of these bacteria are hardly culturable or do not show their characteristic morphologic features under culture conditions. We established a collection of more than 300 iron depositing strains. Phylogenetic analyses showed that we have many yet uncultured strains in pure culture. We obtained many isolates which form distinct branches within long known iron bacteria groups like the Sphaerotilus-Leptothrix cluster. But some of the strains belong to groups, which have not yet been associated with iron oxidation activity. The strains deposit high amounts of oxidized iron and manganese compounds under laboratory conditions. However it is unclear if these precipitations are due to biological oxidation or biological deposition of chemically oxidized iron. We examined the morphologic characteristics of selected isolates under near-natural conditions to assign them to morphologic structures which occur in native samples. Our aim for the future is to describe several strains. References: [1] Weber, K. A. ; Achenbach, L. A. ; Coates, J. D. : Microorganisms pumping iron: anaerobic microbial iron oxidation and reduction. In: Nature Reviews Microbiology 4 (2006) 752-764 [2] Van Capellen, P. ; Wang Y. : Cycling of iron and manganese in surface sediments: a general theory for the coupled transport and reaction of carbon, oxygen, nitrogen, sulfur, iron and manganese. In: American Journal of Science 296 (1996) 197-243 [3] Tebo, B. M. ; Bargar, J. R. ; Clement, B. G. ; Dick, G. J. ; Murray, K. J. ; Parker, D. Verity R. ; Webb, S. M. : Biogenic manganese oxides: properties and mechanisms of formation. In: Annual Reviews Earth Planet Science 32 (2004) 287-328 [4] Erlich, H. L. : Manganese oxide reduction as a form of anaerobic respiration. In: Geomicrobiology Journal 5 (1987) 423-431 [5] Ghiorse W. C. : Biology of iron- and manganese-depositing bacteria. In: Annual Reviews 38 (1984) 515-550
Chemical synthesis of oriented ferromagnetic LaSr-2 × 4 manganese oxide molecular sieve nanowires

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

Carretero-Genevrier, Adrián; Gazquez, Jaume; Magen, Cesar

2012-04-25

Here we report a chemical solution based method using nanoporous track-etched polymer templates for producing long and oriented LaSr-2 × 4 manganese oxide molecular sieve nanowires. Scanning transmission electron microscopy and electron energy loss spectroscopy analyses show that the nanowires are ferromagnetic at room temperature, single crystalline, epitaxially grown and self-aligned.
Mechanisms of Bond Cleavage during Manganese Oxide and UV Degradation of Glyphosate: Results from Phosphate Oxygen Isotopes and Molecular Simulations.

PubMed

Jaisi, Deb P; Li, Hui; Wallace, Adam F; Paudel, Prajwal; Sun, Mingjing; Balakrishna, Avula; Lerch, Robert N

2016-11-16

Degradation of glyphosate in the presence of manganese oxide and UV light was analyzed using phosphate oxygen isotope ratios and density function theory (DFT). The preference of C-P or C-N bond cleavage was found to vary with changing glyphosate/manganese oxide ratios, indicating the potential role of sorption-induced conformational changes on the composition of intermediate degradation products. Isotope data confirmed that one oxygen atom derived solely from water was incorporated into the released phosphate during glyphosate degradation, and this might suggest similar nucleophilic substitution at P centers and C-P bond cleavage both in manganese oxide- and UV light-mediated degradation. The DFT results reveal that the C-P bond could be cleaved by water, OH - or • OH, with the energy barrier opposing bond dissociation being lowest in the presence of the radical species, and that C-N bond cleavage is favored by the formation of both nitrogen- and carbon-centered radicals. Overall, these results highlight the factors controlling the dominance of C-P or C-N bond cleavage that determines the composition of intermediate/final products and ultimately the degradation pathway.

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

DOE PAGES

Ruther, Rose E.; Callender, Andrew F.; Zhou, Hui; ...

2014-11-15

Lithium-rich and manganese-rich (LMR) layered transition metal (TM) oxide composites with general formula xLi 2MnO 3·(1-x)LiMO 2 (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 microscopymore » 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.« less
Magnetic Analysis Techniques Applied to Desert Varnish

NASA Technical Reports Server (NTRS)

Schmidgall, E. R.; Moskowitz, B. M.; Dahlberg, E. D.; Kuhlman, K. R.

2003-01-01

Desert varnish is a black or reddish coating commonly found on rock samples from arid regions. Typically, the coating is very thin, less than half a millimeter thick. Previous research has shown that the primary components of desert varnish are silicon oxide clay minerals (60%), manganese and iron oxides (20-30%), and trace amounts of other compounds [1]. Desert varnish is thought to originate when windborne particles containing iron and manganese oxides are deposited onto rock surfaces where manganese oxidizing bacteria concentrate the manganese and form the varnish [4,5]. If desert varnish is indeed biogenic, then the presence of desert varnish on rock surfaces could serve as a biomarker, indicating the presence of microorganisms. This idea has considerable appeal, especially for Martian exploration [6]. Magnetic analysis techniques have not been extensively applied to desert varnish. The only previous magnetic study reported that based on room temperature demagnetization experiments, there were noticeable differences in magnetic properties between a sample of desert varnish and the substrate sandstone [7]. Based upon the results of the demagnetization experiments, the authors concluded that the primary magnetic component of desert varnish was either magnetite (Fe3O4) or maghemite ( Fe2O3).
Multimode resistive switching in nanoscale hafnium oxide stack as studied by atomic force microscopy

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

Hou, Y., E-mail: houyi@pku.edu.cn, E-mail: lfliu@pku.edu.cn; IMEC, Kapeldreef 75, B-3001 Heverlee; Department of Physics and Astronomy, KU Leuven, Celestijnenlaan 200D, B-3001 Heverlee

2016-07-11

The nanoscale resistive switching in hafnium oxide stack is investigated by the conductive atomic force microscopy (C-AFM). The initial oxide stack is insulating and electrical stress from the C-AFM tip induces nanometric conductive filaments. Multimode resistive switching can be observed in consecutive operation cycles at one spot. The different modes are interpreted in the framework of a low defect quantum point contact theory. The model implies that the optimization of the conductive filament active region is crucial for the future application of nanoscale resistive switching devices.
76 FR 66684 - Foreign-Trade Zone 29-Louisville, KY, Application for Subzone; North American Stainless...

Federal Register 2010, 2011, 2012, 2013, 2014

2011-10-27

...) include: fluorospar, molybdenum oxide, ferromanganese, ferrosilicon, ferrosilicon manganese, charge chrome... spent anodes, nickel, unwrought nickel alloys, aluminum, zinc, zinc alloys, manganese metal, titanium...
Manganese-catalyzed selective oxidation of aliphatic C-H groups and secondary alcohols to ketones with hydrogen peroxide.

PubMed

Dong, Jia Jia; Unjaroen, Duenpen; Mecozzi, Francesco; Harvey, Emma C; Saisaha, Pattama; Pijper, Dirk; de Boer, Johannes W; Alsters, Paul; Feringa, Ben L; Browne, Wesley R

2013-09-01

An efficient and simple method for selective oxidation of secondary alcohols and oxidation of alkanes to ketones is reported. An in situ prepared catalyst is employed based on manganese(II) salts, pyridine-2-carboxylic acid, and butanedione, which provides good-to-excellent conversions and yields with high turnover numbers (up to 10 000) with H2 O2 as oxidant at ambient temperatures. In substrates bearing multiple alcohol groups, secondary alcohols are converted to ketones selectively and, in general, benzyl C-H oxidation proceeds in preference to aliphatic C-H oxidation. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Influence of Fe(2+)-catalysed iron oxide recrystallization on metal cycling.

PubMed

Latta, Drew E; Gorski, Christopher A; Scherer, Michelle M

2012-12-01

Recent work has indicated that iron (oxyhydr-)oxides are capable of structurally incorporating and releasing metals and nutrients as a result of Fe2+-induced iron oxide recrystallization. In the present paper, we briefly review the current literature examining the mechanisms by which iron oxides recrystallize and summarize how recrystallization affects metal incorporation and release. We also provide new experimental evidence for the Fe2+-induced release of structural manganese from manganese-doped goethite. Currently, the exact mechanism(s) for Fe2+-induced recrystallization remain elusive, although they are likely to be both oxide-and metal-dependent. We conclude by discussing some future research directions for Fe2+-catalysed iron oxide recrystallization.
Environmental assessment of MMT fuel additive.

PubMed

Lynam, D R; Pfeifer, G D; Fort, B F; Gelbcke, A A

1990-04-01

Methylcyclopentadienyl Manganese Tricarbonyl (MMT) has been shown to be an effective octane enhancer in gasoline. It is presently used in the U.S. in leaded gasoline and in Canada in both leaded and unleaded gasoline. Because MMT has a low vapor pressure and a short half-life in sunlight, it is unlikely that significant concentrations of MMT could occur in the environment as a result of its use as a gasoline additive. Greater than 99.9% of the manganese from MMT is converted into inorganic oxides of manganese during the combustion of MMT-containing gasoline. Authors of several health assessments on MMT concluded the increase in environmental levels of manganese oxides would be slight compared to the natural background levels of manganese and would present no health hazards. Studies showed that MMT usage had no effect on CO emissions, caused a slight decrease in NOx emissions, and a slight increase in HC emissions. MMT usage caused a decrease in NOx + HC emissions in one test and had no effect in another.
Adsorption of selenium by amorphous iron oxyhydroxide and manganese dioxide

USGS Publications Warehouse

Balistrieri, L.S.; Chao, T.T.

1990-01-01

This work compares and models the adsorption of selenium and other anions on a neutral to alkaline surface (amorphous iron oxyhydroxide) and an acidic surface (manganese dioxide). Selenium adsorption on these oxides is examined as a function of pH, particle concentration, oxidation state, and competing anion concentration in order to assess how these factors might influence the mobility of selenium in the environment. The data indicate that 1. 1) amorphous iron oxyhydroxide has a greater affinity for selenium than manganese dioxide, 2. 2) selenite [Se(IV)] adsorption increases with decreasing pH and increasing particle concentration and is stronger than selenate [Se(VI)] adsorption on both oxides, and 3. 3) selenate does not adsorb on manganese dioxide. The relative affinity of selenate and selenite for the oxides and the lack of adsorption of selenate on a strongly acidic surface suggests that selenate forms outer-sphere complexes while selenite forms inner-sphere complexes with the surfaces. The data also indicate that the competition sequence of other anions with respect to selenite adsorption at pH 7.0 is phosphate > silicate > molybdate > fluoride > sulfate on amorphous iron oxyhydroxide and molybdate ??? phosphate > silicate > fluoride > sulfate on manganese dioxide. The adsorption of phosphate, molybdate, and silicate on these oxides as a function of pH indicates that the competition sequences reflect the relative affinities of these anions for the surfaces. The Triple Layer surface complexation model is used to provide a quantitative description of these observations and to assess the importance of surface site heterogeneity on anion adsorption. The modeling results suggest that selenite forms binuclear, innersphere complexes with amorphous iron oxyhydroxide and monodentate, inner-sphere complexes with manganese dioxide and that selenate forms outer-sphere, monodentate complexes with amorphous iron oxyhydroxide. The heterogeneity of the oxide surface sites is reflected in decreasing equilibrium constants for selenite with increasing adsorption density and both experimental observations and modeling results suggest that manganese dioxide has fewer sites of higher energy for selenite adsorption than amorphous iron oxyhydroxide. Modeling and interpreting the adsorption of phosphate, molybdate, and silicate on the oxides are made difficult by the lack of constraint in choosing surface species and the fact that equally good fits can be obtained with different surface species. Finally, predictions of anion competition using the model results from single adsorbate systems are not very successful because the model does not account for surface site heterogeneity. Selenite adsorption data from a multi-adsorbate system could be fit if the equilibrium constant for selenite is decreased with increasing anion adsorption density. ?? 1990.
Metal Cycling by Bacteria: Moving Electrons Around

ScienceCinema

Nealson, Ken

2017-12-09

About 20 years ago, Shewanella oneidensis MR-1 was isolated from a manganese-rich lack in upstate New York, and subsequently shown to utilize solid forms of oxidized manganese or iron as an electron acceptor. Recent studies of metal-reducing bacterial have unveiled a number of unexpected properties of microbes that have enlarged our view of microbes and their role(s) in natural ecosystems. For example, the processes of metal reduction themselves are fundamental to the carbon cycle in many lakes and sediments, where iron and manganese account for the major portion of organic carbon oxidation in many sediments. On more modest spatial scales, iron and manganese reduction can be linked to the oxidation of a wide variety of carbon compounds, many of them recalcitrant and/or toxic. One remarkable property of metal reducers is their ability to reduce solid, often highly crystalline substrates such as iron and manganese oxides and oxyhydroxides. It is now clear that this is done via the utilization of enzymes located on the outer wall of the bacteria - enzymes that apparently interact directly with these solid substrates. Molecular and genomic studies combined have revealed the genes and protoeins responsible for these activities, and many facets of the regulation. This talk focuses on the general features and properties of these remarkable organisms that seem to communicate via electron transfer across a wide variety of soluable, insoluable, and even "inert" substrates, and the way that these processes may be mechanistically linked.
Structural implications of the C-terminal tail in the catalytic and stability properties of manganese peroxidases from ligninolytic fungi

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

Fernández-Fueyo, Elena; Acebes, Sandra; Ruiz-Dueñas, Francisco J.

2014-12-01

The variable C-terminal tail of manganese peroxidases, a group of enzymes involved in lignin degradation, is implicated in their catalytic and stability properties, as shown by new crystal structures, molecular-simulation and directed-mutagenesis data. Based on this structural–functional evaluation, short and long/extralong manganese peroxidase subfamilies have been accepted; the latter are characterized by exceptional stability, while it is shown for the first time that the former are able to oxidize other substrates at the same site where manganese(II) is oxidized. The genome of Ceriporiopsis subvermispora includes 13 manganese peroxidase (MnP) genes representative of the three subfamilies described in ligninolytic fungi, whichmore » share an Mn{sup 2+}-oxidation site and have varying lengths of the C-terminal tail. Short, long and extralong MnPs were heterologously expressed and biochemically characterized, and the first structure of an extralong MnP was solved. Its C-terminal tail surrounds the haem-propionate access channel, contributing to Mn{sup 2+} oxidation by the internal propionate, but prevents the oxidation of 2, 2′-azino-bis(3-ethylbenzothiazoline-6-sulfonate) (ABTS), which is only oxidized by short MnPs and by shortened-tail variants from site-directed mutagenesis. The tail, which is anchored by numerous contacts, not only affects the catalytic properties of long/extralong MnPs but is also associated with their high acidic stability. Cd{sup 2+} binds at the Mn{sup 2+}-oxidation site and competitively inhibits oxidation of both Mn{sup 2+} and ABTS. Moreover, mutations blocking the haem-propionate channel prevent substrate oxidation. This agrees with molecular simulations that position ABTS at an electron-transfer distance from the haem propionates of an in silico shortened-tail form, while it cannot reach this position in the extralong MnP crystal structure. Only small differences exist between the long and the extralong MnPs, which do not justify their classification as two different subfamilies, but they significantly differ from the short MnPs, with the presence/absence of the C-terminal tail extension being implicated in these differences.« less
Oxidation mechanism of T91 steel in liquid lead-bismuth eutectic: with consideration of internal oxidation

PubMed Central

Ye, Zhongfei; Wang, Pei; Dong, Hong; Li, Dianzhong; Zhang, Yutuo; Li, Yiyi

2016-01-01

Clarification of the microscopic events that occur during oxidation is of great importance for understanding and consequently controlling the oxidation process. In this study the oxidation product formed on T91 ferritic/martensitic steel in oxygen saturated liquid lead-bismuth eutectic (LBE) at 823 K was characterized at the nanoscale using focused-ion beam and transmission electron microscope. An internal oxidation zone (IOZ) under the duplex oxide scale has been confirmed and characterized systematically. Through the microscopic characterization of the IOZ and the inner oxide layer, the micron-scale and nano-scale diffusion of Cr during the oxidation in LBE has been determined for the first time. The micron-scale diffusion of Cr ensures the continuous advancement of IOZ and inner oxide layer, and nano-scale diffusion of Cr gives rise to the typical appearance of the IOZ. Finally, a refined oxidation mechanism including the internal oxidation and the transformation of IOZ to inner oxide layer is proposed based on the discussion. The proposed oxidation mechanism succeeds in bridging the gap between the existing models and experimental observations. PMID:27734928
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).
Nitration and inactivation of manganese superoxide dismutase in chronic rejection of human renal allografts.

PubMed Central

MacMillan-Crow, L A; Crow, J P; Kerby, J D; Beckman, J S; Thompson, J A

1996-01-01

Inflammatory processes in chronic rejection remain a serious clinical problem in organ transplantation. Activated cellular infiltrate produces high levels of both superoxide and nitric oxide. These reactive oxygen species interact to form peroxynitrite, a potent oxidant that can modify proteins to form 3-nitrotyrosine. We identified enhanced immunostaining for nitrotyrosine localized to tubular epithelium of chronically rejected human renal allografts. Western blot analysis of rejected tissue demonstrated that tyrosine nitration was restricted to a few specific polypeptides. Immunoprecipitation and amino acid sequencing techniques identified manganese superoxide dismutase, the major antioxidant enzyme in mitochondria, as one of the targets of tyrosine nitration. Total manganese superoxide dismutase protein was increased in rejected kidney, particularly in the tubular epithelium; however, enzymatic activity was significantly decreased. Exposure of recombinant human manganese superoxide dismutase to peroxynitrite resulted in a dose-dependent (IC50 = 10 microM) decrease in enzymatic activity and concomitant increase in tyrosine nitration. Collectively, these observations suggest a role for peroxynitrite during development and progression of chronic rejection in human renal allografts. In addition, inactivation of manganese superoxide dismutase by peroxynitrite may represent a general mechanism that progressively increases the production of peroxynitrite, leading to irreversible oxidative injury to mitochondria. Images Fig. 1 Fig. 2 Fig. 3 Fig. 4 PMID:8876227
Possible roles of manganese redox chemistry in the sulfur cycle

NASA Technical Reports Server (NTRS)

Nealson, K. H.

1985-01-01

Sulfate reducing bacteria (SRB) are very potent MnO2 reducers by virtue of their sulfide production: H2S reacts rapidly with MnO2 to yield Mn(2), elemental sulfur, and water. In manganese rich zones, Mn cycles rapidly if sulfate is present to drive the reduction and the MnO2 precipitates and sinks into anaerobic zones. The production of sulfide (by organisms requiring organic carbon compounds) to reduce manganese oxides might act to couple the carbon and sulfur cycles in water bodies in which the two cycles are physically separated. Iron has been proposed for this provision of reducing power by (Jorgensen, 1983), but since MnS is soluble and FeS is very insoluble in water, it is equally likely that manganese rather than iron provides the electrons to the more oxidized surface layers.
Role of manganese oxides in peptide synthesis: implication in chemical evolution

NASA Astrophysics Data System (ADS)

Bhushan, Brij; Nayak, Arunima; Kamaluddin

2017-10-01

During the course of chemical evolution the role of metal oxides may have been very significant in catalysing the polymerization of biomonomers. The peptide bond formation of alanine (ala) and glycine (gly) in the presence of various oxides of manganese were performed for a period of 35 days at three different temperatures 50, 90 and 120°C without applying drying/wetting cycling. The reaction was monitored every week. The products formed were characterized by high-performance liquid chromatography and electrospray ionization-mass spectrometry techniques. Trace amount of oligomers was observed at 50°C. Maximum yield of peptides was found after 35 days at 90°C. It is important to note that very high temperatures of 120°C favoured the formation of diketopiperazine derivatives. Different types of manganese oxides [manganosite (MnO), bixbyite (Mn2O3), hausmannite (Mn3O4) and pyrolusite (MnO2)] were used as catalyst. The MnO catalysed glycine to cyclic (Gly)2, (Gly)2 and (Gly)3, and alanine, to cyclic (Ala)2 and (Ala)2. Mn3O4 also produced the same products but in lesser yield, while Mn2O3 and MnO2 produced cyclic anhydride of glycine and alanine with a trace amount of dimers and trimmers. Manganese of lower oxidation state is much more efficient in propagating the reaction than higher oxidation states. The possible mechanism of these reactions and the relevance of the results for the prebiotic chemistry are discussed.
Thermodynamic analysis of a combined-cycle solar thermal power plant with manganese oxide-based thermochemical energy storage

NASA Astrophysics Data System (ADS)

Lei, Qi; Bader, Roman; Kreider, Peter; Lovegrove, Keith; Lipiński, Wojciech

2017-11-01

We explore the thermodynamic efficiency of a solar-driven combined cycle power system with manganese oxide-based thermochemical energy storage system. Manganese oxide particles are reduced during the day in an oxygen-lean atmosphere obtained with a fluidized-bed reactor at temperatures in the range of 750-1600°C using concentrated solar energy. Reduced hot particles are stored and re-oxidized during night-time to achieve continuous power plant operation. The steady-state mass and energy conservation equations are solved for all system components to calculate the thermodynamic properties and mass flow rates at all state points in the system, taking into account component irreversibilities. The net power block and overall solar-to-electric energy conversion efficiencies, and the required storage volumes for solids and gases in the storage system are predicted. Preliminary results for a system with 100 MW nominal solar power input at a solar concentration ratio of 3000, designed for constant round-the-clock operation with 8 hours of on-sun and 16 hours of off-sun operation and with manganese oxide particles cycled between 750 and 1600°C yield a net power block efficiency of 60.0% and an overall energy conversion efficiency of 41.3%. Required storage tank sizes for the solids are estimated to be approx. 5-6 times smaller than those of state-of-the-art molten salt systems.
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
Mechanisms of Pb(II) sorption on a biogenic manganese oxide.

PubMed

Villalobos, Mario; Bargar, John; Sposito, Garrison

2005-01-15

Macroscopic Pb(II) uptake experiments and Pb L3-edge extended X-ray absorption fine structure (EXAFS) spectroscopy were combined to examine the mechanisms of Pb(II) sequestration by a biogenic manganese oxide and its synthetic analogues, all of which are layer-type manganese oxides (phyllomanganates). Relatively fast Pb(II) sorption was observed, as well as extremely high sorption capacities, suggesting Pb incorporation into the structure of the oxides. EXAFS analysis revealed similar uptake mechanisms regardless of the specific nature of the phyllomanganate, electrolyte background, total Pb(II) loading, or equilibration time. One Pb-O and two Pb-Mn shells at distances of 2.30, 3.53, and 3.74 A, respectively, were found, as well as a linear relationship between Brunauer-Emmett-Teller (BET; i.e., external) specific surface area and maximum Pb(II) sorption that also encompassed data from previous work. Both observations support the existence of two bonding mechanisms in Pb(II) sorption: a triple-corner-sharing complex in the interlayers above/ below cationic sheet vacancies (N theoretical = 6), and a double-corner-sharing complex on particle edges at exposed singly coordinated -O(H) bonds (N theoretical = 2). General prevalence of external over internal sorption is predicted, but the two simultaneous sorption mechanisms can account for the widely noted high affinity of manganese oxides for Pb(ll) in natural environments.
High-spin Mn-oxo complexes and their relevance to the oxygen-evolving complex within photosystem II.

PubMed

Gupta, Rupal; Taguchi, Taketo; Lassalle-Kaiser, Benedikt; Bominaar, Emile L; Yano, Junko; Hendrich, Michael P; Borovik, A S

2015-04-28

The structural and electronic properties of a series of manganese complexes with terminal oxido ligands are described. The complexes span three different oxidation states at the manganese center (III-V), have similar molecular structures, and contain intramolecular hydrogen-bonding networks surrounding the Mn-oxo unit. Structural studies using X-ray absorption methods indicated that each complex is mononuclear and that oxidation occurs at the manganese centers, which is also supported by electron paramagnetic resonance (EPR) studies. This gives a high-spin Mn(V)-oxo complex and not a Mn(IV)-oxy radical as the most oxidized species. In addition, the EPR findings demonstrated that the Fermi contact term could experimentally substantiate the oxidation states at the manganese centers and the covalency in the metal-ligand bonding. Oxygen-17-labeled samples were used to determine spin density within the Mn-oxo unit, with the greatest delocalization occurring within the Mn(V)-oxo species (0.45 spins on the oxido ligand). The experimental results coupled with density functional theory studies show a large amount of covalency within the Mn-oxo bonds. Finally, these results are examined within the context of possible mechanisms associated with photosynthetic water oxidation; specifically, the possible identity of the proposed high valent Mn-oxo species that is postulated to form during turnover is discussed.
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 conditions, along with the formation of rhodochrosite in such aggregates. Therefore, this study provides insights into the structure and diversity of soil-borne bacterial communities in Mn(II)-oxidizing habitats and supports the contribution of soil-borne Mn(II)-oxidizing bacteria to Mn oxide mineralization in soils. PMID:24069232

First evidence on phloem transport of nanoscale calcium oxide in groundnut using solution culture technique

NASA Astrophysics Data System (ADS)

Deepa, Manchala; Sudhakar, Palagiri; Nagamadhuri, Kandula Venkata; Balakrishna Reddy, Kota; Giridhara Krishna, Thimmavajjula; Prasad, Tollamadugu Naga Venkata Krishna Vara

2015-06-01

Nanoscale materials, whose size typically falls below 100 nm, exhibit novel chemical, physical and biological properties which are different from their bulk counterparts. In the present investigation, we demonstrated that nanoscale calcium oxide particles (n-CaO) could transport through phloem tissue of groundnut unlike the corresponding bulk materials. n-CaO particles are prepared using sol-gel method. The size of the as prepared n-CaO measured (69.9 nm) using transmission electron microscopic technique (TEM). Results of the hydroponics experiment using solution culture technique revealed that foliar application of n-CaO at different concentrations (10, 50, 100, 500, 1,000 ppm) on groundnut plants confirmed the entry of calcium into leaves and stems through phloem compared to bulk source of calcium sprayed (CaO and CaNO3). After spraying of n-CaO, calcium content in roots, shoots and leaves significantly increased. Based on visual scoring of calcium deficiency correction and calcium content in plant parts, we may establish the fact that nanoscale calcium oxide particles (size 69.9 nm) could move through phloem tissue in groundnut. This is the first report on phloem transport of nanoscale calcium oxide particles in plants and this result points to the use of nanoscale calcium oxide particles as calcium source to the plants through foliar application, agricultural crops in particular, as bulk calcium application through foliar nutrition is restricted due to its non-mobility in phloem.
Characterization of nanoscale oxide and oxyhydroxide powders using EXAFS spectroscopy

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

Darab, J.G.; Linehan, J.C.; Matson, D.W.

1993-06-01

Extended x-ray absorption fine structure (EXAFS) spectroscopy has been used to determine the structural environment local to iron(HI) and zircorium(IV) cations in respectively, nanoscale iron oxyhydroxide and nanoscale zirconium oxide powders. The iron oxyhydroxide powder, produced by the modified reverse micelle (MRM) technology, was found to have a short-range structure most similar to that of goethite ([alpha]-FeOOH). The short-range structure of the zirconium oxide powder, produced using the rapid thermal decomposition of solutes (RTDS) technology, was found to be a mixture of monoclinic zirconia and cubic zirconia environments.
Characterization of nanoscale oxide and oxyhydroxide powders using EXAFS spectroscopy

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

Darab, J.G.; Linehan, J.C.; Matson, D.W.

1993-06-01

Extended x-ray absorption fine structure (EXAFS) spectroscopy has been used to determine the structural environment local to iron(HI) and zircorium(IV) cations in respectively, nanoscale iron oxyhydroxide and nanoscale zirconium oxide powders. The iron oxyhydroxide powder, produced by the modified reverse micelle (MRM) technology, was found to have a short-range structure most similar to that of goethite ({alpha}-FeOOH). The short-range structure of the zirconium oxide powder, produced using the rapid thermal decomposition of solutes (RTDS) technology, was found to be a mixture of monoclinic zirconia and cubic zirconia environments.
Manganese oxide nanowires, films, and membranes and methods of making

DOEpatents

Suib, Steven Lawrence [Storrs, CT; Yuan, Jikang [Storrs, CT

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.
Muti-component nanocomposite of nickel and manganese oxides with enhanced stability and catalytic performance for non-enzymatic glucose sensors

NASA Astrophysics Data System (ADS)

Wang, Dandan; Cai, Daoping; Wang, Chenxia; Liu, Bin; Wang, Lingling; Liu, Yuan; Li, Han; Wang, Yanrong; Li, Qiuhong; Wang, Taihong

2016-06-01

A muti-component nanocomposite of nickel and manganese oxides with a uniformly dispersed microspherical structure has been fabricated by a hydrothermal synthesis method. The as-prepared nanocomposite has been employed as a sensing material for non-enzymatic glucose detection and shown excellent electrocatalytic activity, such as high sensitivities of 82.44 μA mM-1 cm-2 and 27.92 μA mM-1 cm-2 over the linear range of 0.1-1 mM and 1-4.5 mM, respectively, a low detection limit of 0.2 μM and a fast response time of <3 s. Moreover, satisfactory specificity and excellent stability have also been achieved. The results demonstrate that a muti-component nanocomposite of nickel and manganese oxides has great potential applications as glucose sensors.
Recent research progress on iron- and manganese-based positive electrode materials for rechargeable sodium batteries

PubMed Central

Yabuuchi, Naoaki; Komaba, Shinichi

2014-01-01

Large-scale high-energy batteries with electrode materials made from the Earth-abundant elements are needed to achieve sustainable energy development. On the basis of material abundance, rechargeable sodium batteries with iron- and manganese-based positive electrode materials are the ideal candidates for large-scale batteries. In this review, iron- and manganese-based electrode materials, oxides, phosphates, fluorides, etc, as positive electrodes for rechargeable sodium batteries are reviewed. Iron and manganese compounds with sodium ions provide high structural flexibility. Two layered polymorphs, O3- and P2-type layered structures, show different electrode performance in Na cells related to the different phase transition and sodium migration processes on sodium extraction/insertion. Similar to layered oxides, iron/manganese phosphates and pyrophosphates also provide the different framework structures, which are used as sodium insertion host materials. Electrode performance and reaction mechanisms of the iron- and manganese-based electrode materials in Na cells are described and the similarities and differences with lithium counterparts are also discussed. Together with these results, the possibility of the high-energy battery system with electrode materials made from only Earth-abundant elements is reviewed. PMID:27877694
Recent research progress on iron- and manganese-based positive electrode materials for rechargeable sodium batteries.

PubMed

Yabuuchi, Naoaki; Komaba, Shinichi

2014-08-01

Large-scale high-energy batteries with electrode materials made from the Earth-abundant elements are needed to achieve sustainable energy development. On the basis of material abundance, rechargeable sodium batteries with iron- and manganese-based positive electrode materials are the ideal candidates for large-scale batteries. In this review, iron- and manganese-based electrode materials, oxides, phosphates, fluorides, etc, as positive electrodes for rechargeable sodium batteries are reviewed. Iron and manganese compounds with sodium ions provide high structural flexibility. Two layered polymorphs, O3- and P2-type layered structures, show different electrode performance in Na cells related to the different phase transition and sodium migration processes on sodium extraction/insertion. Similar to layered oxides, iron/manganese phosphates and pyrophosphates also provide the different framework structures, which are used as sodium insertion host materials. Electrode performance and reaction mechanisms of the iron- and manganese-based electrode materials in Na cells are described and the similarities and differences with lithium counterparts are also discussed. Together with these results, the possibility of the high-energy battery system with electrode materials made from only Earth-abundant elements is reviewed.
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

2013-03-06

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.
Binder-free manganese oxide/carbon nanomaterials thin film electrode for supercapacitors.

PubMed

Wang, Ning; Wu, Chuxin; Li, Jiaxin; Dong, Guofa; Guan, Lunhui

2011-11-01

A ternary thin film electrode was created by coating manganese oxide onto a network composed of single-walled carbon nanotubes and single-walled carbon nanohorns. The electrode exhibited a porous structure, which is a promising architecture for supercapacitors applications. The maximum specific capacitances of 357 F/g for total electrode at 1 A/g were achieved in 0.1 M Na(2)SO(4) aqueous solution.
Synthesis and Electrochemical Performance of LixMn2-yCoyO4-dCld Cathode Material

DTIC Science & Technology

2016-06-13

Lithium manganese oxide spinel is a potential candidate for Li- ion battery cathodes because of its...240 mAh/g of active material, and 4) high rate charge and discharge. Keywords: Lithium and Li- ion battery , Lithium manganese oxide spinel, Spinel...demonstrate desirable traits for incorporation into lithium - ion batteries for the military. References 1. David Linden (Ed.); Handbook of Batteries
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.
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.
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.
Improving the Thermochemical Energy Storage Performance of the Mn2 O3 /Mn3 O4 Redox Couple by the Incorporation of Iron.

PubMed

Carrillo, Alfonso J; Serrano, David P; Pizarro, Patricia; Coronado, Juan M

2015-06-08

Redox cycles of manganese oxides (Mn2 O3 /Mn3 O4 ) are a promising alternative for thermochemical heat storage systems coupled to concentrated solar power plants as manganese oxides are abundant and inexpensive materials. Although their cyclability for such a purpose has been proved, sintering processes, related to the high-temperature conditions at which charge-discharge cycles are performed, generally cause a cycle-to-cycle decrease in the oxidation rate of Mn3 O4 . To guarantee proper operation, both reactions should present stable reaction rates. In this study, it has been demonstrated that the incorporation of Fe, which is also an abundant material, into the manganese oxides improves the redox performance of this system by increasing the heat storage density, narrowing the redox thermal hysteresis, and, above all, stabilizing and enhancing the oxidation rate over long-term operation, which counteracts the negative effects caused by sintering, although its presence is not avoided. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Selective oxidation of dual phase steel after annealing at different dew points

NASA Astrophysics Data System (ADS)

Lins, Vanessa de Freitas Cunha; Madeira, Laureanny; Vilela, Jose Mario Carneiro; Andrade, Margareth Spangler; Buono, Vicente Tadeu Lopes; Guimarães, Juliana Porto; Alvarenga, Evandro de Azevedo

2011-04-01

Hot galvanized steels have been extensively used in the automotive industry. Selective oxidation on the steel surface affects the wettability of zinc on steel and the grain orientation of inhibition layer (Fe-Al-Zn alloy) and reduces the iron diffusion to the zinc layer. The aim of this work is to identify and quantify selective oxidation on the surface of a dual phase steel, and an experimental steel with a lower content of manganese, annealed at different dew points. The techniques employed were atomic force microscopy, X-ray photoelectron spectroscopy, and glow discharge optical emission spectroscopy. External selective oxidation was observed for phosphorus on steel surface annealed at 0 °C dp, and for manganese, silicon, and aluminum at a lower dew point. The concentration of manganese was higher on the dual phase steel surface than on the surface of the experimental steel. The concentration of molybdenum on the surface of both steels increased as the depth increased.
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.
Synthesis of manganese stearate for high density polyethylene (HDPE) and its biodegradation

NASA Astrophysics Data System (ADS)

Aras, Neny Rasnyanti M.; Arcana, I. Made

2015-09-01

An oxidant additive is one type of additive used for oxo-biodegradable polymers. This additive was prepared by reaction multivalent transition metals and fatty acids to accelerate the degradation process of polymers by providing a thermal treatment or irradiation with light. This study focused on the synthesis of manganese stearate as an additive for application in High Density Polyethylene (HDPE), and the influence of manganese stearate on the characteristics of HDPE including their biodegradability. Manganese stearate was synthesized by the reaction of stearic acid with sodium hydroxide, and sodium stearate formed was reacted with manganese chloride tetrahydrate to form manganese stearate with a melting point of 100-110 °C. Based on the FTIR spectrum showed absorption peak at wave number around 1560 cm-1 which is an asymmetric vibration of CO functional group that binds to the manganese. The films of oxo-biodegradable polymer were prepared by blending HDPE and manganese stearate additives at various concentrations with using the polymer melting method, followed heating at a temperature of 50°C and 70°C for 10 days. The characterizations of the oxo-biodegradable polymers were carried out by analysis the functional groups (FTIR and ATR),thermal properties (TGA), surface properties (SEM), as well as analysis of the biodegradability (the biodegradation test by using activated sludge, % weight loss). Based on COi indicate that the additive of manganese stearate is active in oxidizing polymer by heating treatment. Results of biodegradation by microorganisms from activated sludge showed that the percentage weight loss of polymers increase with the increasing incubation time and the concentration of manganese stearate in HDPE. Biodegradability of HDPE with the addition of manganese stearate and followed by heating at a higher temperature was better observed. The highest percentage weight loss was obtained at the polymer with concentration of 0.2% manganese stearate, and followed by thermal treatment at a temperature of 70 °C and the incubation time for 45 days in the activated sludge.
Proposed mechanisms for water oxidation by Photosystem II and nanosized manganese oxides.

PubMed

Najafpour, Mohamad Mahdi; Heidari, Sima; Balaghi, S Esmael; Hołyńska, Małgorzata; Sadr, Moayad Hossaini; Soltani, Behzad; Khatamian, Maasoumeh; Larkum, Anthony W; Allakhverdiev, Suleyman I

2017-02-01

Plants, algae and cyanobacteria capture sunlight, extracting electrons from H 2 O to reduce CO 2 into sugars while releasing O 2 in the oxygenic photosynthetic process. Because of the important role of water oxidation in artificial photosynthesis and many solar fuel systems, understanding the structure and function of this unique biological catalyst forms a requisite research field. Herein the structure of the water-oxidizing complex and its ligand environment are described with reference to the 1.9Å resolution X-ray-derived crystallographic model of the water-oxidizing complex from the cyanobacterium Thermosynechococcus vulcanus. Proposed mechanisms for water oxidation by Photosystem II and nanosized manganese oxides are also reviewed and discussed in the paper. Copyright © 2016 Elsevier B.V. All rights reserved.
Reverse micelle synthesis of nanoscale metal containing catalysts. [Nickel metal (with a nickel oxide surface layer) and iron oxyhydroxide nanoscale powders

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

Darab, J.G.; Fulton, J.L.; Linehan, J.C.

1993-03-01

The need for morphological control during the synthesis of catalyst precursor powders is generally accepted to be important. In the liquefaction of coal, for example, iron-bearing catalyst precursor particles containing individual crystallites with diameters in the 1-100 nanometer range are believed to achieve good dispersion through out the coal-solvent slurry during liquefaction 2 runs and to undergo chemical transformations to catalytically active iron sulfide phases. The production of the nanoscale powders described here employs the confining spherical microdomains comprising the aqueous phase of a modified reverse micelle (MRM) microemulsion system as nanoscale reaction vessels in which polymerization, electrochemical reduction andmore » precipitation of solvated salts can occur. The goal is to take advantage of the confining nature of micelles to kinetically hinder transformation processes which readily occur in bulk aqueous solution in order to control the morphology and phase of the resulting powder. We have prepared a variety of metal, alloy, and metal- and mixed metal-oxide nanoscale powders from appropriate MRM systems. Examples of nanoscale powders produced include Co, Mo-Co, Ni[sub 3]Fe, Ni, and various oxides and oxyhydroxides of iron. Here, we discuss the preparation and characterization of nickel metal (with a nickel oxide surface layer) and iron oxyhydroxide MRM nanoscale powders. We have used extended x-ray absorption fine structure (EXAFS) spectroscopy to study the chemical polymerization process in situ, x-ray diffraction (XRD), scanning and transmission electron microcroscopies (SEM and TEM), elemental analysis and structural modelling to characterize the nanoscale powders produced. The catalytic activity of these powders is currently being studied.« less
Silver binding in argentiferous manganese oxide minerals investigated by synchrotron radiation X-ray absorption spectroscopy

NASA Astrophysics Data System (ADS)

Fan, Chenzi; Li, Qiaoying; Chu, Binbin; Lu, Guohui; Gao, Yuhong; Xu, Lingxiao

2018-02-01

The knowledge of the nature of silver occurrence and sites in argentiferous manganese oxides is significant for developing better process to extract silver from manganese-silver ores. Synchrotron radiation has been used to collect Ag K-edge X-ray absorption spectroscopy of three natural and five synthetic samples of silver-containing manganese oxide, basically in the phases of tunnel-type cryptomelane or todorokite and layer-type birnessite or chalcophanite. Data were also gathered on five standards including Ag foil, Ag2O, Ag2SO4, Ag2CO3, and AgNO3 to compare the local environments of Ag atoms with the samples. Ag K-edge XANES studies show that Ag is present in most of the samples in Ag+ oxidation state, except in the Ag-Tod sample through annealing step in the form of Ag0 nanoparticles which are also identified by TEM. The natural samples from Xiangguang manganese-silver ores exhibit similar coordination distances as the corresponding tunnel or layer structured synthetic samples. In the argentiferous cryptomelanes, silver cations do not occupy the tunnel centers like K+, but rather place on the common face sites of the cubic cage formed by MnO6 octahedra, coordinated with about four oxygen anions at 2.4 Å bond distances proved by the EXAFS results. In the silver-exchanged birnessites or natural argentiferous chalcophanite, silver cations probably occupy a tetrahedral coordination to interlayer O atoms and a position located above or below the vacant cavities in the Mn octahedra layers.

Direct effects of manganese compounds on dopamine and its metabolite Dopac: an in vitro study

PubMed Central

Sistrunk, Shannon C.; Ross, Matthew K.; Filipov, Nikolay M.

2007-01-01

Following combustion of fuel containing the additive methylcyclopentadienyl-manganese-tricarbonyl (MMT), manganese phosphate (MnPO4) and manganese sulfate (MnSO4) are emitted in the atmosphere. Manganese chloride (MnCl2), another Mn2+ species, is widely used experimentally. Using rat striatal slices, we found that MnPO4 decreased tissue and media dopamine (DA) and media Dopac (a DA metabolite) levels substantially more than either MnCl2 or MnSO4; antioxidants were partially protective. Also, both MnCl2 and MnPO4 (more potently) oxidized DA and Dopac even in the absence of tissue in the media, suggesting a direct interaction between Mn and DA/Dopac. Because aminochrome is a major oxidation product of DA, we next determined whether MnPO4 will be more potent in forming aminochrome than MnCl2 or MnSO4 which, indeed, was the case. Thus, a potential additional mechanism for the neurotoxic effects of environmentally-relevant forms of Mn, MnPO4 in particular, is the generation of reactive DA intermediates. PMID:18449324
Bi-template assisted synthesis of mesoporous manganese oxide nanostructures: Tuning properties for efficient CO oxidation.

PubMed

Roy, Mouni; Basak, Somjyoti; Naskar, Milan Kanti

2016-02-21

A simple soft bi-templating process was used for the synthesis of mesoporous manganese oxide nanostructures using KMnO4 as a precursor and polyethylene glycol and cetyltrimethylammonium bromide as templates in the presence of benzaldehyde as an organic additive in alkaline media, followed by calcination at 400 °C. X-ray diffraction and Raman spectroscopic analysis of the calcined products confirmed the existence of stoichiometric (MnO2 and Mn5O8) and non-stoichiometric mixed phases (MnO2 + Mn5O8) of Mn oxides obtained by tuning the concentration of the additive and the synthesis time. The surface properties of the prepared Mn oxides were determined by X-ray photoelectron spectroscopy. The mesoporosity of the samples was confirmed by N2 adsorption-desorption. Different synthetic conditions resulted in the formation of different morphologies of the Mn oxides (α-MnO2, Mn5O8, and α-MnO2 + Mn5O8), such as nanoparticles, nanorods, and nanowires. The synthesized mesoporous Mn oxide nanostructures were used for the catalytic oxidation of the harmful air pollutant carbon monoxide. The Mn5O8 nanoparticles with the highest Brunauer-Emmett-Teller surface area and the non-stoichiometric manganese oxide (α-MnO2 + Mn5O8) nanorods with a higher Mn(3+) concentration had the best catalytic efficiency.
Electrochemical Performance of LixMn2-yFeyO4-zClz Synthesized Through In-Situ Glycine Nitrate Combustion

DTIC Science & Technology

2016-06-13

Aberdeen Proving Ground, MD, USA, 21005 Abstract: Lithium manganese oxide spinel is an attractive material for lithium - ion battery cathodes due to...performance allows for access to energy at extended cycling and across potential regimes. Keywords: Li- ion battery ; Lithium manganese oxide spinel...materials for lithium - ion batteries due to their affordability and low toxicity while maintaining reasonable capacity [1-3]. However, this spinel
Iron and manganese removal: Recent advances in modelling treatment efficiency by rapid sand filtration.

PubMed

Vries, D; Bertelkamp, C; Schoonenberg Kegel, F; Hofs, B; Dusseldorp, J; Bruins, J H; de Vet, W; van den Akker, B

2017-02-01

A model has been developed that takes into account the main characteristics of (submerged) rapid filtration: the water quality parameters of the influent water, notably pH, iron(II) and manganese(II) concentrations, homogeneous oxidation in the supernatant layer, surface sorption and heterogeneous oxidation kinetics in the filter, and filter media adsorption characteristics. Simplifying assumptions are made to enable validation in practice, while maintaining the main mechanisms involved in iron(II) and manganese(II) removal. Adsorption isotherm data collected from different Dutch treatment sites show that Fe(II)/Mn(II) adsorption may vary substantially between them, but generally increases with higher pH. The model is sensitive to (experimentally) determined adsorption parameters and the heterogeneous oxidation rate. Model results coincide with experimental values when the heterogeneous rate constants are calibrated. Copyright © 2016 Elsevier Ltd. All rights reserved.
Unprecedented Synergistic Effects of Nanoscale Nutrients on Growth, Productivity of Sweet Sorghum [Sorghum bicolor (L.) Moench], and Nutrient Biofortification.

PubMed

Naseeruddin, Ramapuram; Sumathi, Vupprucherla; Prasad, Tollamadugu N V K V; Sudhakar, Palagiri; Chandrika, Velaga; Ravindra Reddy, Balam

2018-02-07

Evidence-based synergistic effects of nanoscale materials (size of <100 nm in at least one dimension) were scantly documented in agriculture at field scale. Herein, we report for the first time on effects of nanoscale zinc oxide (n-ZnO), calcium oxide (n-CaO), and magnesium oxide (n-MgO) on growth and productivity of sweet sorghum [Sorghum bicolor (L.) Moench]. A modified sol-gel method was used to prepare nanoscale materials under study. Characterization was performed using transmission and scanning electron microscopies, X-ray diffraction, and dynamic light scattering. Average sizes (25, 53.7, and 53.5 nm) and ζ potentials (-10.9, -28.2, and -16.2 mV) of n-ZnO, n-CaO, and n-MgO were measured, respectively. The significant grain yield (17.8 and 14.2%), cane yield (7.2 and 8.0%), juice yield (10 and 12%), and higher sucrose yield (21.8 and 20.9%) were recorded with the application of nanoscale materials in the years 2014 and 2015, respectively. Nutrient uptake was significant with foliar application of nanoscale nutrients.
Manganese-Oxygen Intermediates in O-O Bond Activation and Hydrogen-Atom Transfer Reactions.

PubMed

Rice, Derek B; Massie, Allyssa A; Jackson, Timothy A

2017-11-21

Biological systems capitalize on the redox versatility of manganese to perform reactions involving dioxygen and its derivatives superoxide, hydrogen peroxide, and water. The reactions of manganese enzymes influence both human health and the global energy cycle. Important examples include the detoxification of reactive oxygen species by manganese superoxide dismutase, biosynthesis by manganese ribonucleotide reductase and manganese lipoxygenase, and water splitting by the oxygen-evolving complex of photosystem II. Although these enzymes perform very different reactions and employ structurally distinct active sites, manganese intermediates with peroxo, hydroxo, and oxo ligation are commonly proposed in catalytic mechanisms. These intermediates are also postulated in mechanisms of synthetic manganese oxidation catalysts, which are of interest due to the earth abundance of manganese. In this Account, we describe our recent efforts toward understanding O-O bond activation pathways of Mn III -peroxo adducts and hydrogen-atom transfer reactivity of Mn IV -oxo and Mn III -hydroxo complexes. In biological and synthetic catalysts, peroxomanganese intermediates are commonly proposed to decay by either Mn-O or O-O cleavage pathways, although it is often unclear how the local coordination environment influences the decay mechanism. To address this matter, we generated a variety of Mn III -peroxo adducts with varied ligand environments. Using parallel-mode EPR and Mn K-edge X-ray absorption techniques, the decay pathway of one Mn III -peroxo complex bearing a bulky macrocylic ligand was investigated. Unlike many Mn III -peroxo model complexes that decay to oxo-bridged-Mn III Mn IV dimers, decay of this Mn III -peroxo adduct yielded mononuclear Mn III -hydroxo and Mn IV -oxo products, potentially resulting from O-O bond activation of the Mn III -peroxo unit. These results highlight the role of ligand sterics in promoting the formation of mononuclear products and mark an important step in designing Mn III -peroxo complexes that convert cleanly to high-valent Mn-oxo species. Although some synthetic Mn IV -oxo complexes show great potential for oxidizing substrates with strong C-H bonds, most Mn IV -oxo species are sluggish oxidants. Both two-state reactivity and thermodynamic arguments have been put forth to explain these observations. To address these issues, we generated a series of Mn IV -oxo complexes supported by neutral, pentadentate ligands with systematically perturbed equatorial donation. Kinetic investigations of these complexes revealed a correlation between equatorial ligand-field strength and hydrogen-atom and oxygen-atom transfer reactivity. While this trend can be understood on the basis of the two-state reactivity model, the reactivity trend also correlates with variations in Mn III/IV reduction potential caused by changes in the ligand field. This work demonstrates the dramatic influence simple ligand perturbations can have on reactivity but also illustrates the difficulties in understanding the precise basis for a change in reactivity. In the enzyme manganese lipoxygenase, an active-site Mn III -hydroxo adduct initiates substrate oxidation by abstracting a hydrogen atom from a C-H bond. Precedent for this chemistry from synthetic Mn III -hydroxo centers is rare. To better understand hydrogen-atom transfer by Mn III centers, we developed a pair of Mn III -hydroxo complexes, formed in high yield from dioxygen oxidation of Mn II precursors, capable of attacking weak O-H and C-H bonds. Kinetic and computational studies show a delicate interplay between thermodynamic and steric influences in hydrogen-atom transfer reactivity, underscoring the potential of Mn III -hydroxo units as mild oxidants.
Iron, copper, and manganese complexes with in vitro superoxide dismutase and/or catalase activities that keep Saccharomyces cerevisiae cells alive under severe oxidative stress.

PubMed

Ribeiro, Thales P; Fernandes, Christiane; Melo, Karen V; Ferreira, Sarah S; Lessa, Josane A; Franco, Roberto W A; Schenk, Gerhard; Pereira, Marcos D; Horn, Adolfo

2015-03-01

Due to their aerobic lifestyle, eukaryotic organisms have evolved different strategies to overcome oxidative stress. The recruitment of some specific metalloenzymes such as superoxide dismutases (SODs) and catalases (CATs) is of great importance for eliminating harmful reactive oxygen species (hydrogen peroxide and superoxide anion). Using the ligand HPClNOL {1-[bis(pyridin-2-ylmethyl)amino]-3-chloropropan-2-ol}, we have synthesized three coordination compounds containing iron(III), copper(II), and manganese(II) ions, which are also present in the active site of the above-noted metalloenzymes. These compounds were evaluated as SOD and CAT mimetics. The manganese and iron compounds showed both SOD and CAT activities, while copper showed only SOD activity. The copper and manganese in vitro SOD activities are very similar (IC50~0.4 μmol dm(-3)) and about 70-fold higher than those of iron. The manganese compound showed CAT activity higher than that of the iron species. Analyzing their capacity to protect Saccharomyces cerevisiae cells against oxidative stress (H2O2 and the O2(•-) radical), we observed that all compounds act as antioxidants, increasing the resistance of yeast cells mainly due to a reduction of lipid oxidation. Especially for the iron compound, the data indicate complete protection when wild-type cells were exposed to H2O2 or O2(•-) species. Interestingly, these compounds also compensate for both superoxide dismutase and catalase deficiencies; their antioxidant activity is metal ion dependent, in the order iron(III)>copper(II)>manganese(II). The protection mechanism employed by the complexes proved to be independent of the activation of transcription factors (such as Yap1, Hsf1, Msn2/Msn4) and protein synthesis. There is no direct relation between the in vitro and the in vivo antioxidant activities. Copyright © 2014 Elsevier Inc. All rights reserved.
Loss of hfe function reverses impaired recognition memory caused by olfactory manganese exposure in mice.

PubMed

Ye, Qi; Kim, Jonghan

2015-03-01

Excessive manganese (Mn) in the brain promotes a variety of abnormal behaviors, including memory deficits, decreased motor skills and psychotic behavior resembling Parkinson's disease. Hereditary hemochromatosis (HH) is a prevalent genetic iron overload disorder worldwide. Dysfunction in HFE gene is the major cause of HH. Our previous study has demonstrated that olfactory Mn uptake is altered by HFE deficiency, suggesting that loss of HFE function could alter manganese-associated neurotoxicity. To test this hypothesis, Hfe-knockout (Hfe (-/-)) and wild-type (Hfe (+/+)) mice mice were intranasally-instilled with manganese chloride (MnCl2 5 mg/kg) or water daily for 3 weeks and examined for memory function. Olfactory Mn diminished both short-term recognition and spatial memory in Hfe (+/+) mice, as examined by novel object recognition task and Barnes maze test, respectively. Interestingly, Hfe (-/-) mice did not show impaired recognition memory caused by Mn exposure, suggesting a potential protective effect of Hfe deficiency against Mn-induced memory deficits. Since many of the neurotoxic effects of manganese are thought to result from increased oxidative stress, we quantified activities of anti-oxidant enzymes in the prefrontal cortex (PFC). Mn instillation decreased superoxide dismutase 1 (SOD1) activity in Hfe (+/+) mice, but not in Hfe (-/-) mice. In addition, Hfe deficiency up-regulated SOD1 and glutathione peroxidase activities. These results suggest a beneficial role of Hfe deficiency in attenuating Mn-induced oxidative stress in the PFC. Furthermore, Mn exposure reduced nicotinic acetylcholine receptor levels in the PFC, indicating that blunted acetylcholine signaling could contribute to impaired memory associated with intranasal manganese. Together, our model suggests that disrupted cholinergic system in the brain is involved in airborne Mn-induced memory deficits and loss of HFE function could in part prevent memory loss via a potential up-regulation of anti-oxidant enzymes in the PFC.
Iron and manganese oxide mineralization in the Pacific

USGS Publications Warehouse

Hein, J. R.; Koschinsky, A.; Halbach, P.; Manheim, F. T.; Bau, M.; Jung-Keuk, Kang; 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. These processes are discussed.
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.
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.
The Mismetallation of Enzymes during Oxidative Stress*

PubMed Central

Imlay, James A.

2014-01-01

Mononuclear iron enzymes can tightly bind non-activating metals. How do cells avoid mismetallation? The model bacterium Escherichia coli may control its metal pools so that thermodynamics favor the correct metallation of each enzyme. This system is disrupted, however, by superoxide and hydrogen peroxide. These species oxidize ferrous iron and thereby displace it from many iron-dependent mononuclear enzymes. Ultimately, zinc binds in its place, confers little activity, and imposes metabolic bottlenecks. Data suggest that E. coli compensates by using thiols to extract the zinc and by importing manganese to replace the catalytic iron atom. Manganese resists oxidants and provides substantial activity. PMID:25160623
Production of biogenic manganese oxides coupled with methane oxidation in a bioreactor for removing metals from wastewater.

PubMed

Matsushita, Shuji; Komizo, Daisuke; Cao, Linh Thi Thuy; Aoi, Yoshiteru; Kindaichi, Tomonori; Ozaki, Noriatsu; Imachi, Hiroyuki; Ohashi, Akiyoshi

2018-03-01

Biogenic manganese oxide (BioMnO x ) can efficiently adsorb various minor metals. The production of BioMnO x in reactors to remove metals during wastewater treatment processes is a promising biotechnological method. However, it is difficult to preferentially enrich manganese-oxidizing bacteria (MnOB) to produce BioMnO x during wastewater treatment processes. A unique method of cultivating MnOB using methane-oxidizing bacteria (MOB) to produce soluble microbial products is proposed here. MnOB were successfully enriched in a methane-fed reactor containing MOB. BioMnO x production during the wastewater treatment process was confirmed. Long-term continual operation of the reactor allowed simultaneous removal of Mn(II), Co(II), and Ni(II). The Co(II)/Mn(II) and Ni(II)/Mn(II) removal ratios were 53% and 19%, respectively. The degree to which Mn(II) was removed indicated that the enriched MnOB used utilization-associated products and/or biomass-associated products. Microbial community analysis revealed that methanol-oxidizing bacteria belonging to the Hyphomicrobiaceae family played important roles in the oxidation of Mn(II) by using utilization-associated products. Methane-oxidizing bacteria were found to be inhibited by MnO 2 , but the maximum Mn(II) removal rate was 0.49 kg m -3 d -1 . Copyright © 2017 Elsevier Ltd. All rights reserved.
Study on the poisoning effect-of non-vanadium catalysts by potassium

NASA Astrophysics Data System (ADS)

Zeng, Huanmu; Liu, Ying; Yu, Xiaowei; Lin, Yasi

2018-02-01

The poisoning effect of catalyst by alkali metals is one of the problems in the selective catalytic reduction (SCR) of NO by NH3. Serious deactivation by alkali poisoning have been proved to take place in the commercial vanadium catalyst. Recently, non-vanadium catalysts such as copper oxides, manganese oxides, chromium oxides and cerium oxides have attracted special attentions in SCR application. However, their tolerance in the presence of alkali metals is still doubtful. In this paper, copper oxides, manganese oxides, chromium oxides and cerium oxides supported on TiO2 nanoparticle was prepared by impregnating method. Potassium nitrate was chosen as the precursor of poisoner. Catalytic activities of these catalysts were evaluated before and after the addition of potassium. Some characterization methods including X-ray diffraction and temperature programmed desorption was utilized to reveal the main reason of alkali deactivation.
L-DOPA-Coated Manganese Oxide Nanoparticles as Dual MRI Contrast Agents and Drug-Delivery Vehicles.

PubMed

McDonagh, Birgitte Hjelmeland; Singh, Gurvinder; Hak, Sjoerd; Bandyopadhyay, Sulalit; Augestad, Ingrid Lovise; Peddis, Davide; Sandvig, Ioanna; Sandvig, Axel; Glomm, Wilhelm Robert

2016-01-20

Manganese oxide nanoparticles (MONPs) are capable of time-dependent magnetic resonance imaging contrast switching as well as releasing a surface-bound drug. MONPs give T2/T2* contrast, but dissolve and release T1-active Mn(2+) and L-3,4-dihydroxyphenylalanine. Complementary images are acquired with a single contrast agent, and applications toward Parkinson's disease are suggested. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, Ying; Lee, Sungsik; Brown, Dennis E.

Ultrafine manganese oxide-decorated carbon nanofibers (MnOn-CNF) as a new type of electrode materials are facilely fabricated by direct conversion of Mn, Zn-trimesic acid (H3BTC) metal organic framework fibers (Mn-ZnBTC). The construction and evolution of Mn-ZnBTC precursors are investigated by SEM and in situ high-energy XRD. The manganese oxides are highly dispersed onto the porous carbon nanofibers formed simultaneously, verified by TEM, X-ray absorption fine structure (XAFS), Raman, ICP-AES and N2 adsorption techniques. As expected, the resulting MnOn-CNF composites are highly stable, and can be cycled up to 5000 times with a high capacitance retention ratio of 98% in electrochemical capacitormore » measurements. They show a high capacitance of up to 179 F g–1 per mass of the composite electrode, and a remarkable capacitance of up to 18290 F g–1 per active mass of the manganese(IV) oxide, significantly exceeding the theoretical specific capacitance of manganese(IV) oxide (1370 F g–1). The maximum energy density is up to 19.7 Wh kg–1 at the current density of 0.25 A g–1, even orders higher than those of reported electric double-layer capacitors and pseudocapacitors. The excellent capacitive performance can be ascribed to the joint effect of easy accessibility, high porosity, tight contact and superior conductivity integrated in final MnOn-CNF composites.« less
Chemical activation of commercial CNTs with simultaneous surface deposition of manganese oxide nano flakes for the creation of CNTs-graphene supported oxygen reduction ternary composite catalysts applied in air fuel cell

NASA Astrophysics Data System (ADS)

Sun, Ling; Liu, Danxian

2018-07-01

To elevate power performance is crucial for commercally potential metal air fuel cells. Non-precious metal oxide-based oxygen reduction catalytic electrode is much desirable. Rational combination with low-dimension nanomaterials are greatly expected as the supports. Herein, carbon nanotubes (CNTs)-graphene supported manganese oxides composite catalysts (CMnCs) were obtained through activating commercial CNTs, namely, immersing them in acidic KMnO4 solution at room condition. It avoided conventional hydrothermal process and template surfactants. CMnCs-based air cathodes were made via pilot manufacture technology and equipped in fuel cells. Through characterizations, CNTs was found structurally defective and their outer walls suffered cracking into graphene nano pieces during processing, which further enhanced oxygen reduction reaction (ORR). Nano sized manganese oxide flakes were simulataneously grown on the CNTs-graphene surfaces, identified as the manganite. The areal distribution was found closely related to the additive amount of KMnO4 with regard to CNTs, somewhat influencing catalytic performance. The ORR activities of these CMnCs exceeded raw CNTs and referred manganese catalysts under identical conditions, and also the CMnCs air fuel cells were capable of outputting ∼15% more power at 100 mA/cm2. This reseach provided an inspiring pilot evidence for updating air fuel cell power from economical carbon as well as industrialization.
Recent advancements in the cobalt oxides, manganese oxides and their composite as an electrode material for supercapacitor: a review

NASA Astrophysics Data System (ADS)

Uke, Santosh J.; Akhare, Vijay P.; Bambole, Devidas R.; Bodade, Anjali B.; Chaudhari, Gajanan N.

2017-08-01

In this smart edge, there is an intense demand of portable electronic devices such as mobile phones, laptops, smart watches etc. That demands the use of such components which has light weight, flexible, cheap and environmental friendly. So that needs an evolution in technology. Supercapacitors are energy storage devices emerging as one of the promising energy storage devices in the future energy technology. Electrode material is the important part of supercapacitor. There is much new advancement in types of electrode materials as for supercapacitor. In this review, we focused on the recent advancements in the cobalt oxides, manganese oxides and their composites as an electrodes material for supercapacitor.
Spinel lithium manganese oxide nanoparticles: unique molten salt synthesis strategy and excellent electrochemical performances.

PubMed

Wang, Xiong; Zhu, Juanjuan; Liu, Yingjie

2009-11-01

As a promising candidate cathode material, spinel lithium manganese oxide nanoparticles were successfully synthesized through a novel molten salt synthesis route at relatively low temperature, using manganese dioxide nanowires as precursor. A variety of techniques were applied to characterize the spinel nanomaterial, including X-ray diffraction, transmission electron microscopy, field-emission scanning electron microscopy, and X-ray photoelectron spectroscopy. The average particle size of the resulting spinel nanoparticles was about 80 nm with narrow distribution. As cathode material for rechargeable lithium ion battery, the electrochemical properties were investigated. All the results show that the electrochemical performances of the homogeneous spinel nanoparticles were improved, which might be ascribed to large specific surface area, fairly narrow size distribution, and the unique synthesis strategy.
Catalyst and method for reduction of nitrogen oxides

DOEpatents

Ott, Kevin C [Los Alamos, NM

2008-05-27

A Selective Catalytic Reduction (SCR) catalyst was prepared by slurry coating ZSM-5 zeolite onto a cordierite monolith, then subliming an iron salt onto the zeolite, calcining the monolith, and then dipping the monolith either into an aqueous solution of manganese nitrate and cerium nitrate and then calcining, or by similar treatment with separate solutions of manganese nitrate and cerium nitrate. The supported catalyst containing iron, manganese, and cerium showed 80 percent conversion at 113 degrees Celsius of a feed gas containing nitrogen oxides having 4 parts NO to one part NO.sub.2, about one equivalent ammonia, and excess oxygen; conversion improved to 94 percent at 147 degrees Celsius. N.sub.2O was not detected (detection limit: 0.6 percent N.sub.2O).

Catalyst and method for reduction of nitrogen oxides

DOEpatents

Ott, Kevin C [Los Alamos, NM

2008-08-19

A Selective Catalytic Reduction (SCR) catalyst was prepared by slurry coating ZSM-5 zeolite onto a cordierite monolith, then subliming an iron salt onto the zeolite, calcining the monolith, and then dipping the monolith either into an aqueous solution of manganese nitrate and cerium nitrate and then calcining, or by similar treatment with separate solutions of manganese nitrate and cerium nitrate. The supported catalyst containing iron, manganese, and cerium showed 80 percent conversion at 113 degrees Celsius of a feed gas containing nitrogen oxides having 4 parts NO to one part NO.sub.2, about one equivalent ammonia, and excess oxygen; conversion improved to 94 percent at 147 degrees Celsius. N.sub.2O was not detected (detection limit: 0.6 percent N.sub.2O).
Catalyst for reduction of nitrogen oxides

DOEpatents

Ott, Kevin C.

2010-04-06

A Selective Catalytic Reduction (SCR) catalyst was prepared by slurry coating ZSM-5 zeolite onto a cordierite monolith, then subliming an iron salt onto the zeolite, calcining the monolith, and then dipping the monolith either into an aqueous solution of manganese nitrate and cerium nitrate and then calcining, or by similar treatment with separate solutions of manganese nitrate and cerium nitrate. The supported catalyst containing iron, manganese, and cerium showed 80 percent conversion at 113 degrees Celsius of a feed gas containing nitrogen oxides having 4 parts NO to one part NO.sub.2, about one equivalent ammonia, and excess oxygen; conversion improved to 94 percent at 147 degrees Celsius. N.sub.2O was not detected (detection limit: 0.6 percent N.sub.2O).
The oxidation state of iron and manganese in polymetallic nodules from the Central Indian Ocean Basin

NASA Astrophysics Data System (ADS)

Ganwani, Girish; Meena, Samay Singh; Ram, Sahi; Bijlani, N.; Bhatia, Beena; Tripathi, R. P.

2018-05-01

The study of oxidation states of iron (Fe) and manganese (Mn) in polymetallic nodules were carried out by means of X-ray photoelectron spectroscopic techniques. The polymetallic nodules were collected from different locations of the Central Indian Ocean Basin (CIOB). The Mn/Fe ratio allowed the differentiation of these nodules from their origin: "hydrogeneous" or "hydrothermal". The binding energies of Mn 2p3/2 (ranging from 641.5 to 642.4 ev), Fe 2p3/2 (ranging from 711.0 to 711.8 ev) and O 1s (ranging from 530.2 to 530.9 ev) from XPS reveal that most of manganese is in Mn4+ and iron is in Fe3+ state.
Systematic Doping of Cobalt into Layered Manganese Oxide Sheets Substantially Enhances Water Oxidation Catalysis.

PubMed

McKendry, Ian G; Thenuwara, Akila C; Shumlas, Samantha L; Peng, Haowei; Aulin, Yaroslav V; Chinnam, Parameswara Rao; Borguet, Eric; Strongin, Daniel R; Zdilla, Michael J

2018-01-16

The effect on the electrocatalytic oxygen evolution reaction (OER) of cobalt incorporation into the metal oxide sheets of the layered manganese oxide birnessite was investigated. Birnessite and cobalt-doped birnessite were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and conductivity measurements. A cobalt:manganese ratio of 1:2 resulted in the most active catalyst for the OER. In particular, the overpotential (η) for the OER was 420 mV, significantly lower than the η = 780 mV associated with birnessite in the absence of Co. Furthermore, the Tafel slope for Co/birnessite was 81 mV/dec, in comparison to a Tafel slope of greater than 200 mV/dec for birnessite. For chemical water oxidation catalysis, an 8-fold turnover number (TON) was achieved (h = 70 mmol of O 2 /mol of metal). Density functional theory (DFT) calculations predict that cobalt modification of birnessite resulted in a raising of the valence band edge and occupation of that edge by holes with enhanced mobility during catalysis. Inclusion of extra cobalt beyond the ideal 1:2 ratio was detrimental to catalysis due to disruption of the layered structure of the birnessite phase.
Rates of manganese oxidation in aqueous systems

USGS Publications Warehouse

Hem, J.D.

1981-01-01

The rate of crystal growth of Mn3O4 (hausmannite) and ??MnOOH (feitknechtite) in aerated aqueous manganous perchlorate systems, near 0.01 M in total manganese, was determined at pH levels ranging from 7.00 to 9.00 and at temperatures from 0.5 to 37.4??C. The process is autocatalytic, but becomes psuedo first-order in dissolved Mn2+ activity when the amount of precipitate surface is large compared to the amount of unreacted manganese. Reaction rates determined by titrations using an automated pH-stat were fitted to an equation for precipitate growth. The rates are proportional to surface area of oxide and degree of supersaturation with respect to Mn2+. The oxide obtained at the higher temperature was Mn3O4, but at 0.5?? C only ??MnOOH was formed. At intermediate temperatures, mixtures of these solids were formed. The rate of precipitation of hausmannite is strongly influenced by temperature, and that of feitknechtite much less so. The difference in activation energy may be related to differences in crystal structure of the oxides and the geometry of polymeric hydroxy ion precursors. ?? 1981.
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.
The Effects of Ionizing Radiation and Oxidizing Species on Strains of Deinococcus Radiodurans Lacking Endogenous Oxidative Protection Methods

DTIC Science & Technology

Deinococcus radiodurans. In addition to radiation the mutated strains were also exposed to paraquat, an oxidizing herbicide . Strains missing manganese super-oxide dismutase and bacillithiol synthesis showed increased sensitivity.
The role of probe oxide in local surface conductivity measurements

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

Barnett, C. J.; Kryvchenkova, O.; Wilson, L. S. J.

2015-05-07

Local probe methods can be used to measure nanoscale surface conductivity, but some techniques including nanoscale four point probe rely on at least two of the probes forming the same low resistivity non-rectifying contact to the sample. Here, the role of probe shank oxide has been examined by carrying out contact and non-contact I V measurements on GaAs when the probe oxide has been controllably reduced, both experimentally and in simulation. In contact, the barrier height is pinned but the barrier shape changes with probe shank oxide dimensions. In non-contact measurements, the oxide modifies the electrostatic interaction inducing a quantummore » dot that alters the tunneling behavior. For both, the contact resistance change is dependent on polarity, which violates the assumption required for four point probe to remove probe contact resistance from the measured conductivity. This has implications for all nanoscale surface probe measurements and macroscopic four point probe, both in air and vacuum, where the role of probe oxide contamination is not well understood.« less
Selection and Use of Manganese Dioxide by Neanderthals

PubMed Central

Heyes, Peter J.; Anastasakis, Konstantinos; de Jong, Wiebren; van Hoesel, Annelies; Roebroeks, Wil; Soressi, Marie

2016-01-01

Several Mousterian sites in France have yielded large numbers of small black blocs. The usual interpretation is that these ‘manganese oxides’ were collected for their colouring properties and used in body decoration, potentially for symbolic expression. Neanderthals habitually used fire and if they needed black material for decoration, soot and charcoal were readily available, whereas obtaining manganese oxides would have incurred considerably higher costs. Compositional analyses lead us to infer that late Neanderthals at Pech-de-l’Azé I were deliberately selecting manganese dioxide. Combustion experiments and thermo-gravimetric measurements demonstrate that manganese dioxide reduces wood’s auto-ignition temperature and substantially increases the rate of char combustion, leading us to conclude that the most beneficial use for manganese dioxide was in fire-making. With archaeological evidence for fire places and the conversion of the manganese dioxide to powder, we argue that Neanderthals at Pech-de-l’Azé I used manganese dioxide in fire-making and produced fire on demand. PMID:26922901
Synthesis of manganese stearate for high density polyethylene (HDPE) and its biodegradation

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

Aras, Neny Rasnyanti M., E-mail: neny.rasnyanti@gmail.com; Arcana, I Made, E-mail: arcana@chem.itb.ac.id

An oxidant additive is one type of additive used for oxo-biodegradable polymers. This additive was prepared by reaction multivalent transition metals and fatty acids to accelerate the degradation process of polymers by providing a thermal treatment or irradiation with light. This study focused on the synthesis of manganese stearate as an additive for application in High Density Polyethylene (HDPE), and the influence of manganese stearate on the characteristics of HDPE including their biodegradability. Manganese stearate was synthesized by the reaction of stearic acid with sodium hydroxide, and sodium stearate formed was reacted with manganese chloride tetrahydrate to form manganese stearatemore » with a melting point of 100-110 °C. Based on the FTIR spectrum showed absorption peak at wave number around 1560 cm{sup −1} which is an asymmetric vibration of CO functional group that binds to the manganese. The films of oxo-biodegradable polymer were prepared by blending HDPE and manganese stearate additives at various concentrations with using the polymer melting method, followed heating at a temperature of 50°C and 70°C for 10 days. The characterizations of the oxo-biodegradable polymers were carried out by analysis the functional groups (FTIR and ATR),thermal properties (TGA), surface properties (SEM), as well as analysis of the biodegradability (the biodegradation test by using activated sludge, % weight loss). Based on COi indicate that the additive of manganese stearate is active in oxidizing polymer by heating treatment. Results of biodegradation by microorganisms from activated sludge showed that the percentage weight loss of polymers increase with the increasing incubation time and the concentration of manganese stearate in HDPE. Biodegradability of HDPE with the addition of manganese stearate and followed by heating at a higher temperature was better observed. The highest percentage weight loss was obtained at the polymer with concentration of 0.2% manganese stearate, and followed by thermal treatment at a temperature of 70 °C and the incubation time for 45 days in the activated sludge.« less
Property Control of (Perfluorinated Ionomer)/(Inorganic Oxide) Composites by Tailoring the Nanoscale Morphology

DTIC Science & Technology

1994-06-10

RPeport PROPERTY CONTROL OF ( PERFLUORINATED IONOMER)/(INORGANIC OXIDE) COMPOSITES BY TAILORING THE NANOSCALE MORPHOLOGY Kenneth A. Mauritz and Robert...Concept ......................................... 45 B. [Si0 2 -TiO2 (mixed)]/Nafion Nanocomposites: Sorption of Pre-Mixed Alkoxides...Nanocomposites: Sorption of Pre- Mixed Alkoxides ......................................... 49 A. Experimental Procedure ............................. 49 B
Influence Of pH On The Transport Of Nanoscale Zinc Oxide In Saturated Porous Media

EPA Science Inventory

Widespread use of nanoscale zinc oxide (nZnO) in various fields causes subsurface environment contamination. Even though the transport of dissolved zinc ions in subsurface environments such as soils and sediments has been widely studied, the transport mechanism of nZnO in such e...
Interaction of Metal Oxides with Biomolecules: Implication in Astrobiology

NASA Astrophysics Data System (ADS)

Kamaluddin; Iqubal, Md. Asif

2014-08-01

Steps of chemical evolution have been designated as formation of biomonomers followed by their polymerization and then to modify in an organized structure leading to the formation of first living cell. Polymerization of biomonomers could have required some catalyst. In addition to clay, role of metal ions and metal complexes as prebiotic catalyst in the synthesis and polymerization of biomonomers cannot be ruled out. Metal oxides are important constituents of Earth crust and that of other planets. These oxides might have adsorbed organic molecules and catalyzed the condensation processes, which may have led to the formation of first living cell. Different studies were performed in order to investigate the role of metal oxides (especially oxides of iron and manganese) in chemical evolution. Iron oxides (goethite, akaganeite and hematite) as well as manganese oxides (MnO, Mn2O3, Mn3O4 and MnO2) were synthesized and their characterization was done using IR, powder XRD, FE-SEM and TEM. Role of above oxides was studied in the adsorption of ribose nucleotides, formation of nucleobases from formamide and oligomerization of amino acids. Above oxides of iron and manganese were found to have good adsorption affinity towards ribose nucleotides, high catalytic activity in the formation of several nucleobases from formamide and oligomerization of glycine and alanine. Characterization of products was performed using UV, IR, HPLC and ESI-MS techniques. Presence of hematite-water system on Mars has been suggested to be a positive indicator in the chemical evolution on Mars.
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 filling dilatational fractures along with barite.
Evaluation of distribution and manganese availability in soils under soybean cultivation

NASA Astrophysics Data System (ADS)

Mendes Coutinho, Edson Luiz; de Cássia Gomes São João, Andréia; Mendes Coutinho Neto, André; Corá, José Eduardo; Fernandes, Carolina

2013-04-01

Manganese (Mn) deficiency in soybean became a problem in Brazil, mainly, due to soil low fertility use or soil high pH due to incorrect lime use. However, the manganese deficiency have not been thoroughly investigated. The effect of Mn soil application on Mn distribution among exchangeable, organic matter, amorphous Fe and Al oxides, crystalline Fe and Al oxides, and residual fractions were studied on a Typic Quartzipsament (RQ), a clayey Typic Haplustox (LVA) and a sandy clay loam Typic Haplustox (LV), in a greenhouse experiment carried out in Jaboticabal (SP) - Brazil (21°14'05'' S and 48°17'09'' W). A complete randomized design with three replications of treatments in a 3 x 6 factorial arrangement (three soils and six manganese rates) was used. Five soybean plants were grown during 34 days in pots with 2.5 kg of soil. The Mn contents in these fractions were correlated with those extracted by DTPA and by Mehlich-1 extractants and with soybean shoot Mn contents. Mn rates (0, 5, 10, 20, 40 and 60 mg kg-1) were applied using manganese sulphate (MnSO4). In the Oxisols, most of the Mn was associated with the Fe and Al oxides (amorphous and crystalline) and residual fractions. In the sandy soil (RQ), higher contents were found in exchangeable and residual fractions. Exchangeable fraction was the most important Mn supplier to soybean plants. Multiple regression analysis showed that Mn extracted by DTPA and Mehlich-1 were associated with soil exchangeable fraction.
Exchange interactions in a dinuclear manganese (II) complex with cyanopyridine-N-oxide bridging ligands

NASA Astrophysics Data System (ADS)

Markosyan, A. S.; Gaidukova, I. Yu.; Ruchkin, A. V.; Anokhin, A. O.; Irkhin, V. Yu.; Ryazanov, M. V.; Kuz'mina, N. P.; Nikiforov, V. N.

2014-01-01

The magnetic properties of dinuclear manganese(II) complex [Mn(hfa)2cpo]2 (where hfa is hexafluoroacetylacetonate anion and cpo is 4-cyanopyridine-N-oxide) are presented. The non-monotonous dependence of magnetic susceptibility is explained in terms of the hierarchy of exchange parameters by using exact diagonalization. The thermodynamic behavior of pure cpo and [Mn(hfa)2(cpo)]2 is simulated numerically by an extrapolation to spin S=5/2. The Mn-Mn exchange integral is evaluated.
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
Enhanced oxidation of arsenite to arsenate using tunable K+ concentration in the OMS-2 tunnel.

PubMed

Hou, Jingtao; Sha, Zhenjie; Hartley, William; Tan, Wenfeng; Wang, Mingxia; Xiong, Juan; Li, Yuanzhi; Ke, Yujie; Long, Yi; Xue, Shengguo

2018-07-01

Cryptomelane-type octahedral molecular sieve manganese oxide (OMS-2) possesses high redox potential and has attracted much interest in its application for oxidation arsenite (As(III)) species of arsenic to arsenate (As(V)) to decrease arsenic toxicity and promote total arsenic removal. However, coexisting ions such as As(V) and phosphate are ubiquitous and readily bond to manganese oxide surface, consequently passivating surface active sites of manganese oxide and reducing As(III) oxidation. In this study, we present a novel strategy to significantly promote As(III) oxidation activity of OMS-2 by tuning K + concentration in the tunnel. Batch experimental results reveal that increasing K + concentration in the tunnel of OMS-2 not only considerably improved As(III) oxidation kinetics rate from 0.027 to 0.102 min -1 , but also reduced adverse effect of competitive ion on As(III) oxidation. The origin of K + concentration effect on As(III) oxidation was investigated through As(V) and phosphate adsorption kinetics, detection of Mn 2+ release in solution, surface charge characteristics, and density functional theory (DFT) calculations. Experimental results and theoretical calculations confirm that by increasing K + concentration in the OMS-2 tunnel not only does it improve arsenic adsorption on K + doped OMS-2, but also accelerates two electrons transfers from As(III) to each bonded Mn atom on OMS-2 surface, thus considerably improving As(III) oxidation kinetics rate, which is responsible for counteracting the adverse adsorption effects by coexisting ions. Copyright © 2018 Elsevier Ltd. All rights reserved.
Fingerprinting Bacterial and Fungal Manganese Oxidation via Stable Oxygen Isotopes of Manganese Oxides

NASA Astrophysics Data System (ADS)

Sutherland, K. M.; Wankel, S. D.; Hansel, C. M.

2016-12-01

Manganese (Mn) oxides are a ubiquitous mineralogical component of surface Earth and Mars. Mn(III/IV) oxides are potent environmental sorbents and oxidants that play a crucial role in the fate of organic matter. The processes by which Mn(II) oxidation occurs in natural systems are poorly understood, but a number of studies have implicated microogranisms as the primary agents of Mn(II) oxidation in terrestrial and marine environments. The ability of microorganisms to oxidize Mn(II) to Mn(III/IV) oxides transcends the boundaries of biological domain, with an abundance of well-characterized prokaryotes as well as eukaryotic fungi with the ability to oxidize Mn(II) to Mn(III/IV) oxides. Biological Mn(II) oxidation proceeds directly through enzymatic activity or indirectly through the production of reactive oxygen species. Building upon earlier research suggesting that stable oxygen isotope fractionation could be used to fingerprint unique Mn(II)-oxidizing organisms or distinct oxidation pathways, here we use culture-based studies of Mn(II)-oxidizing bacteria and fungi to determine the kinetic oxygen isotope effects associated with Mn(II) oxidation. Since the oxygen molecules in Mn(III/IV) oxides are comprised of oxygen from both precursor water and molecular oxygen, we used a two-fold approach to constrain isotope fractionation with respect to each oxygen source. We used open system oxidation experiments using oxygen-18 labeled water in parallel with closed system Rayleigh distillation oxidation experiments to fully constrain isotope fractionation associated with oxygen atom incorporation during Mn(II) oxidation. Our results suggest commonalities among fractionation factors from groups of Mn(II)-oxidizing organisms that have similar oxidation mechanisms. These results suggest that stable oxygen isotopes of Mn(III/IV) oxides have the potential to distinguish between Mn(II) oxidation pathways in nature, providing a way to determine which groups of Mn(II) oxidizers may be active in present and past surface Earth environments.
Why did Nature choose manganese to make oxygen?

PubMed Central

Armstrong, Fraser A

2007-01-01

This paper discusses the suitability of manganese for its function in catalysing the formation of molecular oxygen from water. Manganese is an abundant element. In terms of its inherent properties, Mn has a particularly rich redox chemistry compared with other d-block elements, with several oxidizing states accessible. The most stable-state Mn2+ behaves like a Group 2 element—it is mobile, weakly complexing, easily taken up by cells and redox-inactive in simple aqueous media. Only in the presence of suitable ligands does Mn2+ become oxidized, so it provides an uncomplicated building unit for the oxygen-evolving centre (OEC). The intermediate oxidation states Mn(III) and Mn(IV) are strongly complexed by O2− and form robust mixed-valence poly-oxo clusters in which the Mn(IV)/Mn(III) ratio can be elevated, one electron at a time, accumulating oxidizing potential and capacity. The OEC is a Mn4CaOx cluster that undergoes sequential oxidations by P680+ at potentials above 1 V, ultimately to a super-oxidized level that includes one Mn(V) or a Mn(IV)-oxyl radical. The latter is powerfully oxidizing and provides the crucial ‘power stroke’ necessary to generate an O–O bond. This leaves a centre still rich in Mn(IV), ensuring a rapid follow-through to O2. PMID:17971329

Water-oxidation catalysis by synthetic manganese oxides--systematic variations of the calcium birnessite theme.

PubMed

Frey, Carolin E; Wiechen, Mathias; Kurz, Philipp

2014-03-21

Layered manganese oxides from the birnessite mineral family have been identified as promising heterogeneous compounds for water-oxidation catalysis (WOC), a key reaction for the conversion of renewable energy into storable fuels. High catalytic rates were especially observed for birnessites which contain calcium as part of their structures. With the aim to systematically improve the catalytic performance of such oxide materials, we used a flexible synthetic route to prepare three series of calcium birnessites, where we varied the calcium concentrations, the ripening times of the original precipitates and the temperature of the heat treatment following the initial synthetic steps (tempering) during the preparation process. The products were carefully analysed by a number of analytical techniques and then probed for WOC activity using the Ce(4+)-system. We find that our set of twenty closely related manganese oxides shows large, but somewhat systematic alterations in catalytic rates, indicating the importance of synthesis parameters for maximum catalytic performance. The catalyst of the series for which the highest water-oxidation rate was found is a birnessite of medium calcium content (Ca : Mn ratio 0.2 : 1) that had been subjected to a tempering temperature of 400 °C. On the basis of the detailed analysis of the results, a WOC reaction scheme for birnessites is proposed to explain the observed trends in reactivity.
Effect of Manganese on some aspects of carbohydrate metabolism in rats. [None

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

Husain, R.; Mushtaq, M.; Seth, P.K.

1980-10-01

Numerous biochemical and toxicological studies have indicated that chronic exposure to manganese leads to neurological abnormalities. Increasing use of manganese compounds as antiknocks in gasoline and diesel fuel has aroused a great concern over the toxicological potential of this metal and stressed the need for understanding the mechanism of its poisoning. Reports of alerations in the levels of biogenic amines have helped in understanding the basis of neurological disorders. However, little is known about the mechanism by which manganese exposure leads to hypoglycemia in workers. This study deals with the influence of manganese exposure on metabolism of glucose, the chiefmore » fuel of the brain, and some enzymes involved in its oxidation. These studies will provide an assessment of the extent to which manganese affects the various processes controlling carbohydrate metabolism.« less
Manganese: it turns iron into steel (and does so much more)

USGS Publications Warehouse

Cannon, William F.

2014-01-01

Manganese is a common ferrous metal with atomic weight of 25 and the chemical symbol Mn. It constitutes roughly 0.1 percent of the Earth’s crust, making it the 12th most abundant element. Its early uses were limited largely to pigments and oxidants in chemical processes and experiments, but the significance of manganese to human societies exploded with the development of modern steelmaking technology in the 1860s. U.S consumption of manganese is about 500,000 metric tons each year, predominantly by the steel industry. Because manganese is essential and irreplaceable in steelmaking and its global mining industry is dominated by just a few nations, it is considered one of the most critical mineral commodities for the United States.
[Factors affecting biological removal of iron and manganese in groundwater].

PubMed

Xue, Gang; He, Sheng-Bing; Wang, Xin-Ze

2006-01-01

Factors affecting biological process for removing iron and manganese in groundwater were analyzed. When DO and pH in groundwater after aeration were 7.0 - 7.5 mg/L and 6.8 - 7.0 respectively, not only can the activation of Mn2+ oxidizing bacteria be maintained, but also the demand of iron and manganese removal can be satisfied. A novel inoculating approach of grafting mature filter material into filter bed, which is easier to handle than selective culture media, was employed in this research. However, this approach was only suitable to the filter material of high-quality manganese sand with strong Mn2+ adsorption capacity. For the filter material of quartz sand with weak adsorption capacity, only culturing and domesticating Mn2+ oxidizing bacteria by selective culture media can be adopted as inoculation in filter bed. The optimal backwashing rate of biological filter bed filled with manganese sand and quartz sand should be kept at a relatively low level of 6 - 9 L/(m2 x s) and 7 -11 L/( m2 x s), respectively. Then the stability of microbial phase in filter bed was not disturbed, and iron and manganese removal efficiency recovered in less than 5h. Moreover, by using filter material with uniform particle size of 1.0 - 1.2 mm in filter bed, the filtration cycle reached as long as 35 - 38h.
Discovery of Unusual Minerals in Paleolithic Black Pigments from Lascaux (France) and Ekain (Spain)

NASA Astrophysics Data System (ADS)

Chalmin, E.; Farges, F.; Vignaud, C.; Susini, J.; Menu, M.; Brown, G. E.

2007-02-01

Analyses of archaeological materials aim to rediscover the know-how of Prehistoric people by determining the nature of the painting matter, its preparation mode, and the geographic origin of its raw materials. This study deals with identification of manganese oxides in black pigments by micro-XANES (X-ray absorption near-edge structure) based on previous TEM (transmission electron microscopy) studies. Complex mixtures of the manganese oxides studied are present in some of mankind's oldest known paintings, namely those from the caves of Lascaux (Dordogne, France) and Ekain (Basque country, Spain). Scarce manganese oxide minerals, including groutite, hausmannite, and manganite, were found for the first time in Paleolithic art at these archaeological sites. Because there are no known deposits of such minerals in these areas, more distant origins and trade routes are inferred. The closest known Mn-rich geological province for Lascaux is the central Pyrénées, which is ≈ 250 km from the Dordogne area.
Fungi and bacteria involved in desert varnish formation

NASA Technical Reports Server (NTRS)

Taylor-George, S.; Palmer, F.; Staley, J. T.; Curtiss, B.; Adams, J. B.; Borns, D. J.

1983-01-01

Desert varnish is a coating of ferromanganese oxides and clays that develops on rock surfaces in arid to semi-arid regions. Active respiration but not photosynthesis was detected on varnished rock surfaces from the Sonoran Desert. Light microscopy, scanning electron microscopy (SEM) and transmission electron microscopy (TEM) observations, and cultivation experiments indicate that both fungi, primarily dematiaceous hyphomycetes, and bacteria are found on and within desert varnish coatings from the arid regions studied. Some fungi grow as microcolonial fungi (MCF) on rocks, and microscopic observations suggest MCF become incorporated in the varnish coating. SEM-EDAX (energy dispersive X-ray systems) analyses indicate the MCF contain 3 of the characteristic elements of varnish: iron, aluminum, and silicon. In some locations, MCF are also enriched in manganese relative to the rock substratum. Furthermore, some of the dematiaceous hyphomycetes that have been cultivated are able to oxidize manganese under laboratory conditions. It is possible that manganese-oxidizing bacteria, which are found in varnish, also play an important role in varnish formation.
Discovery of Unusual Minerals in Paleolithic Black Pigments from Lascaux (France) and Ekain (Spain)

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

Chalmin, E.; /Marne la Vallee U.; Farges, F.

2006-12-13

Analyses of archaeological materials aim to rediscover the know-how of Prehistoric people by determining the nature of the painting matter, its preparation mode, and the geographic origin of its raw materials. This study deals with identification of manganese oxides in black pigments by micro-XANES (X-ray absorption near-edge structure) based on previous TEM (transmission electron microscopy) studies. Complex mixtures of the manganese oxides studied are present in some of mankind's oldest known paintings, namely those from the caves of Lascaux (Dordogne, France) and Ekain (Basque country, Spain). Scarce manganese oxide minerals, including groutite, hausmannite, and manganite, were found for the firstmore » time in Paleolithic art at these archaeological sites. Because there are no known deposits of such minerals in these areas, more distant origins and trade routes are inferred. The closest known Mn-rich geological province for Lascaux is the central Pyrenees, which is {approx} 250 km from the Dordogne area.« less
In Situ Atom Probe Deintercalation of Lithium-Manganese-Oxide.

PubMed

Pfeiffer, Björn; Maier, Johannes; Arlt, Jonas; Nowak, Carsten

2017-04-01

Atom probe tomography is routinely used for the characterization of materials microstructures, usually assuming that the microstructure is unaltered by the analysis. When analyzing ionic conductors, however, gradients in the chemical potential and the electric field penetrating dielectric atom probe specimens can cause significant ionic mobility. Although ionic mobility is undesirable when aiming for materials characterization, it offers a strategy to manipulate materials directly in situ in the atom probe. Here, we present experimental results on the analysis of the ionic conductor lithium-manganese-oxide with different atom probe techniques. We demonstrate that, at a temperature of 30 K, characterization of the materials microstructure is possible without measurable Li mobility. Also, we show that at 298 K the material can be deintercalated, in situ in the atom probe, without changing the manganese-oxide host structure. Combining in situ atom probe deintercalation and subsequent conventional characterization, we demonstrate a new methodological approach to study ionic conductors even in early stages of deintercalation.
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).
Immobilization of hexavalent chromium in contaminated soils using biochar supported nanoscale iron sulfide composite.

PubMed

Lyu, Honghong; Zhao, Hang; Tang, Jingchun; Gong, Yanyan; Huang, Yao; Wu, Qihang; Gao, Bin

2018-03-01

Biochar supported carboxymethyl cellulose (CMC)-stabilized nanoscale iron sulfide (FeS) composite (CMC-FeS@biochar) was prepared and tested for immobilization of hexavalent chromium Cr(VI) in soil. Results of UV-vis and transmission electron microscopy (TEM) showed that the backbone of biochar suppressed the aggregation of FeS, resulting in smaller particle size and more sorption sites than bare FeS. The composite at a dosage of 2.5 mg per gram soil displayed an enhanced Cr(VI) immobilization efficiency (a 94.7% reduction in the toxicity characteristic leaching procedure (TCLP) based leachability and a 95.6% reduction in the CaCl 2 extraction) compared to plain biochar and bare FeS. Sequential extraction procedure (SEP) and X-ray photoelectron spectroscopy (XPS) analysis suggested that CMC-FeS@biochar promoted the conversion of more accessible Cr (exchangeable and carbonate-bound fractions) into the less accessible forms (iron-manganese oxides-bound, organic material-bound, and residual fractions) to reduce the toxicity of Cr(VI) and that surface sorption and reduction were dominant mechanisms for Cr(VI) immobilization. CMC-FeS@biochar greatly reduced the bioavailability of Cr(VI) to wheat and earthworms (Eisenia fetida). Moreover, the application of CMC-FeS@biochar enhanced soil organic matter content and microbial activity. This work highlighted the potential of CMC-FeS@biochar composite as a low-cost, "green", and effective amendment for immobilizing Cr(VI) in contaminated soils and improving soil properties. Copyright © 2017 Elsevier Ltd. All rights reserved.
The Impact of Potassium Manganate (VII) on the Effectiveness of Coagulation in the Removal of Iron and Manganese from Groundwater with an Increased Content of Organic Substances

NASA Astrophysics Data System (ADS)

Krupińska, Izabela

2017-12-01

The article presents the results of studies concerning the impact of the method of Fe(II) ion oxidisation (dissolved oxygen and potassium manganate (VII)) on the effectiveness of coagulation in the removal of iron and manganese from groundwater with an increased content of organic substances. The efficiencies of two coagulants were compared: aluminium sulphate (VI) and polyaluminium chloride (Flokor 1.2A). Among the used methods of iron (II) oxidisation, the best effects have been achieved by potassium manganate (VII) because one of the oxidation products was manganese oxide (IV) precipitating from water. Better results in purifying the water were obtained with the use of a prehydrolysed coagulant Flokor 1.2 A than aluminium sulphate (VI).
A systematic probe in the properties of spray coated mixed spinel films of cobalt and manganese

NASA Astrophysics Data System (ADS)

Grace Victoria, S.; Moses Ezhil Raj, A.

2018-01-01

The multiple oxidation states of manganese and cobalt in cobalt manganese oxides play a crucial role in shaping up the vivid properties thus evoking curiosity among researchers. In the present work, mixed spinel films of CoMn(CoMn)2O4 were coated on glass substrates by the spray pyrolysis technique with different precursor concentrations of the acetate salts of the metals in ethyl alcohol. XRD investigations revealed an intermediate tetragonal spinel structure between cubic MnCo2O4 and tetragonal Mn3O4 (JCPDS 18-0410) with predominant orientation along (311) plane. The tetragonal distortion from cubic symmetry may be due to high Mn2+ ion content at octahedral sites. Raman spectroscopy highlighted two typical emission peaks characteristic of the deposited mixed spinel oxides. Functional groups were assigned with the aid of FTIR spectral analysis to the observed absorption bands. The binding energies of the photo-electron peaks observed for the transition metal ions and the oxygenated ions were recorded by XPS. The results indicated that the divalent and trivalent ions of cobalt co-existed with the divalent manganese ions. AFM images revealed vertically aligned columnar grains. The electrical measurements indicated conduction mechanism through jumps of polarons. Optical absorption revealed wide band gap energy of 3.76 eV.
Energy metabolism in astrocytes and neurons treated with manganese: relation among cell-specific energy failure, glucose metabolism, and intercellular trafficking using multinuclear NMR-spectroscopic analysis.

PubMed

Zwingmann, Claudia; Leibfritz, Dieter; Hazell, Alan S

2003-06-01

A central question in manganese neurotoxicity concerns mitochondrial dysfunction leading to cerebral energy failure. To obtain insight into the underlying mechanism(s), the authors investigated cell-specific pathways of [1-13C]glucose metabolism by high-resolution multinuclear NMR-spectroscopy. Five-day treatment of neurons with 100-micro mol/L MnCl(2) led to 50% and 70% decreases of ATP/ADP and phosphocreatine-creatine ratios, respectively. An impaired flux of [1-13C]glucose through pyruvate dehydrogenase, which was associated with Krebs cycle inhibition and hence depletion of [4-13C]glutamate, [2-13C]GABA, and [13C]glutathione, hindered the ability of neurons to compensate for mitochondrial dysfunction by oxidative glucose metabolism and further aggravated neuronal energy failure. Stimulated glycolysis and oxidative glucose metabolism protected astrocytes against energy failure and oxidative stress, leading to twofold increased de novo synthesis of [3-13C]lactate and fourfold elevated [4-13C]glutamate and [13C]glutathione levels. Manganese, however, inhibited the synthesis and release of glutamine. Comparative NMR data obtained from cocultures showed disturbed astrocytic function and a failure of astrocytes to provide neurons with substrates for energy and neurotransmitter metabolism, leading to deterioration of neuronal antioxidant capacity (decreased glutathione levels) and energy metabolism. The results suggest that, concomitant to impaired neuronal glucose oxidation, changes in astrocytic metabolism may cause a loss of intercellular homeostatic equilibrium, contributing to neuronal dysfunction in manganese neurotoxicity.
Nanoscale electrical and structural modification induced by rapid thermal oxidation of AlGaN/GaN heterostructures.

PubMed

Greco, Giuseppe; Fiorenza, Patrick; Giannazzo, Filippo; Alberti, Alessandra; Roccaforte, Fabrizio

2014-01-17

In this paper, the structural and electrical modifications induced, in the nanoscale, by a rapid thermal oxidation process on AlGaN/GaN heterostructures, are investigated. A local rapid oxidation (900 ° C in O2, 10 min) localized under the anode region of an AlGaN/GaN diode enabled a reduction of the leakage current with respect to a standard Schottky contact. The insulating properties of the near-surface oxidized layer were probed by a nanoscale electrical characterization using scanning probe microscopy techniques. The structural characterization indicated the formation of a thin uniform oxide layer on the surface, with preferential oxidation paths along V-shaped defects penetrating through the AlGaN/GaN interface. The oxidation process resulted in an expansion of the lattice parameters due to the incorporation of oxygen atoms, accompanied by an increase of the crystal mosaicity. As a consequence, a decrease of the sheet carrier density of the two-dimensional electron gas and a positive shift of the threshold voltage are observed. The results provide useful insights for a possible future integration of rapid oxidation processes during GaN device fabrication.
Effect of land use pattern change from paddy soil to vegetable soil on the adsorption-desorption of cadmium by soil aggregates.

PubMed

Zhang, Qiu; Li, Zhongwu; Huang, Bin; Luo, Ninglin; Long, Lingzhi; Huang, Mei; Zhai, Xiuqing; Zeng, Guangming

2017-01-01

The influence of land use change from paddy soil to vegetable soil on the adsorption-desorption behavior of Cd in soil aggregates and the variation in soil properties were investigated. The vegetable soil was characterized by lower pH, organic matter content, cation exchange capacity (CEC), free iron oxides, manganese oxides, and catalase activity and higher urease activity compared with the paddy soil. In the isothermal adsorption and desorption experiments, the adsorption characteristics of Cd of the two soils could be well described by Langmuir and Freundlich equations. The adsorption capacity of vegetable soil decreased 22.72 %, and the desorption rate increased 35 % with respect to paddy soil. Therefore, conversion from paddy to vegetable field can reduce the adsorption ability to Cd of the soil to a certain extent. Both the two soils reached the maximum adsorption capacity and the minimum desorption rate in the <0.002-mm faction. The adsorption capacity of Cd in paddy and vegetable soils exhibited great reliance on the content of CEC. Desorption rate was negatively correlated with the four indicators: organic matter, CEC, free iron oxides, and manganese oxides, and specific adsorption was primarily controlled by soil organic matter and manganese oxides.
Heavy Metal Soil Contamination at U.S. Army Installations: Proposed Research and Strategy for Technology Development

DTIC Science & Technology

1994-03-01

substrates that form the basis of the soil, such as carbonates, clay minerals, organic matter, iron and manganese oxides and hydroxides, sulfides, or...32 10 25 2.5 32 to 64 7 20 1.4 Total 100 200.7 interstitial water, clay minerals, sulfides, carbonates, organic matter, hydrous iron and manganese ...condensation reaction with OH- groups on the surface of (silicon, iron, manganese , and aluminum) com- pounds (Calmano and Forsmer 1983). Sorption-based
Thin film passivation of laser generated 3D micro patterns in lithium manganese oxide cathodes

NASA Astrophysics Data System (ADS)

Pröll, J.; Kohler, R.; Bruns, M.; Oberst, V.; Weidler, P. G.; Heißler, S.; Kübel, C.; Scherer, T.; Prang, R.; Seifert, H. J.; Pfleging, W.

2013-03-01

The increasing need for long-life lithium-ion batteries requires the further development of electrode materials. Especially on the cathode side new materials or material composites are needed to increase the cycle lifetime. On the one hand, spinel-type lithium manganese oxide is a promising candidate to be used as cathode material due to its non-toxicity, low cost and good thermal stability. On the other hand, the spinel structure suffers from change in the oxidation state of manganese during cycling which is also accompanied by loss of active material into the liquid electrolyte. The general trend is to enhance the active surface area of the cathode in order to increase lithium-ion mobility through the electrode/electrolyte interface, while an enhanced surface area will also promote chemical degradation. In this work, laser microstructuring of lithium manganese oxide thin films was applied in a first step to increase the active surface area. This was done by using 248 nm excimer laser radiation and chromium/quartz mask imaging techniques. In a second step, high power diode laser-annealing operating at a wavelength of 940 nm was used for forming a cubic spinel-like battery phase. This was verified by means of Raman spectroscopy and cyclic voltammetric measurements. In a last step, the laser patterned thin films were coated with indium tin oxide (ITO) layers with a thickness of 10 nm to 50 nm. The influence of the 3D surface topography as well as the ITO thickness on the electrochemical performance was studied by cyclic voltammetry. Post-mortem studies were carried out by using scanning electron microscopy and focused ion beam analysis.
Enhancement of arsenite removal using manganese oxide coupled with iron (III) trimesic

NASA Astrophysics Data System (ADS)

Phanthasri, Jakkapop; Khamdahsag, Pummarin; Jutaporn, Panitan; Sorachoti, Kwannapat; Wantala, Kitirote; Tanboonchuy, Visanu

2018-01-01

A simultaneous removal of As(III) was investigated on a mixture of manganese oxide based octahedral molecular sieves (K-OMS2) and iron-benzenetricarboxylate (Fe-BTC). As(III) removal was stimulated by an oxidation cooperated with adsorption process. K-OMS2 and Fe-BTC were separately synthesized and characterized by X-ray diffraction (XRD), Transmission Electron Microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). K-OMS2 showed characters of pure cryptomelane phase, nanorod structure, and a mixed-valent manganese framework with the coexistence of Mn(IV) and Mn(III). As(III) was successfully oxidized to As(V) by K-OMS2 in a temperature range of 303-333 K. An intermediate adsorption of As(V) was carried out with Fe-BTC in the same batch. A maximum adsorption capacity, described by Langmuir isotherm model, was observed at 76.34 mg/g. With an As(III) initial concentration of 5 mg/L, when K-OMS2 and Fe-BTC were simultaneously introduced into the solution, the As(III) removal process was completed within 60 min. Thus, it shortened the process time compared to the case where K-OMS2 was added first, followed by the addition of Fe-BTC.
Rates of manganese oxidation in aqueous systems

NASA Astrophysics Data System (ADS)

Hem, John D.

1981-08-01

The rate of crystal growth of Mn 3O 4 (hausmannite) and βMnOOH (feitknechtite) in aerated aqueous manganous perchlorate systems, near 0.01 M in total manganese, was determined at pH levels ranging from 7.00 to 9.00 and at temperatures from 0.5 to 37.4°C. The process is autocatalytic, but becomes psuedo first-order in dissolved Mn 2+ activity when the amount of precipitate surface is large compared to the amount of unreacted manganese. Reaction rates determined by titrations using an automated pH-stat were fitted to an equation for precipitate growth. The rates are proportional to surface area of oxide and degree of supersaturation with respect to Mn 2+. The oxide obtained at the higher temperature was Mn 3O 4, but at 0.5° C only βMnOOH was formed. At intermediate temperatures, mixtures of these solids were formed. The rate of precipitation of hausmannite is strongly influenced by temperature, and that of feitknechtite much less so. The difference in activation energy may be related to differences in crystal structure of the oxides and the geometry of polymeric hydroxy ion precursors.
Formation of secondary minerals in a lysimeter approach - A mineral-microbe interaction

NASA Astrophysics Data System (ADS)

Schäffner, F.; Merten, D.; De Giudici, G.; Beyer, A.; Akob, D. M.; Ricci, P. C.; Küsel, K.; Büchel, G.

2012-04-01

Heavy metal contamination of large areas due to uranium mining operations poses a serious long-term environmental problem. In the Ronneburg district (eastern Thuringia, Germany), leaching of low grade uranium bearing ores (uranium content < 300 g/t) occurred from 1972 to 1990 using acid mine drainage (AMD; pH 2.7-2.8) and diluted sulphuric acid (10 g/l). Secondary mineral phases like birnessite, todorokite and goethite occur within a natural attenuation process associated with enrichment of heavy metals, especially Cd, Ni, Co, Cu and Zn due to a residual contamination even after remediation efforts. To reveal the processes of secondary mineral precipitation in the field a laboratory lysimeter approach was set up under in situ-like conditions. Homogenized soil from the field site and pure quartz sand were used as substrates. In general, in situ measurements of redox potentials in the substrates showed highly oxidizing conditions (200-750 mV). Water was supplied to the lysimeter from below via a mariottés bottle containing contaminated groundwater from the field. Evaporation processes were allowed, providing a continuous flow of water. This led to precipitation of epsomite and probably aplowite on the top layer of substrate, similar to what is observed in field investigations. After 4 weeks, the first iron and manganese bearing secondary minerals became visible. Soil water samples were used to monitor the behaviour of metals within the lysimeter. Saturation indices (SI) for different secondary minerals were calculated with PHREEQC. The SI of goethite showed oversaturation with respect to the soil solution. SEM-EDX analyses and IR spectroscopy confirmed the formation of goethite. Geochemical data revealed that goethite formation was mainly dominated by Eh/pH processes and that heavy metals, e.g. Zn and U, could be enriched in this phase. Although Eh/pH data does not support formation of manganese minerals, Mn(II)-oxidizing bacteria (MOB) could be isolated from field soil samples, supporting the fact that microorganisms may influence this natural attenuation process. Laser ablation ICP-MS data reveal accumulation of manganese in MOB biomass on Mn(II)-containing agar plates. Furthermore, it was possible to show the importance of iron on this process, as some MOB isolates were able to oxidize manganese independently from the iron content, whereas some are not. The latter isolates are only able to oxidize manganese if iron is present in the media. In the lysimeter, SEM-EDX data showed microorganisms in organic rich phases together with the occurrence of manganese, oxygen, and nickel, indicating manganese oxides enriched in nickel. Although this new mineral phases could not yet be identified microprobe EDX results from polished thin sections showed needle-like mineral structures that are similar to the birnessite and todorokite samples observed from field samples. Hence, the lysimeter experiment revealed that the formation of iron and manganese minerals that are involved in heavy metal natural attenuation is result of both abiotic and biotic processes.

Method for removing soot from exhaust gases

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

Suib, Steven L.; Dharmarathna, D. A. Saminda; Pahalagedara, Lakshitha R.

A method for oxidizing soot from diesel exhaust gas from a diesel engine. The method involves providing a diesel particulate filter for receiving the diesel exhaust gas; coating a catalyst composition on the diesel particulate filter; and contacting the soot from the diesel exhaust gas with the catalyst coated diesel particulate filter at a temperature sufficient to oxidize the soot to carbon dioxide. The catalyst composition is a doped or undoped manganese oxide octahedral molecular sieve (OMS-2) material. A diesel exhaust gas treatment system that includes a diesel particulate filter for receiving diesel exhaust gas from a diesel engine andmore » collecting soot; and a catalyst composition coated on the diesel particulate filter. The catalyst composition is a doped or undoped manganese oxide octahedral molecular sieve (OMS-2).« less
Modeling Manganese Silicate Inclusion Composition Changes during Ladle Treatment Using FactSage Macros

NASA Astrophysics Data System (ADS)

Piva, Stephano P. T.; Kumar, Deepoo; Pistorius, P. Chris

2017-02-01

This work investigated the use of FactSage macros to simulate steel-slag and steel-inclusion reaction kinetics in silicon-manganese killed steels, and predict oxide inclusion composition changes during ladle treatment. These changes were assessed experimentally using an induction furnace to simulate deoxidation and slag addition. The average steel mass transfer coefficient for the experimental setup was calculated from the analyzed aluminum pick-up by steel. Average oxide inclusion composition was measured using scanning electron microscopy and energy-dispersive X-ray spectroscopy. Confocal laser scanning microscopy was used to assess the physical state (solid or liquid) of oxide inclusions in selected samples. The changes in the chemical compositions of the oxide inclusions and the steel agreed with the FactSage macro simulations.
Respiration-linked proton translocation coupled to anaerobic reduction of manganese(IV) and iron(III) in Shewanella putrefaciens MR-1.

PubMed Central

Myers, C R; Nealson, K H

1990-01-01

An oxidant pulse technique, with lactate as the electron donor, was used to study respiration-linked proton translocation in the manganese- and iron-reducing bacterium Shewanella putrefaciens MR-1. Cells grown anaerobically with fumarate or nitrate as the electron acceptor translocated protons in response to manganese (IV), fumarate, or oxygen. Cells grown anaerobically with fumarate also translocated protons in response to iron(III) and thiosulfate, whereas those grown with nitrate did not. Aerobically grown cells translocated protons only in response to oxygen. Proton translocation with all electron acceptors was abolished in the presence of the protonophore carbonyl cyanide m-chlorophenylhydrazone (20 microM) and was partially to completely inhibited by the electron transport inhibitor 2-n-heptyl-4-hydroxyquinoline N-oxide (50 microM). PMID:2172208
Anchoring alpha-manganese oxide nanocrystallites on multi-walled carbon nanotubes as electrode materials for supercapacitor

NASA Astrophysics Data System (ADS)

Li, Li; Qin, Zong-Yi; Wang, Ling-Feng; Liu, Hong-Jin; Zhu, Mei-Fang

2010-09-01

The partial coverage of manganese oxide (MnO2) particles was achieved on the surfaces of multi-walled carbon nanotubes (MWCNTs) through a facile hydrothermal process. These particles were demonstrated to be alpha-manganese dioxide (α-MnO2) nanocrystallites, and exhibited the appearance of the whisker-shaped crystals with the length of 80-100 nm. In such a configuration, the uncovered CNTs in the nanocomposite acted as a good conductive pathway and the whisker-shaped MnO2 nanocrystallites efficiently increased the contact of the electrolyte with the active materials. Thus, the highest specific capacitance of 550 F g-1 was achieved using the resulting nanocomposites as the supercapacitor electrode. In addition, the enhancement of the capacity retention was observed, with the nanocomposite losing only 10% of the maximum capacity after 1,500 cycles.
Reverse micelle synthesis of nanoscale metal containing catalysts

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

Darab, J.G.; Fulton, J.L.; Linehan, J.C.

1993-03-01

The need for morphological control during the synthesis of catalyst precursor powders is generally accepted to be important. In the liquefaction of coal, for example, iron-bearing catalyst precursor particles containing individual crystallites with diameters in the 1-100 nanometer range are believed to achieve good dispersion through out the coal-solvent slurry during liquefaction 2 runs and to undergo chemical transformations to catalytically active iron sulfide phases. The production of the nanoscale powders described here employs the confining spherical microdomains comprising the aqueous phase of a modified reverse micelle (MRM) microemulsion system as nanoscale reaction vessels in which polymerization, electrochemical reduction andmore » precipitation of solvated salts can occur. The goal is to take advantage of the confining nature of micelles to kinetically hinder transformation processes which readily occur in bulk aqueous solution in order to control the morphology and phase of the resulting powder. We have prepared a variety of metal, alloy, and metal- and mixed metal-oxide nanoscale powders from appropriate MRM systems. Examples of nanoscale powders produced include Co, Mo-Co, Ni{sub 3}Fe, Ni, and various oxides and oxyhydroxides of iron. Here, we discuss the preparation and characterization of nickel metal (with a nickel oxide surface layer) and iron oxyhydroxide MRM nanoscale powders. We have used extended x-ray absorption fine structure (EXAFS) spectroscopy to study the chemical polymerization process in situ, x-ray diffraction (XRD), scanning and transmission electron microcroscopies (SEM and TEM), elemental analysis and structural modelling to characterize the nanoscale powders produced. The catalytic activity of these powders is currently being studied.« less
Manganese(II)-oxidizing Bacillus spores in Guaymas Basin hydrothermal sediments and plumes.

PubMed

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

2006-05-01

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.
Molecular Cloning and Expression of Sequence Variants of Manganese Superoxide Dismutase Genes from Wheat

USDA-ARS?s Scientific Manuscript database

Reactive oxygen species (ROS) are very harmful to living organisms due to the potential oxidation of membrane lipids, DNA, proteins, and carbohydrates. Transformed E.coli strain QC 871, superoxide dismutase (SOD) double-mutant, with three sequence variant MnSOD1, MnSOD2, and MnSOD3 manganese supero...
Simple synthetic route to manganese-containing nanowires with the spinel crystal structure

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

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

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

NASA Astrophysics Data System (ADS)

Coutinho, M. L.; Veiga, J. P.; Alves, L. C.; Mirão, J.; Dias, L.; Lima, A. M.; Muralha, V. S.; Macedo, M. F.

2016-07-01

The glaze and in-glaze pigments of the historical nineteenth-century glazed tiles from the Pena National Palace (Sintra, Portugal) were characterized using a multi-analytical approach. Chemical composition and microstructural characterization were ascertained by µ-PIXE, µ-Raman, optical microscopy and VP-SEM-EDS. The manufacturing technique and colour palette in these tiles were found to be close to the ceramic pigments used in traditional majolica. The blue and purple colours derive from cobalt oxide and manganese oxide, respectively. A mixture of Pb-Sn-Sb yellow with cobalt oxide and iron oxide was used for green and dark yellow, respectively, while grey tonalities consist of a complex mixture of cobalt oxide, manganese oxide and Pb-Sn-Sb yellow in different proportions. Results obtained allowed the determination of the oxides and elements used in pigments as well as production techniques, resorting to traditional majolica manufacture, although the tiles were produced by the end of the nineteenth century.
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
Magnetic iron oxide and manganese-doped iron oxide nanoparticles for the collection of alpha-emitting radionuclides from aqueous solutions

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

O'Hara, Matthew J.; Carter, Jennifer C.; Warner, Cynthia L.

Magnetic nanoparticles are well known to possess chemically active surfaces and large surface areas that can be employed to extract a range of ions from aqueous solutions. In addition, their superparamagnetic properties provide a convenient means for bulk collection of the material from solution after the targeted ions have been adsorbed. We evaluated two nanoscale amphoteric metal oxides, each possessing useful magnetic attributes for their ability to collect trace levels of a chemically diverse range of alpha emitting radioactive isotopes (polonium (Po), radium (Ra), uranium (U), and americium (Am)) from a wide range of aqueous solutions. The nanomaterials include commerciallymore » available magnetite (Fe3O4) and magnetite modified to incorporate manganese (Mn) into the crystal structure. The chemical stability of these nanomaterials was evaluated in Hanford Site, WA ground water between the natural pH (~8) and pH 1. Whereas the magnetite was observed to have good stability over the pH range, the Mn-doped material was observed to leach Mn at low pH. The materials were evaluated in parallel to characterize their uptake performance of the alpha-emitting radionuclide spikes from ground water across a range of pH (from ~8 down to 2). In addition, radiotracer uptake experiments were performed on Columbia River water, seawater, and human urine at their natural pH and at pH 2. Despite the observed leaching of Mn from the Mn-doped nanomaterial in the lower pH range, it exhibited generally superior analyte extraction performance compared to the magnetite, and analyte uptake was observed across a broader pH range. We show that the uptake behavior of the various radiotracers on these two materials at different pH levels can generally be explained by the amphoteric nature of the nanoparticle surfaces. Finally, the rate of sorption of the radiotracers on the two materials in unacidified ground water was evaluated. The uptake curves generally indicate that equilibrium is obtained within a few minutes, which is attributed to the high surface areas of the nanomaterials and the high level of dispersion in the liquids. In sum, our results indicate that these nanomaterials may have the potential to be employed for a range of applications to extract radionuclides from aqueous solutions.« less
Magnetic iron oxide and manganese-doped iron oxide nanoparticles for the collection of alpha-emitting radionuclides from aqueous solutions

DOE PAGES

O'Hara, Matthew J.; Carter, Jennifer C.; Warner, Cynthia L.; ...

2016-10-31

Magnetic nanoparticles are well known to possess chemically active surfaces and large surface areas that can be employed to extract a range of ions from aqueous solutions. In addition, their superparamagnetic properties provide a convenient means for bulk collection of the material from solution after the targeted ions have been adsorbed. We evaluated two nanoscale amphoteric metal oxides, each possessing useful magnetic attributes for their ability to collect trace levels of a chemically diverse range of alpha emitting radioactive isotopes (polonium (Po), radium (Ra), uranium (U), and americium (Am)) from a wide range of aqueous solutions. The nanomaterials include commerciallymore » available magnetite (Fe3O4) and magnetite modified to incorporate manganese (Mn) into the crystal structure. The chemical stability of these nanomaterials was evaluated in Hanford Site, WA ground water between the natural pH (~8) and pH 1. Whereas the magnetite was observed to have good stability over the pH range, the Mn-doped material was observed to leach Mn at low pH. The materials were evaluated in parallel to characterize their uptake performance of the alpha-emitting radionuclide spikes from ground water across a range of pH (from ~8 down to 2). In addition, radiotracer uptake experiments were performed on Columbia River water, seawater, and human urine at their natural pH and at pH 2. Despite the observed leaching of Mn from the Mn-doped nanomaterial in the lower pH range, it exhibited generally superior analyte extraction performance compared to the magnetite, and analyte uptake was observed across a broader pH range. We show that the uptake behavior of the various radiotracers on these two materials at different pH levels can generally be explained by the amphoteric nature of the nanoparticle surfaces. Finally, the rate of sorption of the radiotracers on the two materials in unacidified ground water was evaluated. The uptake curves generally indicate that equilibrium is obtained within a few minutes, which is attributed to the high surface areas of the nanomaterials and the high level of dispersion in the liquids. In sum, our results indicate that these nanomaterials may have the potential to be employed for a range of applications to extract radionuclides from aqueous solutions.« less
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
Nanostructured Metal Oxide Sorbents for the Collection and Recovery of Uranium from Seawater

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

Chouyyok, Wilaiwan; Warner, Cynthia L.; Mackie, Katherine E.

2016-02-07

The ability to collect uranium from seawater offers the potential for a long-term green fuel supply for nuclear energy. However, extraction of uranium, and other trace minerals, is challenging due to the high ionic strength and low mineral concentrations in seawater. Herein we evaluate the use of nanostructured metal oxide sorbents for the collection and recovery of uranium from seawater. Chemical affinity, chemical adsorption capacity and kinetics of preferred sorbent materials were evaluated. High surface area manganese and iron oxide nanomaterials showed excellent performance for uranium collection from seawater. Inexpensive nontoxic carbonate solutions were demonstrated to be an effective andmore » environmental benign method of stripping the uranium from the metal oxide sorbents. Various formats for the utilization of the nanostructured metals oxide sorbent materials are discussed including traditional and nontraditional methods such as magnetic separation. Keywords: Uranium, nano, manganese, iron, sorbent, seawater, magnetic, separations, nuclear energy« less
Spin-Orbit-Enhanced Functionality in LaAlO3/SrTiO3 Nanostructures

DTIC Science & Technology

2015-09-16

34 J. Vis. Exp. 89 , e51886 (2014). http://dx.doi.org/doi:10.3791/51886 J. A. Sulpizio, S. Ilani, P. Irvin, and J. Levy, "Nanoscale Phenomena in Oxide... 89 , e51886 (2014). http://dx.doi.org/doi:10.3791/51886 J. A. Sulpizio, S. Ilani, P. Irvin, and J. Levy, "Nanoscale Phenomena in Oxide
Dissection of the mechanism of manganese porphyrin-catalyzed chlorine dioxide generation.

PubMed

Umile, Thomas P; Wang, Dong; Groves, John T

2011-10-17

Chlorine dioxide, an industrially important biocide and bleach, is produced rapidly and efficiently from chlorite ion in the presence of water-soluble, manganese porphyrins and porphyrazines at neutral pH under mild conditions. The electron-deficient manganese(III) tetra-(N,N-dimethyl)imidazolium porphyrin (MnTDMImP), tetra-(N,N-dimethyl)benzimidazolium (MnTDMBImP) porphyrin, and manganese(III) tetra-N-methyl-2,3-pyridinoporphyrazine (MnTM23PyPz) were found to be the most efficient catalysts for this process. The more typical manganese tetra-4-N-methylpyridiumporphyrin (Mn-4-TMPyP) was much less effective. Rates for the best catalysts were in the range of 0.24-32 TO/s with MnTM23PyPz being the fastest. The kinetics of reactions of the various ClO(x) species (e.g., chlorite ion, hypochlorous acid, and chlorine dioxide) with authentic oxomanganese(IV) and dioxomanganese(V)MnTDMImP intermediates were studied by stopped-flow spectroscopy. Rate-limiting oxidation of the manganese(III) catalyst by chlorite ion via oxygen atom transfer is proposed to afford a trans-dioxomanganese(V) intermediate. Both trans-dioxomanganese(V)TDMImP and oxoaqua-manganese(IV)TDMImP oxidize chlorite ion by 1-electron, generating the product chlorine dioxide with bimolecular rate constants of 6.30 × 10(3) M(-1) s(-1) and 3.13 × 10(3) M(-1) s(-1), respectively, at pH 6.8. Chlorine dioxide was able to oxidize manganese(III)TDMImP to oxomanganese(IV) at a similar rate, establishing a redox steady-state equilibrium under turnover conditions. Hypochlorous acid (HOCl) produced during turnover was found to rapidly and reversibly react with manganese(III)TDMImP to give dioxoMn(V)TDMImP and chloride ion. The measured equilibrium constant for this reaction (K(eq) = 2.2 at pH 5.1) afforded a value for the oxoMn(V)/Mn(III) redox couple under catalytic conditions (E' = 1.35 V vs NHE). In subsequent processes, chlorine dioxide reacts with both oxomanganese(V) and oxomanganese(IV)TDMImP to afford chlorate ion. Kinetic simulations of the proposed mechanism using experimentally measured rate constants were in agreement with observed chlorine dioxide growth and decay curves, measured chlorate yields, and the oxoMn(IV)/Mn(III) redox potential (1.03 V vs NHE). This acid-free catalysis could form the basis for a new process to make ClO(2).
Hydrothermal vanadium manganese oxides: Anode and cathode materials for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Simões, Mário; Surace, Yuri; Yoon, Songhak; Battaglia, Corsin; Pokrant, Simone; Weidenkaff, Anke

2015-09-01

Vanadium manganese oxides with Mn content up to 33 at% were synthesized by a low temperature hydrothermal route allowing for the preparation of both anodic and cathodic materials for Li-ion batteries. Low amounts of manganese (below 13 at%) lead to the formation of elongated particles of layered hydrated vanadium oxides with manganese and water intercalated between the V2O5 slabs, while for higher Mn content of 33 at%, monoclinic MnV2O6 is formed. Former materials are suitable for high energy cathodes while the latter one is an anodic compound. The material containing 10 at% Mn has the composition Mn0.2V2O5·0.9H2O and shows the best cathodic activity with 20% capacity improvement over V2O5·0.5H2O. Lithiated MnV2O6 with Li5MnV2O6 composition prepared electrochemically was evaluated for the first time as anode in a full-cell against Mn0.2V2O5·0.9H2O cathode. An initial capacity ca. 300 A h kg-1 was measured with this battery corresponding to more than 500 Wh kg-1. These results confirm the prospect of using Li5MnV2O6 anodes in lithium-ion batteries as well as high-capacity layered hydrated vanadium oxides cathodes such as V2O5·0.5H2O and Mn0.2V2O5·0.9H2O.
Experimental and thermodynamic study of Co-Fe and Mn-Fe based mixed metal oxides for thermochemical energy storage application

NASA Astrophysics Data System (ADS)

André, Laurie; Abanades, Stéphane; Cassayre, Laurent

2017-06-01

Metal oxides are potential materials for thermochemical heat storage, and among them, cobalt oxide and manganese oxide are attracting attention. Furthermore, studies on mixed oxides are ongoing, as the synthesis of mixed oxides could be a way to answer the drawbacks of pure metal oxides, such as slow reaction kinetics, loss-in-capacity over cycles or sintering, selected for thermochemical heat storage application. The addition of iron oxide is under investigation and the obtained results are presented. This work proposes a comparison of thermodynamic modelling with experimental data in order to identify the impact of iron oxide addition to cobalt oxide and manganese oxide. Fe addition decreased the redox activity and energy storage capacity of Co3O4, whereas the cycling stability of Mn2O3 was significantly improved with added Fe amounts above 20 mol% while the energy storage capacity was unchanged. The thermodynamic modelling method to predict the behavior of the Mn-Fe-O and Co-Fe-O systems was validated, and the possibility to identify other mixed oxides becomes conceivable, by enabling the selection of transition metals additives for metal oxides destined for thermochemical energy storage applications.
One-electron oxidation of electronically diverse manganese(III) and nickel(II) salen complexes: transition from localized to delocalized mixed-valence ligand radicals.

PubMed

Kurahashi, Takuya; Fujii, Hiroshi

2011-06-01

Ligand radicals from salen complexes are unique mixed-valence compounds in which a phenoxyl radical is electronically linked to a remote phenolate via a neighboring redox-active metal ion, providing an opportunity to study electron transfer from a phenolate to a phenoxyl radical mediated by a redox-active metal ion as a bridge. We herein synthesize one-electron-oxidized products from electronically diverse manganese(III) salen complexes in which the locus of oxidation is shown to be ligand-centered, not metal-centered, affording manganese(III)-phenoxyl radical species. The key point in the present study is an unambiguous assignment of intervalence charge transfer bands by using nonsymmetrical salen complexes, which enables us to obtain otherwise inaccessible insight into the mixed-valence property. A d(4) high-spin manganese(III) ion forms a Robin-Day class II mixed-valence system, in which electron transfer is occurring between the localized phenoxyl radical and the phenolate. This is in clear contrast to a d(8) low-spin nickel(II) ion with the same salen ligand, which induces a delocalized radical (Robin-Day class III) over the two phenolate rings, as previously reported by others. The present findings point to a fascinating possibility that electron transfer could be drastically modulated by exchanging the metal ion that bridges the two redox centers. © 2011 American Chemical Society
Aqueous Speciation and Electrochemical Properties of a Water-Soluble Manganese Phthalocyanine Complex#

PubMed Central

Blakemore, James D.; Hull, Jonathan F.

2012-01-01

The speciation behavior of a water-soluble manganese(III) tetrasulfonated phthalocyanine complex was investigated with UV-visible and electron paramagnetic resonance (EPR) spectroscopies, as well as cyclic voltammetry. Parallel-mode EPR (in dimethylformamide:pyridine solvent mix) reveals a six-line hyperfine signal, centered at a g-value of 8.8, for the manganese(III) monomer, characteristic of the d4 S=2 system. The color of an aqueous solution containing the complex is dependent upon the pH of the solution; the phthalocyanine complex can exist as a water-bound monomer, a hydroxide-bound monomer, or an oxo-bridged dimer. Addition of coordinating bases such as borate or pyridine changes the speciation behavior by coordinating the manganese center. From the UV-visible spectra, complete speciation diagrams are plotted by global analysis of the pH-dependent UV-visible spectra, and a complete set of pKa values is obtained by fitting the data to a standard pKa model. Electrochemical studies reveal a pH-independent quasi-reversible oxidation event for the monomeric species, which likely involves oxidation of the organic ligand to the radical cation species. Adsorption of the phthalocyanine complex on the carbon working electrode was sometimes observed. The pKa values and electrochemistry data are discussed in the context of the development of mononuclear water-oxidation catalysts. PMID:22585306

Morphology, structure, and metal binding mechanisms of biogenic manganese oxides in a superfund site treatment system.

PubMed

Duckworth, O W; Rivera, N A; Gardner, T G; Andrews, M Y; Santelli, C M; Polizzotto, M L

2017-01-25

Manganese oxides, which may be biogenically produced in both pristine and contaminated environments, have a large affinity for many trace metals. In this study, water and Mn oxide-bearing biofilm samples were collected from the components of a pump and treat remediation system at a superfund site. To better understand the factors leading to their formation and their effects on potentially toxic metal fate, we conducted a chemical, microscopic, and spectroscopic characterization of these biofilm samples. Scanning electron microscopy revealed the presence of Mn oxides in close association with biological structures with morphologies consistent with fungi. X-ray absorption spectroscopy (XAS) and X-ray diffraction (XRD) revealed the oxides to be a mixture of layer and tunnel structure Mn(iv) oxides. In addition, XAS suggested that Ba, Co, and Zn all primarily bind to oxides in the biofilm in a manner that is analogous to synthetic or laboratory grown bacteriogenic Mn oxides. The results indicate that Mn oxides produced by organisms in the system may effectively scavenge metals, thus highlighting the potential utility of these organisms in designed remediation systems.
Redox-inactive metal ions promoted the catalytic reactivity of non-heme manganese complexes towards oxygen atom transfer.

PubMed

Choe, Cholho; Yang, Ling; Lv, Zhanao; Mo, Wanling; Chen, Zhuqi; Li, Guangxin; Yin, Guochuan

2015-05-21

Redox-inactive metal ions can modulate the reactivity of redox-active metal ions in a variety of biological and chemical oxidations. Many synthetic models have been developed to help address the elusive roles of these redox-inactive metal ions. Using a non-heme manganese(II) complex as the model, the influence of redox-inactive metal ions as a Lewis acid on its catalytic efficiency in oxygen atom transfer was investigated. In the absence of redox-inactive metal ions, the manganese(II) catalyst is very sluggish, for example, in cyclooctene epoxidation, providing only 9.9% conversion with 4.1% yield of epoxide. However, addition of 2 equiv. of Al(3+) to the manganese(II) catalyst sharply improves the epoxidation, providing up to 97.8% conversion with 91.4% yield of epoxide. EPR studies of the manganese(II) catalyst in the presence of an oxidant reveal a 16-line hyperfine structure centered at g = 2.0, clearly indicating the formation of a mixed valent di-μ-oxo-bridged diamond core, Mn(III)-(μ-O)2-Mn(IV). The presence of a Lewis acid like Al(3+) causes the dissociation of this diamond Mn(III)-(μ-O)2-Mn(IV) core to form monomeric manganese(iv) species which is responsible for improved epoxidation efficiency. This promotional effect has also been observed in other manganese complexes bearing various non-heme ligands. The findings presented here have provided a promising strategy to explore the catalytic reactivity of some di-μ-oxo-bridged complexes by adding non-redox metal ions to in situ dissociate those dimeric cores and may also provide clues to understand the mechanism of methane monooxygenase which has a similar diiron diamond core as the intermediate.
Sulfur oxide adsorbents and emissions control

DOEpatents

Li, Liyu [Richland, WA; King, David L [Richland, WA

2006-12-26

High capacity sulfur oxide absorbents utilizing manganese-based octahedral molecular sieve (Mn--OMS) materials are disclosed. An emissions reduction system for a combustion exhaust includes a scrubber 24 containing these high capacity sulfur oxide absorbents located upstream from a NOX filter 26 or particulate trap.
Exposure and Health Effects Review of Engineered Nanoscale Cerium and Cerium Dioxide Associated with its Use as a Fuel Additive - NOW IN PRINT IN THE JOURNAL

EPA Science Inventory

Advances of nanoscale science have produced nanomaterials with unique physical and chemical properties at commercial levels that are now incorporated into over 1000 products. Nanoscale cerium (di) oxide (Ce02) has recently gained a wide range of applications which includes coatin...
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. Copyright © 2015 Elsevier Inc. All rights reserved.
Lithium sorption properties of HMnO in seawater and wastewater.

PubMed

Park, HyunJu; Singhal, Naresh; Jho, Eun Hea

2015-12-15

The lithium concentration in seawater is 0.17 mg/L, which is very low, but the overall quantity is approximately 2.5 × 10(14) kg. Therefore, seawater, which contains a vast amount of lithium, could be a major alternative source that might supply the rising demand for lithium. This research was undertaken to evaluate the feasibility of a manganese oxide (HMnO) adsorbent, which was produced after leaching lithium from lithium manganese oxide, for lithium collection from seawater. The HMnO was synthesized and deformed to a plastic after wet blending of manganese oxide and lithium hydroxide, and subsequently, the influence of pH, sorption isotherms, sorption rates, sorption energies, and effects of the co-ions were measured. Thermodynamic parameters such as ΔG°, ΔH°, and ΔS° indicated that the nature of the lithium sorption was both spontaneous and endothermic. The used HMnO could be regenerated by washing it with an HCl solution. The results demonstrated that HMnO could be effectively used for the collection of lithium from seawater with good selectivity. Copyright © 2015 Elsevier Ltd. All rights reserved.
Precursor effects on the morphology and crystallinity of manganese oxides and their catalytic application for methylene blue degradation

NASA Astrophysics Data System (ADS)

Awaluddin, Amir; Agustina, Mutia; Aulia, Rizki Rilda; Muhdarina

2017-03-01

The cryptomelane-type manganese oxide catalysts have been prepared by sol-gel method based on the redox reaction between potassium permanganate and glucose or oxalic acid. These catalysts belong to a class of porous manganese oxides known as octahedral molecular sieves (OMS). The SEM results indicated that the marked difference between the morphology of the cyptomelanes produced from glucose and oxalic acid. The glucose precursor produces cotton-shaped morphology, whereas the oxalic acid precursor leads to the formation of the disk-like appearances. The XRD results indicated that the glucose precursor produces more crystalline cryptomelane than that of oxalic acid. The effect of catalyst dosage on methyelene blue degradation was evaluated. Dye-decomposing activity was proportional to the amount of catalyst used, increasing of the catalyst amount leads to higher degradation of methyelene blue at short period of reaction. With different crystalline structures and morphology appearances of the cyptomelanes, however, the total degradation of methylene blue is relatively the same at 120 minute of reaction time with catalyst amount of 100 mg.
Cost and energy demand of producing nickel manganese cobalt cathode material for lithium ion batteries

DOE PAGES

Ahmed, Shabbir; Nelson, Paul A.; Gallagher, Kevin G.; ...

2017-01-05

The price of the cathode active materials in lithium ion batteries is a key cost driver and thus significantly impacts consumer adoption of devices that utilize large energy storage contents (e.g. electric vehicles). A process model has been developed and used to study the production process of a common lithium-ion cathode material, lithiated nickel manganese cobalt oxide, using the co-precipitation method. The process was simulated for a plant producing 6500 kg day –1. The results indicate that the process will consume approximately 4 kWh kg NMC –1 of energy, 15 L kg NMC –1 of process water, and cost $23more » to produce a kg of Li-NMC333. The calculations were extended to compare the production cost using two co-precipitation reactions (with Na 2CO 3 and NaOH), and similar cathode active materials such as lithium manganese oxide and lithium nickel cobalt aluminum oxide. Finally, a combination of cost saving opportunities show the possibility to reduce the cost of the cathode material by 19%.« less
A High-Pressure Study of Manganese Metal and its Reactions with CO2 at 6, 23, and 44 GPa

NASA Astrophysics Data System (ADS)

Sawchuk, K. L. S.; McGuire, C. P.; Greenburg, A.; Makhluf, A.; Kavner, A.

2017-12-01

The free energies of formation of oxides and carbonates at the extreme pressures and temperatures of Earth's interior provides some of the thermodynamic constrains for models of mantle/core formation and subsequent chemical evolution. The broad goal of our research program is to measure the pressure- and temperature-dependence of free energies of formation of transition metal oxides and carbonates. This requires measurements of the phase stability, density, and thermoelastic properties of metals, oxides, and carbonates at deep-Earth and planetary conditions. Manganese is of interest because it is one of the most abundant transition metal geochemical tracers, it readily forms a carbonate at ambient pressure, and its high-pressure carbonate and oxide densities and equation of state parameters are relatively unknown. Here we report new data on the pressure/volume equation of state and structure of manganese metal as well as its reactions with CO2. These measurements were made using a laser heated diamond anvil cell in conjunction with synchrotron-based X-ray diffraction at beamline 12.2.2 at the Advanced Light Source. Three samples of manganese metal were gas-loaded in a CO2 pressure medium and pressurized to 6, 23, and 44 GPa. Upon laser heating, the CO2 reacted with the Mn metal generating new phases. To analyze the diffraction patterns, we we use a python-based program developed in-house for extracting high resolution 2-dimensional diffraction peak position and intensity information from two-dimensional X-ray diffraction patterns. At each pressure step, the structure and density of the quenched Mn metal phase was determined. At 6 GPa, Mn metal adopts a BCC structure, and at 23 GPa a tetragonal distortion is observed in the lattice. The measured equation of state is in good agreement with an existing meaurement by Fujihisa and Takemura (1995). MnCO3 rhodochrosite is observed in the sample quenched after heating at 6 GPa. Additional high pressure phases are evident in the diffraction patterns from the samples at 23 GPa and 44 GPa. The density and equation of state parameters for our observed oxide, carbonate, and metal manganese structures are used in conjunction with existing thermodynamic information to predict how the free energies of formation of Mn- oxide and Mn-carbonate change as a function of pressure.
Non-oxidic nanoscale composites: single-crystalline titanium carbide nanocubes in hierarchical porous carbon monoliths.

PubMed

Sonnenburg, Kirstin; Smarsly, Bernd M; Brezesinski, Torsten

2009-05-07

We report the preparation of nanoscale carbon-titanium carbide composites with carbide contents of up to 80 wt%. The synthesis yields single-crystalline TiC nanocubes 20-30 nm in diameter embedded in a hierarchical porous carbon matrix. These composites were generated in the form of cylindrical monoliths but can be produced in various shapes using modern sol-gel and nanocasting methods in conjunction with carbothermal reduction. The monolithic material is characterized by a combination of microscopy, diffraction and physisorption. Overall, the results presented in this work represent a concrete design template for the synthesis of non-oxidic nanoscale composites with high surface areas.
Role of metal oxides in chemical evolution

NASA Astrophysics Data System (ADS)

Kamaluddin

2013-06-01

Steps of chemical evolution have been designated as formation of biomonomers followed by their polymerization and then to modify in an organized structure leading to the formation of first living cell. Formation of small molecules like amino acids, organic bases, sugar etc. could have occurred in the reducing atmosphere of the primitive Earth. Polymerization of these small molecules could have required some catalyst. In addition to clay, role of metal ions and metal complexes as prebiotic catalyst in the synthesis and polymerization of biomonomers cannot be ruled out. Metal oxides are important constituents of Earth crust and that of other planets. These oxides might have adsorbed organic molecules and catalyzed the condensation processes, which may have led to the formation of first living cell. Different studies were performed in order to investigate the role of metal oxides (especially oxides of iron and manganese) in chemical evolution. Iron oxides (goethite, akaganeite and hematite) as well as manganese oxides (MnO, Mn2O3, Mn3O4 and MnO2) were synthesized and their characterization was done using IR, powder XRD, FE-SEM and TEM. Role of above oxides was studied in the adsorption of ribose nucleotides, formation of nucleobases from formamide and oligomerization of amino acids. Above oxides of iron and manganese were found to have good adsorption affinity towards ribose nucleotides, high catalytic activity in the formation of several nucleobases from formamide and oligomerization of glycine and alanine. Characterization of products was performed using UV, IR, HPLC and ESI-MS techniques. Presence of hematite-water system on Mars has been suggested to be a positive indicator in the chemical evolution on Mars.
Low-temperature abatement of toluene over Mn-Ce oxides catalysts synthesized by a modified hydrothermal approach

NASA Astrophysics Data System (ADS)

Du, Jinpeng; Qu, Zhenping; Dong, Cui; Song, Lixin; Qin, Yuan; Huang, Na

2018-03-01

Mn-Ce oxides catalysts were synthesized by a novel method combining redox-precipitation and hydrothermal approach. The results indicate that the ratio between manganese and cerium plays a crucial role in the formation of catalysts, and the textual properties as well as catalytic activity are remarked affected. Mn0.6Ce0.4O2 possesses a predominant catalytic activity in the oxidation of toluene, over 70% of toluene is converted at 200 °C, and the complete conversion temperature is 210 °C. The formation of Mn-Ce solid solution markedly improves the surface area as well as pore volume of Mn-Ce oxide catalyst, and Mn0.6Ce0.4O2 possesses the largest surface area of 298.5 m2/g. The abundant Ce3+ and Mn3+ on Mn0.6Ce0.4O2 catalyst facilitate the formation of oxygen vacancies, and improve the transfer of oxygen in the catalysts. Meanwhile, it is found that cerium in Mn-Ce oxide plays a key role in the adsorption of toluene, while manganese is proved to be crucial in the oxidation of toluene, the cooperation between manganese and cerium improves the catalytic reaction process. In addition, the reaction process is investigated by in situ DRIFT measurement, and it is found that the adsorbed toluene could be oxidized to benzyl alcohol as temperature rises around 80-120 °C that can be further be oxidized to benzoic acid. Then benzoic acid could be decomposed to formate and/or carbonate species as temperature rises to form CO2 and H2O. In addition, the formed by-product phenol could be further oxidized into CO2 and H2O when the temperature is high enough.
Manganese oxides-based composite electrodes for supercapacitors

NASA Astrophysics Data System (ADS)

Su, Dongyun; Ma, Jun; Huang, Mingyu; Liu, Feng; Chen, Taizhou; Liu, Chao; Ni, Hongjun

2017-06-01

In recent, nanostructured transition metal oxides as a new class of energy storage materials have widely attracted attention due to its excellent electrochemical performance for supercapacitors. The MnO2 based transition metal oxides and their composite electrode materials were focused in the review for supercapacitor applications. The researches on different nanostructures of manganese oxides such as Nano rods, Nano sheets, nanowires, nanotubes and so on have been discovered in recent years, together with brief explanations of their properties. Research on enhancing materials’ properties by designing combination of different materials on the micron or Nano scale is too limited, and therefore we discuss the effects of different components’ sizes and their synergy on the performance. Moreover, the low-cost and large-scale fabrication of flexible supercapacitors with high performance (high energy density and cycle stability) have been pointed out and studied.
Assembling a supercapacitor electrode with dual metal oxides and activated carbon using a liquid phase plasma.

PubMed

Ki, Seo Jin; Jeon, Ki-Joon; Park, Young-Kwon; Park, Hyunwoong; Jeong, Sangmin; Lee, Heon; Jung, Sang-Chul

2017-12-01

Developing supercapacitor electrodes at an affordable cost while improving their energy and/or power density values is still a challenging task. This study introduced a recipe which assembled a novel electrode composite using a liquid phase plasma that was applied to a reactant solution containing an activated carbon (AC) powder with dual metal precursors of iron and manganese. A comparison was made between the composites doped with single and dual metal components as well as among those synthesized under different precursor concentrations and plasma durations. The results showed that increasing the precursor concentration and plasma duration raised the content of both metal oxides in the composites, whereas the deposition conditions were more favorable to iron oxide than manganese oxide, due to its higher standard potential. The composite treated with the longest plasma duration and highest manganese concentration was superior to the others in terms of cyclic stability and equivalent series resistance. In addition, the new composite selected out of them showed better electrochemical performance than the raw AC material only and even two types of single metal-based composites, owing largely to the synergistic effect of the two metal oxides. Therefore, the proposed methodology can be used to modify existing and future composite electrodes to improve their performance with relatively cheap host and guest materials. Copyright © 2017 Elsevier Ltd. All rights reserved.
The Mineralogy and Geochemistry of Manganese Nodules From the Southern Ocean

DTIC Science & Technology

1968-02-01

accumulations. Quartz, plagioclase, montmorillonite , and phillipsite are almost invariably present, while clinoptilolite ii and amphibole occur less... Montmorillonite Diffraction Data ........... 125 16. Phillipsite Diffraction Data .. ......... ... 126 17. Sources of X-ray Diffraction Data...concretion. (Crust from ELTANIN 5-4; nucleus probably phillipsite- montmorillonite ; glacial erratics incorporated in ferro- manganese oxide crust.) 0 cm I
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...
Bioaccumulation of manganese and its toxicity in feral pigeons (Columba livia) exposed to manganese oxide dust (Mn{sub 3}O{sub 4})

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

Sierra, P.; Chakrabarti, S.; Tounkara, R.

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 ofmore » 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.« less
Hepatoprotective effect of manganese chloride against CCl4-induced liver injury in rats.

PubMed

Eidi, Akram; Mortazavi, Pejman; Behzadi, Khodabakhsh; Rohani, Ali Haeri; Safi, Shahabeddin

2013-11-01

The aim of the present study is to evaluate the protective effect of manganese chloride against carbon tetrachloride (CCl4)-induced liver injury in rats. Manganese chloride (0.001, 0.01, 0.05 and 0.1 g/kg bw) was administered intragastrically for 28 consecutive days to male CCl4-treated rats. The hepatoprotective activity was assessed using various biochemical parameters such as alanine aminotransferase (ALT), aspartate aminotransferase (AST), alkaline phosphatase (ALP), γ-glutamyltransferase (GGT) and superoxide dismutase (SOD). Histopathological changes in the liver of different groups were also studied. Administration of CCl4 increased the serum ALT, AST, ALP and GGT but decreased SOD levels in rats. Treatment with manganese chloride significantly attenuated these changes to nearly normal levels. The animals treated with manganese chloride have shown decreased necrotic zones and hepatocellular degeneration when compared to the liver exposed to CCl4 intoxication alone. Thus, the histopathological studies also supported the protective effect of manganese chloride. Therefore, the results of this study suggest that manganese chloride exerts hepatoprotection via promoting antioxidative properties against CCl4-induced oxidative liver damage.
Chronic manganese poisoning in the dry battery industry

PubMed Central

Emara, A. M.; El-Ghawabi, S. H.; Madkour, O. I.; El-Samra, G. H.

1971-01-01

Emara, A. M., El-Ghawabi, S. H., Madkour, O. I., and El-Samra, G. H. (1971). Brit. J. industr. Med., 28, 78-82. Chronic manganese poisoning in the dry battery industry. A survey was carried out on 36 workers in the dry battery industry exposed to dust containing 65 to 70% manganese oxide. Eight (22·2%) were found to have neuropsychiatric manifestations, six (16·6%) had chronic manganese psychosis, one had left hemi-parkinsonism, and one had left choreoathetosis. An environmental study revealed a high concentration of manganese dust at the main working areas, far exceeding the accepted MAC. The manganese level in blood was almost within the normal range. Coproporphyrin in urine was normal. The electroencephalogram was abnormal in only two of the affected workers (25%) but there was no association between this and the clinical manifestations or duration of exposure. The concentration of manganese dust in air showed some association with the prevalence and rapidity of effect on workers according to their occupation. However, individual susceptibility was apparent. The shortest latent period was one year. PMID:5101169
Review of Manganese Processing for Production of TRIP/TWIP Steels, Part 2: Reduction Studies

NASA Astrophysics Data System (ADS)

Elliott, R.; Coley, K.; Mostaghel, S.; Barati, M.

2018-02-01

Production of ultrahigh-manganese steels is expected to result in significant increase in demand for low-carbon (LC) ferromanganese (FeMn) and silicomanganese (SiMn). Current manganese processing techniques are energy intensive and typically yield a high-carbon product. The present work therefore reviews available literature regarding carbothermic reduction of Mn oxides and ores, with the objective of identifying opportunities for future process development to mitigate the cost of LC FeMn and SiMn. In general, there is consensus that carbothermic reduction of Mn oxides and ores is limited by gasification of carbon. Conditions which enhance or bypass this step (e.g., by application of CH4) show higher rates of reduction at lower temperatures. This phenomenon has potential application in solid-state reduction of Mn ore. Other avenues for process development include optimization of the prereduction step in conventional FeMn production and metallothermic reduction as a secondary reduction step.

Tailoring nanostructured MnO2 as anodes for lithium ion batteries with high reversible capacity and initial Coulombic efficiency

NASA Astrophysics Data System (ADS)

Zhang, Lifeng; Song, Jiajia; Liu, Yi; Yuan, Xiaoyan; Guo, Shouwu

2018-03-01

Developing high energy storage lithium ion batteries (LIBs) using manganese oxides as anodes is an attractive challenge due to their high theoretical capacity and abundant resources. However, the manganese oxides anodes still suffer from the low initial Coulombic efficiency and poor rate performance. Herein, we demonstrate that nano-sized morphological engineering is a facile and effective strategy to improve the electrochemical performance of the manganese dioxide (MnO2) for LIBs. The tailored MnO2 nanoparticles (NPs) exhibit high reversible capacity (1095 mAh g-1 at 100 mA g-1), high initial Coulombic efficiency (94.5%) and good rate capability (464 mAh g-1 at 2000 mA g-1). The enhanced electrochemical performance of MnO2 NPs can be attributed to the presences of numerous electrochemically active sites and interspaces among the NPs.
Low-spin manganese(II) and high-spin manganese(III) complexes derived from disalicylaldehyde oxaloyldihydrazone: Synthesis, spectral characterization and electrochemical studies

NASA Astrophysics Data System (ADS)

Syiemlieh, Ibanphylla; Kumar, Arvind; Kurbah, Sunshine D.; De, Arjune K.; Lal, Ram A.

2018-01-01

Low-spin manganese(II) complexes [MnII(H2slox)].H2O (1), [MnII(H2slox)(SL)] (where SL (secondary ligand) = pyridine (py, 2), 2-picoline (2-pic, 3), 3-picoline (3-pic, 4), and 4-picoline (4-pic, 5) and high-spin manganese(III) complex Na(H2O)4[MnIII(slox)(H2O)2].2.5H2O have been synthesized from disalicyaldehyde oxaloyldihydrazone in methanolic - water medium. The composition of complexes has been established by elemental analyses and thermoanalytical data. The structures of the complexes have been discussed on the basis of data obtained from molar conductance, UV visible, 1H NMR, infrared spectra, magnetic moment and electron paramagnetic resonance spectroscopic studies. Conductivity measurements in DMF suggest that the complexes (1-5) are non-electrolyte while the complex (6) is 1:1 electrolyte. The electronic spectral studies and magnetic moment data suggest five - coordinate square pyramidal structure for the complexes (2-5) and square planar geometry for manganese(II) in complex (1). In complex (6), both sodium and manganese(III) have six coordinate octahedral geometry. IR spectral studies reveal that the dihydrazone coordinates to the manganese centre in keto form in complexes (1-5) and in enol form in complex (6). In all complexes, the ligand is present in anti-cis configuration. Magnetic moment and EPR studies indicate manganese in +2 oxidation state in complexes (1-5), with low-spin square planar complex (1) and square pyramidal stereochemistries complexes (2-5) while in +3 oxidation state in high-spin distorted octahedral stereochemistry in complex (6). The complex (1) involves significant metal - metal interaction in the solid state. All of the complexes show only one metal centred electron transfer reaction in DMF solution in cyclic voltammetric studies. The complexes (1-5) involve MnII→MnI redox reaction while the complex (6) involves MnIII→MnII redox reaction, respectively.
Nanoscale assembly of lanthanum silica with dense and porous interfacial structures.

PubMed

Ballinger, Benjamin; Motuzas, Julius; Miller, Christopher R; Smart, Simon; Diniz da Costa, João C

2015-02-03

This work reports on the nanoscale assembly of hybrid lanthanum oxide and silica structures, which form patterns of interfacial dense and porous networks. It was found that increasing the molar ratio of lanthanum nitrate to tetraethyl orthosilicate (TEOS) in an acid catalysed sol-gel process alters the expected microporous metal oxide silica structure to a predominantly mesoporous structure above a critical lanthanum concentration. This change manifests itself by the formation of a lanthanum silicate phase, which results from the reaction of lanthanum oxide nanoparticles with the silica matrix. This process converts the microporous silica into the denser silicate phase. Above a lanthanum to silica ratio of 0.15, the combination of growth and microporous silica consumption results in the formation of nanoscale hybrid lanthanum oxides, with the inter-nano-domain spacing forming mesoporous volume. As the size of these nano-domains increases with concentration, so does the mesoporous volume. The absence of lanthanum hydroxide (La(OH)3) suggests the formation of La2O3 surrounded by lanthanum silicate.
The Structure and Properties of Plasma Sprayed Iron Oxide Doped Manganese Cobalt Oxide Spinel Coatings for SOFC Metallic Interconnectors

NASA Astrophysics Data System (ADS)

Puranen, Jouni; Lagerbom, Juha; Hyvärinen, Leo; Kylmälahti, Mikko; Himanen, Olli; Pihlatie, Mikko; Kiviaho, Jari; Vuoristo, Petri

2011-01-01

Manganese cobalt oxide spinel doped with Fe2O3 was studied as a protective coating on ferritic stainless steel interconnects. Chromium alloying causes problems at high operation temperatures in such oxidizing conditions where chromium compounds evaporate and poison the cathode active area, causing the degradation of the solid oxide fuel cell. In order to prevent chromium evaporation, these interconnectors need a protective coating to block the chromium evaporation and to maintain an adequate electrical conductivity. Thermal spraying is regarded as a promising way to produce dense and protective layers. In the present work, the ceramic Mn-Co-Fe oxide spinel coatings were produced by using the atmospheric plasma spray process. Coatings with low thickness and low amount of porosity were produced by optimizing deposition conditions. The original spinel structure decomposed because of the fast transformation of solid-liquid-solid states but was partially restored by using post-annealing treatment.
Multilayered films of cobalt oxyhydroxide nanowires/manganese oxide nanosheets for electrochemical capacitor

NASA Astrophysics Data System (ADS)

Zheng, Huajun; Tang, Fengqiu; Lim, Melvin; Mukherji, Aniruddh; Yan, Xiaoxia; Wang, Lianzhou; (Max) Lu, Gao Qing

Multilayered films of cobalt oxyhydroxide nanowires (CoOOHNW) and exfoliated manganese oxide nanosheet (MONS) are fabricated by potentiostatic deposition and electrostatic self-assembly on indium-tin oxide coated glass substrates. The morphology and chemical composition of these films are characterized by scanning electron microscopy (SEM) and X-ray photoelectron spectra (XPS) and the potential application as electrochemical supercapacitors are investigated using cyclic voltammetry and charge-discharge measurements. These ITO/CoOOHNW/MONS multilayered film electrodes exhibit excellent electrochemical capacitance properties, including high specific capacitance (507 F g -1) and long cycling durability (less 2% capacity loss after 5000 charge/discharge cycles). These characteristics indicate that these newly developed films may find important application for electrochemical capacitors.
Power sources for search and rescue 406 MHz beacons

NASA Technical Reports Server (NTRS)

Attia, Alan I.; Perrone, David E.

1987-01-01

The results of a study directed at the selection of a commercially available, safe, low cost, light weight and long storage life battery for search and rescue (Sarsat) 406 MHz emergency beacons are presented. In the course of this work, five electrochemical systems (lithium-manganese dioxide, lithium-carbon monofluoride, lithium-silver vanadium oxide, alkaline cells, and cadmium-mercuric oxide) were selected for limited experimental studies to determine their suitability for this application. Two safe, commercially available batteries (lithium-manganese dioxide and lithium-carbon monofluoride) which meet the near term requirements and several alternatives for the long term were identified.
Dual Effect of Manganese Oxide Micromotors: Catalytic Degradation and Adsorptive Bubble Separation of Organic Pollutants.

PubMed

Wani, Owies M; Safdar, Muhammad; Kinnunen, Niko; Jänis, Janne

2016-01-22

Manganese oxide (MnO2 ) based micromotors exhibiting a dual effect, that is, catalytic degradation and adsorptive bubble separation, were employed for water remediation. The dual effect of MnO2 microparticles led to a greater than 90 % of decolorization of non-biodegradable organic dyes in just 1 h, without the need for external agitation or bubble generation. These findings suggest high potential of MnO2 micromotors for decontamination of organic pollutants from wastewaters or natural water reserves. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Photo-catalytic Degradation and Sorption of Radio-cobalt from EDTA-Co Complexes Using Manganese Oxide Materials - 12220

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

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 onmore » 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 very promising for the treatment of EDTA complexed Co solutions. The better performance values and cheaper production cost of manganese oxide, compared to titanium dioxide, is so big driving force that further studies on the material are evident. The possibilities for continuous treatment, instead of the fluidized bed -type batch experiment are investigated and the effects of other compounds affecting the de-complexation of Co-EDTA are further studied. (authors)« less
Dynamic observation on the growth behaviors in manganese silicide/silicon nanowire heterostructures.

PubMed

Hsieh, Yu-Hsun; Chiu, Chung-Hua; Huang, Chun-Wei; Chen, Jui-Yuan; Lin, Wan-Jhen; Wu, Wen-Wei

2015-02-07

Metal silicide nanowires (NWs) are very interesting materials with diverse physical properties. Among the silicides, manganese silicide nanostructures have attracted wide attention due to their several potential applications, including in microelectronics, optoelectronics, spintronics and thermoelectric devices. In this work, we exhibited the formation of pure manganese silicide and manganese silicide/silicon nanowire heterostructures through solid state reaction with line contacts between manganese pads and silicon NWs. Dynamical process and phase characterization were investigated by in situ transmission electron microscopy (in situ TEM) and spherical aberration corrected scanning transmission electron microscopy (Cs-corrected STEM), respectively. The growth dynamics of the manganese silicide phase under thermal effects were systematically studied. Additionally, Al2O3, serving as the surface oxide, altered the growth behavior of the MnSi nanowire, enhancing the silicide/Si epitaxial growth and effecting the diffusion process in the silicon nanowire as well. In addition to fundamental science, this significant study has great potential in advancing future processing techniques in nanotechnology and related applications.
Measurement of benzenethiol adsorption to nanostructured Pt, Pd, and PtPd films using Raman spectroelectrochemistry.

PubMed

Pomfret, Michael B; Pietron, Jeremy J; Owrutsky, Jeffrey C

2010-05-04

Raman spectroscopy and electrochemical methods were used to study the behavior of the model adsorbate benzenethiol (BT) on nanostructured Pt, Pd, and PtPd electrodes as a function of applied potential. Benzenethiol adsorbs out of ethanolic solutions as the corresponding thiolate, and voltammetric stripping data reveal that BT is oxidatively removed from all of the nanostructured metals upon repeated oxidative and reductive cycling. Oxidative stripping potentials for BT increase in the order Pt < PtPd < Pd, indicating that BT adsorbs most strongly to nanoscale Pd. Yet, BT Raman scattering intensities, measured in situ over time scales of minutes to hours, are most persistent on the film of nanostructured Pt. Raman spectra indicate that adsorbed BT desorbs from nanoscale Pt at oxidizing potentials via cleavage of the Pt-S bond. In contrast, on nanoscale Pd and PtPd, BT is irreversibly lost due to cleavage of BT C-S bonds at oxidizing potentials, which leaves adsorbed sulfur oxides on Pd and PtPd films and effects the desulfurization of BT. While Pd and PtPd films are less sulfur-resistant than Pt films, palladium oxides, which form at higher potentials than Pt oxides, oxidatively desulfurize BT. In situ spectroelectrochemical Raman spectroscopy provides real-time, chemically specific information that complements the cyclic voltammetric data. The combination of these techniques affords a powerful and convenient method for guiding the development of sulfur-tolerant PEMFC catalysts.
Formation of soluble mercury oxide coatings: Transformation of elemental mercury in soils

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

Miller, Carrie L.; Watson, David B.; Lester, Brian P.

2015-09-21

In this study, the impact of mercury (Hg) on human and ecological health has been known for decades. Although a treaty signed in 2013 by 147 nations regulates future large-scale mercury emissions, legacy Hg contamination exists worldwide and small-scale releases will continue. The fate of elemental mercury, Hg(0), lost to the subsurface and its potential chemical transformation that can lead to changes in speciation and mobility are poorly understood. Here, we show that Hg(0) beads interact with soil or manganese oxide solids and X-ray spectroscopic analysis indicates that the soluble mercury coatings are HgO. Dissolution studies show that, after reactingmore » with a composite soil, >20 times more Hg is released into water from the coated beads than from a pure liquid mercury bead. An even larger, >700 times, release occurs from coated Hg(0) beads that have been reacted with manganese oxide, suggesting that manganese oxides are involved in the transformation of the Hg(0) beads and creation of the soluble mercury coatings. Although the coatings may inhibit Hg(0) evaporation, the high solubility of the coatings can enhance Hg(II) migration away from the Hg(0)-spill site and result in potential changes in mercury speciation in the soil and increased mercury mobility.« less
Investigations into Recycling Zinc from Used Metal Oxide Varistors via pH Selective Leaching: Characterization, Leaching, and Residue Analysis

PubMed Central

Gutknecht, Toni; Gustafsson, Anna; Forsgren, Christer; Steenari, Britt-Marie

2015-01-01

Metal oxide varistors (MOVs) are a type of resistor with significantly nonlinear current-voltage characteristics commonly used in power lines to protect against overvoltages. If a proper recycling plan is developed MOVs can be an excellent source of secondary zinc because they contain over 90 weight percent zinc oxide. The oxides of antimony, bismuth, and to a lesser degree cobalt, manganese, and nickel are also present in varistors. Characterization of the MOV showed that cobalt, nickel, and manganese were not present in the varistor material at concentrations greater than one weight percent. This investigation determined whether a pH selective dissolution (leaching) process can be utilized as a starting point for hydrometallurgical recycling of the zinc in MOVs. This investigation showed it was possible to selectively leach zinc from the MOV without coleaching of bismuth and antimony by selecting a suitable pH, mainly higher than 3 for acids investigated. It was not possible to leach zinc without coleaching of manganese, cobalt, and nickel. It can be concluded from results obtained with the acids used, acetic, hydrochloric, nitric, and sulfuric, that sulfate leaching produced the most desirable results with respect to zinc leaching and it is also used extensively in industrial zinc production. PMID:26421313
Development of Functional Inorganic Materials by Soft Chemical Process Using Ion-Exchange Reactions

NASA Astrophysics Data System (ADS)

Feng, Qi

Our study on soft chemical process using the metal oxide and metal hydroxide nanosheets obtained by exfoliation their layered compounds were reviewed. Ni(OH)2⁄MnO2 sandwich layered nanostructure can be prepared by layer by-layer stacking of exfoliated manganese oxide nanosheets and nickel hydroxide layers. Manganese oxide nanotubes can be obtained by curling the manganese oxide nanosheets using the cationic surfactants as the template. The layered titanate oriented thin film can be prepared by restacking the titanate nanosheets on a polycrystalline substrate, and transformed to the oriented BaTiO3 and TiO2 thin films by the topotactic structural transformation reactions, respectively. The titanate nanosheets can be transformed anatase-type TiO2 nanocrystals under hydrothermal conditions. The TiO2 nanocrystals are formed by a topotactic structural transformation reaction. The TiO2 nanocrystals prepared by this method expose specific crystal plane on their surfaces, and show high photocatalytic activity and high dye adsorption capacity for high performance dye-sensitized solar cell. A series of layered basic metal salt (LBMS) compounds were prepared by hydrothermal reactions of transition metal hydroxides and organic acids. We succeeded in the exfoliation of these LBMS compounds in alcohol solvents, and obtained the transition metal hydroxide nanosheets for the first time.
Interrogation of bimetallic particle oxidation in three dimensions at the nanoscale

PubMed Central

Han, Lili; Meng, Qingping; Wang, Deli; Zhu, Yimei; Wang, Jie; Du, Xiwen; Stach, Eric A.; Xin, Huolin L.

2016-01-01

An understanding of bimetallic alloy oxidation is key to the design of hollow-structured binary oxides and the optimization of their catalytic performance. However, one roadblock encountered in studying these binary oxide systems is the difficulty in describing the heterogeneities that occur in both structure and chemistry as a function of reaction coordinate. This is due to the complexity of the three-dimensional mosaic patterns that occur in these heterogeneous binary systems. By combining real-time imaging and chemical-sensitive electron tomography, we show that it is possible to characterize these systems with simultaneous nanoscale and chemical detail. We find that there is oxidation-induced chemical segregation occurring on both external and internal surfaces. Additionally, there is another layer of complexity that occurs during the oxidation, namely that the morphology of the initial oxide surface can change the oxidation modality. This work characterizes the pathways that can control the morphology in binary oxide materials. PMID:27928998
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 matter. ?? 1981.
Phenolic Wastewater Treatment Alternatives.

DTIC Science & Technology

1980-06-01

15 Potassium Permanganate ................ 19 Iron (VI) Ferrate ..................... 22 Catalytic Oxidation ..................... 22...carbon dioxide, potassium hydroxide, and manganese dioxide which were readily handled by the existing system. d. Iron (VI) Ferrate Ferrate is iron in...the following systems/processes: Granular Activated Carbon (GAC) adsorption, ozone oxidation, hydrogen peroxide oxidation, potassium permanganate
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.
Coprecipitation and redox reactions of manganese oxides with copper and nickel

NASA Astrophysics Data System (ADS)

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

1989-11-01

Open-system, continuous-titration experiments have been done in which a slow flux of ˜0.02 molar solution of Mn 2+ chloride, nitrate, or perchlorate with Cu 2+ or Ni 2+ 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 Cu 2Mn 3O 8 in which all Mn is in the 4+ oxidation state. A major component in all precipitates is feitknechtite, βMnOOH. These forms are supplemented by CuO or by birnessite or ramsdellite forms of MnO 2 where stoichiometry and thermodynamic calculations predict them. In systems that contained nickel and manganese, identifiable components included βMnOOH, Ni(OH) 2, and the same two forms of MnO 2. 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 Cu 2+ and Ni 2+ generally decreased to values substantially below those predicted by oxide or hydroxide equilibrium. Scavenging effects of this type are common in natural aqueous systems.
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 ΣREEs for hydrogenetic and mixed hydrogenetic-diagenetic deposits, whereas the Ce anomaly is negative for hydrothermal deposits and ΣREE 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 the redox conditions of seawater. The concentration of elements in hydrogenetic Fe-Mn crusts depends on a wide variety of water column and crust surface characteristics, whereas concentration of elements in hydrothermal oxide deposits depends of the intensity of leaching, rock types leached, and precipitation of sulphides at depth in the hydrothermal system.
Nano-metal Oxides: Exposure and Engineering Control Assessment

PubMed Central

Garcia, Alberto; Sparks, Christopher; Martinez, Kenneth; Topmiller, Jennifer L.; Eastlake, Adrienne; Geraci, Charles L.

2017-01-01

This paper discusses the evaluation of a facility that produces high quality engineered nanomaterials. These ENMs consist of various metals including iron, nickel, silver, manganese, and palladium. Although occupational exposure levels are not available for these metals, studies have indicated that it may be prudent to keep exposures to the nano-scale metal as low as possible. Previous In vitro studies indicated that in comparison with a material’s larger (parent) counterpart, nanomaterials can move easily through cell membranes and can cause severe toxic effects on human health. The in vitro studies showed that the toxicological effects specific to exposure to nanoscale nickel oxide and nickel have been found to be more inflammatory and toxic than larger-sized nickel particles and can decrease cell metabolic activity, arrest the G2-M cell cycle, and increase cell death. An in vitro study on exposure to iron nanoparticles indicated that the reactive oxygen species produced by exposure may increase cell permeability thereby increasing the potential for vascular movement. Much of the data available on palladium focus on dermal or ingestion exposure; the chronic effects are not well understood. Given the available limited data on the metals evaluated, caution is warranted. One should always keep in mind that the current OELs were not developed specifically for nanoscale particles. With limited data suggesting that certain nanoparticles may be more toxic than the larger counterparts of the same material; employers should attempt to control emissions of these particles at the source, to limit the potential for exposure. Evidence suggests that in general some nanomaterials can be more toxic than their macro-scale counterparts, and therefore caution is warranted. It appears that the personal protective equipment utilized by the employee was appropriate for this type of operation. It should be noted that the use of respiratory protection should not be used as sole protection for any worker, but providing a fit-tested respirator will serve to further decrease the potential for exposure. Instead, it is recommended to control the dispersion of product at the source using local exhaust ventilation, ventilated containment, or fume hoods. Data obtained from the direct reading instruments suggest that reactor cleanout increased the overall particle concentration in the immediate area. However, it does not appear that these concentrations affect areas outside of the production floor. As the distance between the reactor and the sample location increased, the observed particle number concentrations decreased, creating a concentration gradient with respect to the reactor. PMID:28609256

Solid state electrochemical current source

DOEpatents

Potanin, Alexander Arkadyevich; Vedeneev, Nikolai Ivanovich

2002-04-30

A cathode and a solid state electrochemical cell comprising said cathode, a solid anode and solid fluoride ion conducting electrolyte. The cathode comprises a metal oxide and a compound fluoride containing at least two metals with different valences. Representative compound fluorides include solid solutions of bismuth fluoride and potassium fluoride; and lead fluoride and potassium fluoride. Representative metal oxides include copper oxide, lead oxide, manganese oxide, vanadium oxide and silver oxide.
Novel MntR-Independent Mechanism of Manganese Homeostasis in Escherichia coli by the Ribosome-Associated Protein HflX

PubMed Central

Kaur, Gursharan; Sengupta, Sandeepan; Kumar, Vineet; Kumari, Aruna; Ghosh, Aditi; Parrack, Pradeep

2014-01-01

Manganese is a micronutrient required for activities of several important enzymes under conditions of oxidative stress and iron starvation. In Escherichia coli, the manganese homeostasis network primarily constitutes a manganese importer (MntH) and an exporter (MntP), which are regulated by the MntR dual regulator. In this study, we find that deletion of E. coli hflX, which encodes a ribosome-associated GTPase with unknown function, renders extreme manganese sensitivity characterized by arrested cell growth, filamentation, lower rate of replication, and DNA damage. We demonstrate that perturbation by manganese induces unprecedented influx of manganese in ΔhflX cells compared to that in the wild-type E. coli strain. Interestingly, our study indicates that the imbalance in manganese homeostasis in the ΔhflX strain is independent of the MntR regulon. Moreover, the influx of manganese leads to a simultaneous influx of zinc and inhibition of iron import in ΔhflX cells. In order to review a possible link of HflX with the λ phage life cycle, we performed a lysis-lysogeny assay to show that the Mn-perturbed ΔhflX strain reduces the frequency of lysogenization of the phage. This observation raises the possibility that the induced zinc influx in the manganese-perturbed ΔhflX strain stimulates the activity of the zinc-metalloprotease HflB, the key determinant of the lysis-lysogeny switch. Finally, we propose that manganese-mediated autophosphorylation of HflX plays a central role in manganese, zinc, and iron homeostasis in E. coli cells. PMID:24794564
Controlling the Electrostatic Discharge Ignition Sensitivity of Composite Energetic Materials Using Carbon Nanotube Additives

DTIC Science & Technology

2014-08-10

Electrostatic discharge Ignition Aluminum Thermites Energetic materials a b s t r a c t Powder energetic materials are highly sensitive to electrostatic...Fundamentals, in: Heat Conduction, Wiley, Hoboken, NJ, 2012. [12] Davin G. Piercey, Thomas M. Klapotke, Nanoscale aluminum metal oxide ( thermite ) reactions for...propagation velocity in thermites with a nanoscale oxidizer, Propellants Explos. Pyrotechn. 39 (3) (2014) 407 415. [18] Kevin Moore, Michelle L
Reduction of mixed Mn-Zr oxides: in situ XPS and XRD studies.

PubMed

Bulavchenko, O A; Vinokurov, Z S; Afonasenko, T N; Tsyrul'nikov, P G; Tsybulya, S V; Saraev, A A; Kaichev, V V

2015-09-21

A series of mixed Mn-Zr oxides with different molar ratios Mn/Zr (0.1-9) have been prepared by coprecipitation of manganese and zirconium nitrates and characterized by X-ray diffraction (XRD) and BET methods. It has been found that at concentrations of Mn below 30 at%, the samples are single-phase solid solutions (MnxZr1-xO2-δ) based on a ZrO2 structure. X-ray photoelectron spectroscopy (XPS) measurements showed that manganese in these solutions exists mainly in the Mn(4+) state on the surface. An increase in Mn content mostly leads to an increase in the number of Mn cations in the structure of solid solutions; however, a part of the manganese cations form Mn2O3 and Mn3O4 in the crystalline and amorphous states. The reduction of these oxides with hydrogen was studied by a temperature-programmed reduction technique, in situ XRD, and near ambient pressure XPS in the temperature range from 100 to 650 °C. It was shown that the reduction of the solid solutions MnxZr1-xO2-δ proceeds via two stages. During the first stage, at temperatures between 100 and 500 °C, the Mn cations incorporated into the solid solutions MnxZr1-xO2-δ undergo partial reduction. During the second stage, at temperatures between 500 and 700 °C, Mn cations segregate on the surface of the solid solution. In the samples with more than 30 at% Mn, the reduction of manganese oxides was observed: Mn2O3 → Mn3O4 → MnO.
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.
Fabricating Ohmic contact on Nb-doped SrTiO{sub 3} surface in nanoscale

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

Wang, Yuhang; National Key Laboratory of Shock Wave and Detonation Physics, Institute of Fluid Physics, Chinese Academy of Engineering Physics, Mianyang, Sichuan 621999; Shi, Xiaolan

2016-05-09

Fabricating reliable nano-Ohmic contact on wide gap semiconductors is an important yet difficult step in oxide nanoelectronics. We fabricated Ohmic contact on the n-type wide gap oxide Nb-doped SrTiO{sub 3} in nanoscale by mechanically scratching the surface using an atomic force microscopy tip. Although contacted to high work function metal, the scratched area exhibits nearly linear IV behavior with low contact resistance, which maintains for hours in vacuum. In contrast, the unscratched area shows Fowler–Nordheim tunneling dominated Schottky rectifying behavior with high contact resistance. It was found that the Ohmic conductivity in the scratched area was drastically suppressed by oxygenmore » gas indicating the oxygen vacancy origin of the Ohmic behavior. The surface oxygen vacancy induced barrier width reduction was proposed to explain the phenomena. The nanoscale approach is also applicable to macroscopic devices and has potential application in all-oxide devices.« less
Oxidizability of unsaturated fatty acids and of a non-phenolic lignin structure in the manganese peroxidase-dependent lipid peroxidation system

Treesearch

Alexander N. Kapich; Tatyana V. Korneichik; Annele Hatakka; Kenneth E. Hammel

2010-01-01

Unsaturated fatty acids have been proposed to mediate the oxidation of recalcitrant, non-phenolic lignin structures by fungal manganese peroxidases (MnP), but their precise role remains unknown. We investigated the oxidizability of three fatty acids with varying degrees of polyunsaturation (linoleic, linolenic, and arachidonic acids) by measuring conjugated dienes...
PRECIPITATION OF ZIRCONIUM, NIOBIUM, AND RUTHENIUM FROM AQUEOUS SOLUTIONS

DOEpatents

Wilson, A.S.

1958-08-12

An improvement on the"head end process" for decontaminating dissolver solutions of their Zr, Ni. and Ru values. The process consists in adding a water soluble symmetrical dialkyl ketone. e.g. acetone, before the formation of the manganese dioxide precipitate. The effect is that upon digestion, the ruthenium oxide does not volatilize, but is carried on the manganese dioxide precipitate.
Microbial community response reveals underlying mechanism of industrial-scale manganese sand biofilters used for the simultaneous removal of iron, manganese and ammonia from groundwater.

PubMed

Zhang, Yu; Sun, Rui; Zhou, Aijuan; Zhang, Jiaguang; Luan, Yunbo; Jia, Jianna; Yue, Xiuping; Zhang, Jie

2018-01-08

Most studies have employed aeration-biofiltration process for the simultaneous removal of iron, manganese and ammonia in groundwater. However, what's inside the "black box", i.e., the potential contribution of functional microorganisms behavior and interactions have seldom been investigated. Moreover, little attention has been paid to the correlations between environmental variables and functional microorganisms. In this study, the performance of industrial-scale biofilters for the contaminated groundwater treatment was studied. The effluent were all far below the permitted concentration level in the current drinking water standard. Pyrosequencing illustrated that shifts in microbial community structure were observed in the microbial samples from different depths of filter. Microbial networks showed that the microbial community structure in the middle- and deep-layer samples was similar, in which a wide range of manganese-oxidizing bacteria was identified. By contrast, canonical correlation analysis showed that the bacteria capable of ammonia-oxidizing and nitrification was enriched in the upper-layer, i.e., Propionibacterium, Nitrosomonas, Nitrosomonas and Candidatus Nitrotoga. The stable biofilm on the biofilter media, created by certain microorganisms from the groundwater microflora, played a crucial role in the simultaneous removal of the three pollutants.
Manganese deposition in drinking water distribution systems.

PubMed

Gerke, Tammie L; Little, Brenda J; Barry Maynard, J

2016-01-15

This study provides a physicochemical assessment of manganese deposits on brass and lead components from two fully operational drinking water distributions systems. One of the systems was maintained with chlorine; the other, with secondary chloramine disinfection. Synchrotron-based in-situ micro X-ray adsorption near edge structure was used to assess the mineralogy. In-situ micro X-ray fluorescence mapping was used to demonstrate the spatial relationships between manganese and potentially toxic adsorbed metal ions. The Mn deposits ranged in thickness from 0.01 to 400 μm. They were composed primarily of Mn oxides/oxhydroxides, birnessite (Mn(3+) and Mn(4+)) and hollandite (Mn(2+) and Mn(4+)), and a Mn silicate, braunite (Mn(2+) and Mn(4+)), in varying proportions. Iron, chromium, and strontium, in addition to the alloying elements lead and copper, were co-located within manganese deposits. With the exception of iron, all are related to specific health issues and are of concern to the U.S. Environmental Protection Agency (U.S. EPA). The specific properties of Mn deposits, i.e., adsorption of metals ions, oxidation of metal ions and resuspension are discussed with respect to their influence on drinking water quality. Copyright © 2015 Elsevier B.V. All rights reserved.
Zinc oxide varistors and/or resistors

DOEpatents

Arnold, W.D. Jr.; Bond, W.D.; Lauf, R.J.

1993-07-27

Varistors and/or resistors are described that include doped zinc oxide gel microspheres. The doped zinc oxide gel microspheres preferably have from about 60 to about 95% by weight zinc oxide and from about 5 to about 40% by weight dopants based on the weight of the zinc oxide. The dopants are a plurality of dopants selected from silver salts, boron oxide, silicon oxide and hydrons oxides of aluminum, bismuth, cobalt, chromium, manganese, nickel, and antimony.
Zinc oxide varistors and/or resistors

DOEpatents

Arnold, Jr., Wesley D.; Bond, Walter D.; Lauf, Robert J.

1993-01-01

Varistors and/or resistors that includes doped zinc oxide gel microspheres. The doped zinc oxide gel microspheres preferably have from about 60 to about 95% by weight zinc oxide and from about 5 to about 40% by weight dopants based on the weight of the zinc oxide. The dopants are a plurality of dopants selected from silver salts, boron oxide, silicon oxide and hydrons oxides of aluminum, bismuth, cobalt, chromium, manganese, nickel, and antimony.
Oxidation/volatilization rates in air for candidate fusion reactor blanket materials, PCA and HT-9

NASA Astrophysics Data System (ADS)

Piet, S. J.; Kraus, H. G.; Neilson, R. M.; Jones, J. L.

1986-11-01

Large uncertainties exist in the quantity of neutron-induced activation products that can be mobilized in potential fusion accidents. The accidental combination of high temperatures and oxidizing conditions might lead to mobilization of a significant amount of activation products from structural materials. Here, the volatilization of constituents of PCA and HT-9 resulting form oxidation in air was investigated. Tests were conducted in flowing air at temperatures from 600 to 1300°C for 1, 5, or 20 h. Elemental volatility was calculated in terms of the weight fraction of the element volatilized from the initial alloy. Molybdenum and manganese were the radiologically significant primary constituents most volatilized, suggesting that molybdenum and manganese should be minimized in fusion steel compositions. Higher chromium content appears beneficial in reducing hazards from mobile activation products. Scanning electron microscopy and energy dispersive spectroscopy were used to study the oxide layer on samples.
[Removal Characteristics of Elemental Mercury by Mn-Ce/molecular Sieve].

PubMed

Tan, Zeng-qiang; Niu, Guo-ping; Chen, Xiao-wen; An, Zhen

2015-06-01

The impregnation method was used to support molecular sieve with active manganese and cerium components to obtain a composite molecular sieve catalyst. The mercury removal performance of the catalyst was studied with a bench-scale setup. XPS analysis was used to characterize the sample before and after the modification in order to study the changes in the active components of the catalyst prepared. The results showed that the catalyst carrying manganese and cerium components had higher oxidation ability of elemental mercury in the temperature range of 300 degrees C - 450 degrees C, especially at 450 degrees C, the oxidation efficiency of elemental mercury was kept above 80%. The catalyst had more functional groups that were conducive to the oxidation of elemental mercury, and the mercury removal mainly depended on the chemical adsorption. The SO2 and NO in flue gas could inhibit the oxidation of elemental mercury to certain extent.
Two-step oxalate approach for the preparation of high performance LiNi0.5Mn1.5O4 cathode material with high voltage

NASA Astrophysics Data System (ADS)

Liu, Zushan; Jiang, Yangmei; Zeng, Xiaoyuan; Xiao, Guan; Song, Huiyu; Liao, Shijun

2014-02-01

A high voltage cathode material, LiNi0.5Mn1.5O4, is synthesized with a two-step approach, in which the nickel-manganese oxalate precipitate is firstly obtained by adding oxalic acid to the solution of nickel and manganese ions precursors, followed by calcining the oxalates to obtain spinel nickel-manganese oxide, incorporating lithium ions with ball milling and calcining at 900 °C for 15 h. The materials are characterized with TG, XRD, SEM, BET and FTIR; it is revealed that both nickel-manganese oxide and final LiNi0.5Mn1.5O4 have well defined spinel structure. The LiNi0.5Mn1.5O4 spinel materials exhibit high capacities and good cyclic stability, the capacity of the materials is in the range from 126 to 136 mAh -1, depending on the calcining temperatures. The sample calcined at an optimal temperature of 900 °C exhibits best performance, the capacity is high up to 136 mAh g-1 at tenth cycle and the capacity retention after 50 cycles is 93%. For the sample prepared by mixing and milling oxalate with lithium salt, the discharge capacity is only 115 mAh g-1. We suggest that the spinel oxide derived from oxalate may play an important role for the high performance and high stability of the final cathode materials.
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
Battery manganese dioxide - a survey of its history and etymology

NASA Astrophysics Data System (ADS)

Euler, Karl-Jaochim

1982-10-01

Manganese dioxide was known two thousand years ago. It was described by Plinius. Later, Basilius Valentinus named it "Braunstein", the brownstone. Its chemical nature was recognized by Scheele and his student Gahn. Its first application in the field of batteries seems to have been by Ritter. Following Leclanchéś invention it has been used on a large scale in dry batteries. In 1977 about 300 000 metric tons of battery grade manganese dioxide were consumed. More than 50% of the oxide is derived from natural ores, and about one third is obtained as electrochemically deposited dioxide.
NASA Curiosity at Site of Clues About Ancient Oxygen

NASA Image and Video Library

2016-06-27

This scene shows NASA's Curiosity Mars rover at a location called "Windjana," where the rover found rocks containing manganese-oxide minerals, which require abundant water and strongly oxidizing conditions to form. In front of the rover are two holes from the rover's sample-collection drill and several dark-toned features that have been cleared of dust (see inset images). These flat features are erosion-resistant fracture fills containing manganese oxides. The discovery of these materials suggests the Martian atmosphere might once have contained higher abundances of free oxygen than it does now. The rover used the Mars Hand Lens Imager (MAHLI) camera in April and May 2014 to take dozens of images that were combined into this self-portrait. http://photojournal.jpl.nasa.gov/catalog/PIA20752
Fate of manganese associated with the inhalation of welding fumes: potential neurological effects.

PubMed

Antonini, James M; Santamaria, Annette B; Jenkins, Neil T; Albini, Elisa; Lucchini, Roberto

2006-05-01

Welding fumes are a complex mixture composed of different metals. Most welding fumes contain a small percentage of manganese. There is an emerging concern among occupational health officials about the potential neurological effects associated with the exposure to manganese in welding fumes. Little is known about the fate of manganese that is complexed with other metals in the welding particles after inhalation. Depending on the welding process and the composition of the welding electrode, manganese may be present in different oxidation states and have different solubility properties. These differences may affect the biological responses to manganese after the inhalation of welding fumes. Manganese intoxication and the associated neurological symptoms have been reported in individual cases of welders who have been exposed to high concentrations of manganese-containing welding fumes due to work in poorly ventilated areas. However, the question remains as to whether welders who are exposed to low levels of welding fumes over long periods of time are at risk for the development of neurological diseases. For the most part, questions remain unanswered. There is still paucity of adequate scientific reports on welders who suffered significant neurotoxicity, hence there is a need for well-designed epidemiology studies that combine complete information on the occupational exposure of welders with both behavioral and biochemical endpoints of neurotoxicity.
Diverse manganese(II)-oxidizing bacteria are prevalent in drinking water systems.

PubMed

Marcus, Daniel N; Pinto, Ameet; Anantharaman, Karthik; Ruberg, Steven A; Kramer, Eva L; Raskin, Lutgarde; Dick, Gregory J

2017-04-01

Manganese (Mn) oxides are highly reactive minerals that influence the speciation, mobility, bioavailability and toxicity of a wide variety of organic and inorganic compounds. Although Mn(II)-oxidizing bacteria are known to catalyze the formation of Mn oxides, little is known about the organisms responsible for Mn oxidation in situ, especially in engineered environments. Mn(II)-oxidizing bacteria are important in drinking water systems, including in biofiltration and water distribution systems. Here, we used cultivation dependent and independent approaches to investigate Mn(II)-oxidizing bacteria in drinking water sources, a treatment plant and associated distribution system. We isolated 29 strains of Mn(II)-oxidizing bacteria and found that highly similar 16S rRNA gene sequences were present in all culture-independent datasets and dominant in the studied drinking water treatment plant. These results highlight a potentially important role for Mn(II)-oxidizing bacteria in drinking water systems, where biogenic Mn oxides may affect water quality in terms of aesthetic appearance, speciation of metals and oxidation of organic and inorganic compounds. Deciphering the ecology of these organisms and the factors that regulate their Mn(II)-oxidizing activity could yield important insights into how microbial communities influence the quality of drinking water. © 2016 Society for Applied Microbiology and John Wiley & Sons Ltd.

Interlocked by nanoscale sculpturing: pure aluminum copper contacts (Conference Presentation)

NASA Astrophysics Data System (ADS)

Gerngross-Baytekin, Melike; Gerngross, Mark Daniel; Carstensen, Jürgen; Adelung, Rainer

2017-06-01

Connecting metals reliable with different corrosion potential is a well-known challenge. An extreme example are copper aluminum contacts. Galvanic corrosion occurs if the two different metals are in contact with each other and an electrolyte, the aluminum becomes susceptible to corrosion under current flow. Usually, antioxidant pastes containing metals are employed but create difficulties e.g. for fatigue resistant power electronic connections. The recently described process of nanoscale sculpturing [1] offers an alternative. Usually, if the surface of metals like aluminium are prepared they are just arbitrary cuts through the bulk. There is no optimization of the surface grain structure towards stability at all. Neither the crystalline facets in the grains are in their most stable orientation nor is the protective oxide shell the most stable one. The nanoscale sculpturing approach is carving out the most stable grains and planes by chemical or electrochemical treatment. The decisive trick is that the chemistry is targeting towards the instable oxide and not the metal. Aluminium sample surfaces including alloys like AA575 exhibit afterwards single crystalline surface facets covered with nanoscale stable oxide films. Galvanically deposited copper forms extremely reliable interlocked connections on top, even allowing for soldering on top of their surface.
The aluminosilicate fraction of North Pacific manganese nodules

USGS Publications Warehouse

Bischoff, J.L.; Piper, D.Z.; Leong, K.

1981-01-01

Nine nodules collected from throughout the deep North Pacific were analyzed for their mineralogy and major-element composition before and after leaching with Chester-Hughes solution. Data indicate that the mineral phillipsite accounts for the major part (> 75%) of the aluminosilicate fraction of all nodules. It is suggested that formation of phillipsite takes place on growing nodule surfaces coupled with the oxidation of absorbed manganous ion. All the nodules could be described as ternary mixtures of amorphous iron fraction (Fe-Ti-P), manganese oxide fraction (Mn-Mg Cu-Ni), and phillipsite fraction (Al-Si-K-Na), these fractions accounting for 96% of the variability of the chemical composition. ?? 1981.
Dietary supplementation of green synthesized manganese-oxide nanoparticles and its effect on growth performance, muscle composition and digestive enzyme activities of the giant freshwater prawn Macrobrachium rosenbergii.

PubMed

Asaikkutti, Annamalai; Bhavan, Periyakali Saravana; Vimala, Karuppaiya; Karthik, Madhayan; Cheruparambath, Praseeja

2016-05-01

The green synthesized Mn3O4 nanoparticles (manganese-oxide nanoparticles) using Ananas comosus (L.) peel extract was characterized by various techniques. HR-SEM photograph showed that manganese-oxide nanoparticles (Mn-oxide NPs) were spherical in shape, with an average size of 40-50 nm. The Zeta potential revealed the surface charge of Mn-oxide NPs to be negative. Further, the Mn-oxide NPs were dietary supplemented for freshwater prawn Macrobrachium rosenbergii. The experimental basal diets were supplemented with Mn-oxide NPs at the rates of 0 (control), 3.0, 6.0, 9.0, 12, 15 and 18 mg/kg dry feed weight. The as-supplemented Mn-oxide NPs were fed in M. rosenbergii for a period of 90 days. The experimental study demonstrated that prawns fed with diet supplemented with 3-18 mg Mn-oxide NPs/kg shows enhanced (P<0.05) growth performance, including final weight and weight gain (WG). Significant differences (P<0.05) in feed conversion ratio (FCR) were observed in prawn fed with different diets. Additionally, prawns fed with 3.0-18 mg/kg Mn-oxide NPs supplemented diets achieved significant (P<0.05) improvement in growth performance, digestive enzyme activities and muscle biochemical compositions, while, the prawns fed with 16 mg/kg of Mn-oxide NPs showed enhanced performance. Prawns fed on diet supplemented with 16 mg/kg Mn-oxide NPs showed significantly (P<0.05) higher total protein level. The antioxidants enzymatic activity (SOD and CAT) metabolic enzymes status in muscle and hepatopancreas showed no significant (P>0.05) alterations in prawns fed with 3.0-18 mg/kg of Mn-oxide NPs supplemented diets. Consequently, the present work proposed that 16 mg/kg of Mn-oxide NPs could be supplemented for flexible enhanced survival, growth and production of M. rosenbergii. Therefore, the data of the present study recommend the addition of 16 mg/kg of Mn-oxide NPs diet to developed prawn growth and antioxidant defense system. Copyright © 2016 Elsevier GmbH. All rights reserved.
Pyroprocessing of oxidized sodium-bonded fast reactor fuel - An experimental study of treatment options for degraded EBR-II fuel

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

Hermann, S.D.; Gese, N.J.; Wurth, L.A.

An experimental study was conducted to assess pyrochemical treatment options for degraded EBR-II fuel. As oxidized material, the degraded fuel would need to be converted back to metal to enable electrorefining within an existing electro-metallurgical treatment process. A lithium-based electrolytic reduction process was studied to assess the efficacy of converting oxide materials to metal with a particular focus on the impact of zirconium oxide and sodium oxide on this process. Bench-scale electrolytic reduction experiments were performed in LiCl-Li{sub 2}O at 650 C. degrees with combinations of manganese oxide (used as a surrogate for uranium oxide), zirconium oxide, and sodium oxide.more » In the absence of zirconium or sodium oxide, the electrolytic reduction of MnO showed nearly complete conversion to metal. The electrolytic reduction of a blend of MnO-ZrO{sub 2} in LiCl - 1 wt% Li{sub 2}O showed substantial reduction of manganese, but only 8.5% of the zirconium was found in the metal phase. The electrolytic reduction of the same blend of MnO-ZrO{sub 2} in LiCl - 1 wt% Li{sub 2}O - 6.2 wt% Na{sub 2}O showed substantial reduction of manganese, but zirconium reduction was even less at 2.4%. This study concluded that ZrO{sub 2} cannot be substantially reduced to metal in an electrolytic reduction system with LiCl - 1 wt% Li{sub 2}O at 650 C. degrees due to the perceived preferential formation of lithium zirconate. This study also identified a possible interference that sodium oxide may have on the same system by introducing a parasitic and cyclic reaction of dissolved sodium metal between oxidation at the anode and reduction at the cathode. When applied to oxidized sodium-bonded EBR-II fuel (e.g., U-10Zr), the prescribed electrolytic reduction system would not be expected to substantially reduce zirconium oxide, and the accumulation of sodium in the electrolyte could interfere with the reduction of uranium oxide, or at least render it less efficient.« less
The tunable optical magneto-electric effect in patterned manganese oxide superlattices

NASA Astrophysics Data System (ADS)

Pei, H. Y.; Zhang, Y. J.; Guo, S. J.; Ren, L. X.; Yan, H.; Chen, C. L.; Jin, K. X.; Luo, B. C.

2018-05-01

The optical magneto-electric (OME) effect has been widely investigated in magnetic materials, but obtaining the large and tunable OME effect is an ongoing challenge. We here design a tri-color superlattice composed of manganese oxides, Pr0.9Ca0.1MnO3, La0.9Sr0.1MnO3, and La0.9Sb0.1MnO3, where the space-inversion and time-reversal symmetries are broken. With the aid of the grating structure, the OME effect for near-infrared light in tri-color superlattices is investigated systematically through the Bragg diffraction method. The relative change of diffracted light intensity of the order n = ±1 has a strong dependence on the magnetization and polarization of the tri-color superlattice, whether the superlattice is irradiated in reflection or transmission geometries. Otherwise, the relative change of diffracted light intensity increases with the increase in the superlattice period and with the decrease in the grating period. The maximum relative change of diffracted light intensity in tri-color superlattices with the grating structure patterned is as large as 8.27%. These results pave the way for designing next-generation OME devices based on manganese oxides.
Ultrasensitive Detection of Methylmercaptan Gas Using Layered Manganese Oxide Nanosheets with a Quartz Crystal Microbalance Sensor.

PubMed

Tokura, Yuki; Nakada, Gentoku; Moriyama, Yukari; Oaki, Yuya; Imai, Hiroaki; Shiratori, Seimei

2017-11-21

Methylmercaptan (MM) is a marker of periodontal disease; however, the required sensitivity for MM is parts per billion, which has been challenging to realize with a simple sensor. Here, we report the capability to detect MM at concentrations as low as 20 ppb using layered manganese oxide nanosheets with a quartz crystal microbalance sensor. The sensing capabilities of the manganese oxide nanosheets are promoted by adsorbed water present on and between the nanosheets. The strong adsorption of MM to the sensor, which is necessary for the high sensitivity, leads to significant hysteresis in the response on cycling due to irreversible adsorption. However, the sensor can be readily reset by heating to 80 °C, which leads to highly reproducible response to MM vapor at low concentrations. A key aspect of this sensor design is the high selectivity toward MM in comparison to other compounds such as ethanol, ammonia, acetaldehyde, acetic acid, toluene, and pyridine. This layered nanosheets design for high-sensitivity sensors, demonstrated here for dilute MM, holds significant promise for addressing needs to identify sulfur compounds associated for environmental protection and medical diagnostics.
Arsenic transformation and adsorption by iron hydroxide/manganese dioxide doped straw activated carbon

NASA Astrophysics Data System (ADS)

Xiong, Ying; Tong, Qiang; Shan, Weijun; Xing, Zhiqiang; Wang, Yuejiao; Wen, Siqi; Lou, Zhenning

2017-09-01

Iron hydroxide/manganese dioxide doped straw activated carbon was synthesized for As(III) adsorption. The Fe-Mn-SAc adsorbent has two advantages, on the one hand, the straw active carbon has a large surface area (1360.99 m2 g-1) for FeOOH and MnO2 deposition, on the other hand, the manganese dioxide has oxidative property as a redox potential of (MnO2 + H+)/Mn2+, which could convert As(III) into As(V). Combined with the arsenic species after reacting with Fe-Mn-SAc, the As(III) transformation and adsorption mechanism was discussed. H2AsO4-oxidized from As(III) reacts with the Fe-Mn-SAc by electrostatic interaction, and unoxidized As(III) as H3AsO3 reacts with SAc and/or iron oxide surface by chelation effect. The adsorption was well-described by Langmuir isotherms model, and the adsorption capacity of As(III) was 75.82 mg g-1 at pH 3. Therefore, considering the straw as waste biomass material, the biosorbent (Fe-Mn-SAc) is promising to be exploited for applications in the treatment of industrial wastewaters containing a certain ratio of arsenic and germanium.
Tunnel structured manganese oxide nanowires as redox active electrodes for hybrid capacitive deionization

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

Byles, Bryan W.; Cullen, David A.; More, Karren Leslie

We report that hybrid capacitive deionization (HCDI), which combines a capacitive carbon electrode and a redox active electrode in a single device, has emerged as a promising method for water desalination, enabling higher ion removal capacity than devices containing two carbon electrodes. However, to date, the desalination performance of few redox active materials has been reported. For the first time, we present the electrochemical behavior of manganese oxide nanowires with four different tunnel crystal structures as faradaic electrodes in HCDI cells. Two of these phases are square tunnel structured manganese oxides, α-MnO 2 and todorokite-MnO 2. The other two phasesmore » have novel structures that cross-sectional scanning transmission electron microscopy analysis revealed to have ordered and disordered combinations of structural tunnels with different dimensions. The ion removal performance of the nanowires was evaluated not only in NaCl solution, which is traditionally used in laboratory experiments, but also in KCl and MgCl 2 solutions, providing better understanding of the behavior of these materials for desalination of brackish water that contains multiple cation species. High ion removal capacities (as large as 27.8 mg g -1, 44.4 mg g -1, and 43.1 mg g -1 in NaCl, KCl, and MgCl 2 solutions, respectively) and high ion removal rates (as large as 0.112 mg g -1 s -1, 0.165 mg g -1 s -1, and 0.164 mg g -1 s -1 in NaCl, KCl, and MgCl 2 solutions, respectively) were achieved. By comparing ion removal capacity to structural tunnel size, it was found that smaller tunnels do not favor the removal of cations with larger hydrated radii, and more efficient removal of larger hydrated cations can be achieved by utilizing manganese oxides with larger structural tunnels. Extended HCDI cycling and ex situ X-ray diffraction analysis revealed the excellent stability of the manganese oxide electrodes in repeated ion removal/ion release cycles, and compositional analysis of the electrodes indicated that ion removal is achieved through both surface redox reactions and intercalation of ions into the structural tunnels. In conclusion, this work contributes to the understanding of the behavior of faradaic materials in electrochemical water desalination and elucidates the relationship between the electrode material crystal structure and the ion removal capacity/ion removal rate in various salt solutions.« less
Tunnel structured manganese oxide nanowires as redox active electrodes for hybrid capacitive deionization

DOE PAGES

Byles, Bryan W.; Cullen, David A.; More, Karren Leslie; ...

2017-12-18

We report that hybrid capacitive deionization (HCDI), which combines a capacitive carbon electrode and a redox active electrode in a single device, has emerged as a promising method for water desalination, enabling higher ion removal capacity than devices containing two carbon electrodes. However, to date, the desalination performance of few redox active materials has been reported. For the first time, we present the electrochemical behavior of manganese oxide nanowires with four different tunnel crystal structures as faradaic electrodes in HCDI cells. Two of these phases are square tunnel structured manganese oxides, α-MnO 2 and todorokite-MnO 2. The other two phasesmore » have novel structures that cross-sectional scanning transmission electron microscopy analysis revealed to have ordered and disordered combinations of structural tunnels with different dimensions. The ion removal performance of the nanowires was evaluated not only in NaCl solution, which is traditionally used in laboratory experiments, but also in KCl and MgCl 2 solutions, providing better understanding of the behavior of these materials for desalination of brackish water that contains multiple cation species. High ion removal capacities (as large as 27.8 mg g -1, 44.4 mg g -1, and 43.1 mg g -1 in NaCl, KCl, and MgCl 2 solutions, respectively) and high ion removal rates (as large as 0.112 mg g -1 s -1, 0.165 mg g -1 s -1, and 0.164 mg g -1 s -1 in NaCl, KCl, and MgCl 2 solutions, respectively) were achieved. By comparing ion removal capacity to structural tunnel size, it was found that smaller tunnels do not favor the removal of cations with larger hydrated radii, and more efficient removal of larger hydrated cations can be achieved by utilizing manganese oxides with larger structural tunnels. Extended HCDI cycling and ex situ X-ray diffraction analysis revealed the excellent stability of the manganese oxide electrodes in repeated ion removal/ion release cycles, and compositional analysis of the electrodes indicated that ion removal is achieved through both surface redox reactions and intercalation of ions into the structural tunnels. In conclusion, this work contributes to the understanding of the behavior of faradaic materials in electrochemical water desalination and elucidates the relationship between the electrode material crystal structure and the ion removal capacity/ion removal rate in various salt solutions.« less
Analysis of in situ manganese(II) oxidation in the Columbia River and offshore plume: Linking microbial community structure to active biogeochemical cycles

PubMed Central

Anderson, C. R.; Davis, R. E.; Bandolin, N. S.; Baptista, A. M.; Tebo, B. M.

2017-01-01

The Columbia River is a major source of dissolved nutrients and trace metals for the west coast of North America. A large proportion of these nutrients are sourced from the Columbia River Estuary where coastal and terrestrial waters mix and resuspend particulate matter within the water column. As estuarine water is discharged off the coast it transports the particulate matter, dissolved nutrients and microorganisms forming nutrient rich and metabolically dynamic plumes. In this study, bacterial manganese oxidation within the plume and estuary was investigated during spring and neap tides. The microbial community proteome was fractionated and assayed for Mn oxidation activity. Proteins from the outer membrane and the loosely bound outer membrane fractions were separated using size exclusion chromatography and Mn(II)-oxidizing eluates were analyzed with tandem mass spectrometry to identify potential Mn oxidase protein targets. Multi-copper oxidase (MCO) and heme-peroxidase enzymes were identified in active fractions. T-RFLP cluster analysis indicates that the organisms oxidizing the most Mn(II) were sourced from the Columbia River estuary and nearshore coastal ocean. These organisms are producing up to 10 fM MnO2 cell−1 day−1. Evidence for the presence of Mn(II)-oxidizing bacterial isolates from the genera Aurantimonas, Rhodobacter, Bacillus, and Shewanella was found in T-RFLP profiles. Q-PCR was used to quantify the gene copies of the heme-peroxidase, Aurantimonas SSU rRNA and total bacterial SSU rRNA gene copies. The probes used suggested that Aurantimonas could only account for 1.7% of heme-peroxidase genes quantified suggesting that peroxidase driven manganese oxidation capabilities are widespread throughout other organisms in this environment. PMID:21418498
Effect of enhanced manganese oxidation in the hyporheic zone on basin-scale geochemical mass balance

USGS Publications Warehouse

Harvey, Judson W.; Fuller, Christopher 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, 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 hyporheic exchange in Pinal Creek basin was to remove approximately 20% of the dissolved manganese flowing out of the drainage basin. Our results illustrate that the cumulative significance of reactive uptake in the hyporheic zone depends on the balance between chemical reaction rates, hyporheic porewater residence time, and turnover of streamflow through hyporheic flow paths. The similarity between the hyporheic reaction timescale (1/λs ≈ 1.3 hours), and the hyporheic porewater residence timescale (ts ≈ 8 min) ensured that there was adequate time for the reaction to progress. Furthermore, it was the similarity between the turnover length for stream water flow through hyporheic flow paths (Ls = stream velocity/storage-zone exchange coefficient ≈ 1.3 km) and the length of Pinal Creek (L ≈ 7 km), which ensured that all stream water passed through hyporheic flow paths several times. As a means to generalize our findings to other sites where similar types of hydrologic and chemical information are available, we suggest a cumulative significance index for hyporheic reactions, Rs = λstsL/Ls (dimensionless); higher values indicate a greater potential for hyporheic reactions to influence geochemical mass balance. Our experience in Pinal Creek basin suggests that values of Rs > 0.2 characterize systems where hyporheic reactions are likely to influence geochemical mass balance at the drainage-basin scale.
Comparative evaluation of manganese peroxidase- and Mn(III)-initiated peroxidation of C18 unsaturated fatty acids by different methods

Treesearch

Alexander N. Kapich; Tatyana V. Korneichik; Kenneth E. Hammel; Annele Hatakka

2011-01-01

The peroxidation of C18 unsaturated fatty acids by fungal manganese peroxidase (MnP)/Mn(II) and by chelated Mn(III) was studied with application of three different methods: by monitoring oxygen consumption, by measuring conjugated dienes and by thiobarbituric acid-reactive substances (TBARS) formation. All tested polyunsaturated fatty acids (PUFAs) were oxidized by MnP...
Development of a Protocol and a Screening Tool for Selection of DNAPL Source Area Remediation

DTIC Science & Technology

2012-05-01

sensitivity study completed to investigate the potential influence of manganese dioxide rind formation during permanganate treatment... permanganate as the oxidant. This evaluation is specific to permanganate treatment and the corresponding manganese dioxide rind formation; however...forms within close proximity of the DNAPL phase, as occurs when permanganate reacts with the DNAPL. 1.4 IMPLEMENTATION ISSUES DNAPL TEST has been
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 iron, 1.50 mg/L increase in dissolved manganese, and 0.24 mg/L decrease in dissolved oxygen concentration.
Heavy metal bioaccumulation in Great Basin submersed aquatic macrophytes

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

Lytle, C.M.

1994-01-01

Seasonal element cycling and nutritional quality were determined in sago pondweed plant tissue. Leaf protein was 27% in July and 15% in December. Sago drupelet protein content was 9% in July and 6.5% in October. Sago plant tissue mineral, trace metal and non-structural carbohydrate content were high in the Fall. Submersed aquatic plant species from the Provo River drainage, Bear River MBR and Utah Lake - Provo Bay were significantly higher in heavy metals than aquatic species from remote wetlands. Extreme sodium concentrations were found in water, sediment and plant tissue in Ibis and Harrison pools (Fish Springs NWR). Boron,more » arsenic and selenium concentrations in plant tissue were much lower than those at Kesterson Reservoir, California. Submersed aquatic plants may act as channels that expedite the trophic movement of metal ions. The chemical structure of accumulated manganese and iron in sago pondweed plant tissue differed with time of year. June plant tissue manganese was fully hydrated. Accumulated manganese in October plant tissue was a Mn(II)Mn(III) mineral oxide. Accumulated iron was Fe(III) in both leaf and root tissue. Methylmercury was toxic to Lesser duckweed at very low doses (>0.1 [mu]g ml[sup [minus]1]). Increased pH improved frond survival in organic and inorganic mercury solutions. Duckweed should be considered as a sensitive phytoassay of methylmercury toxicity. Soil manganese and lead concentrations are correlated with distance from the roadway and traffic volume. Soil lead concentrations have moved deeper into the profile. Roadside aquatic plants were higher in manganese than herbaceous plants and grasses. Roadside snow and water were low in manganese and lead. Roadside soil and plants were apparently contaminated by Mn oxides from motor vehicle exhaust.« less
Removal of iron and manganese using biological roughing up flow filtration technology.

PubMed

Pacini, Virginia Alejandra; María Ingallinella, Ana; Sanguinetti, Graciela

2005-11-01

The removal of iron and manganese from groundwater using biological treatment methods is almost unknown in Latin America. Biological systems used in Europe are based on the process of double rapid biofiltration during which dissolved oxygen and pH need to be strictly controlled in order to limit abiotic iron oxidation. The performance of roughing filter technology in a biological treatment process for the removal of iron and manganese, without the use of chemical agents and under natural pH conditions was studied. Two pilot plants, using two different natural groundwaters, were operated with the following treatment line: aeration, up flow roughing filtration and final filtration (either slow or rapid). Iron and manganese removal efficiencies were found to be between 85% and 95%. The high solid retention capability of the roughing filter means that it is possible to remove iron and manganese simultaneously by biotic and abiotic mechanisms. This system combines simple, low-cost operation and maintenance with high iron and manganese removal efficiencies, thus constituting a technology which is particularly suited to small waterworks.
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 correlations were found between EC50 values and reduction potential, electronegativity and the covalent index. Thus, metal toxicity in P. putida GB-1 appears to be modulated by the metals’ propensity to participate in covalent interactions and generate oxidative stress. This study provides a quantitative measure of metal tolerance in P. putida GB-1, as well as operational limits for Mn oxidation in this model system, both of which have important implications for the reactivity of P. putida-MnO2 assemblages formed in metal-impacted ecosystems.
REGIOSELECTIVE OXIDATIONS OF EQUILENIN DERIVATIVES CATALYZED BY A RHODIUM (III) PORPHYRIN COMPLEX-CONTRAST WITH THE MANGANESE (III) PORPHYRIN. (R826653)

EPA Science Inventory

Abstract
Equilenin acetate and dihydroequilenin acetate were oxidized with iodosobenzene and a rhodium(III) porphyrin catalyst. The selectivity of the reactions differs from that with the corresponding Mn(III) catalyst, or from that of free radical chain oxidation.
Reactions of metal ions at surfaces of hydrous iron oxide

USGS Publications Warehouse

Hem, J.D.

1977-01-01

Cu, Ag and Cr concentrations in natural water may be lowered by mild chemical reduction involving ferric hydroxide-ferrous ion redox processes. V and Mo solubilities may be controlled by precipitation of ferrous vanadate or molybdate. Concentrations as low as 10-8.00 or 10-9.00 M are readily attainable for all these metals in oxygen-depleted systems that are relatively rich in Fe. Deposition of manganese oxides such as Mn3O4 can be catalyzed in oxygenated water by coupling to ferrous-ferric redox reactions. Once formed, these oxides may disproportionate, giving Mn4+ oxides. This reaction produces strongly oxidizing conditions at manganese oxide surfaces. The solubility of As is significantly influenced by ferric iron only at low pH. Spinel structures such as chromite or ferrites of Cu, Ni, and Zn, are very stable and if locally developed on ferric hydroxide surfaces could bring about solubilities much below 10-9.00 M for divalent metals near neutral pH. Solubilities calculated from thermodynamic data are shown graphically and compared with observed concentrations in some natural systems. ?? 1977.
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. Copyright © 2011 Elsevier Ltd. All rights reserved.

Synthesis and reaction of [[HC(CMeNAr)2]Mn]2 (Ar = 2,6-iPr2C6H3): the complex containing three-coordinate manganese(I) with a Mn-Mn bond exhibiting unusual magnetic properties and electronic structure.

PubMed

Chai, Jianfang; Zhu, Hongping; Stückl, A Claudia; Roesky, Herbert W; Magull, Jörg; Bencini, Alessandro; Caneschi, Andrea; Gatteschi, Dante

2005-06-29

This paper reports on the synthesis, X-ray structure, magnetic properties, and DFT calculations of [[HC(CMeNAr)2]Mn]2 (Ar = 2,6-iPr2C6H3) (2), the first complex with three-coordinate manganese(I). Reduction of the iodide [[HC(CMeNAr)2]Mn(mu-I)]2 (1) with Na/K in toluene afforded 2 as dark-red crystals. The molecule of 2 contains a Mn2(2+) core with a Mn-Mn bond. The magnetic investigations show a rare example of a high-spin manganese(I) complex with an antiferromagnetic interaction between the two Mn(I) centers. The DFT calculations indicate a strong s-s interaction of the two Mn(I) ions with the open shell configuration (3d54s1). This suggests that the magnetic behavior of 2 could be correctly described as the coupling between two S1 = S2 = 5/2 spin centers. The Mn-Mn bond energy is estimated at 44 kcal mol(-1) by first principle calculations with the B3LYP functional. The further oxidative reaction of 2 with KMnO4 or O2 resulted in the formation of manganese(III) oxide [[HC(CMeNAr)2]Mn(mu-O)]2 (3). Compound 3 shows an antiferromagnetic coupling between the two oxo-bridged manganese(III) centers by magnetic measurements.
Nitrated metalloporphyrins as catalysts for alkane oxidation

DOEpatents

Ellis, P.E. Jr.; Lyons, J.E.

1994-01-18

Compositions of matter comprising nitro-substituted metal complexes of porphyrins are catalysts for the oxidation of alkanes. The metal is iron, chromium, manganese, ruthenium, copper or cobalt. The porphyrin ring has nitro groups attached thereto in meso and/or [beta]-pyrrolic positions.
Chemistry Notes

ERIC Educational Resources Information Center

School Science Review, 1976

1976-01-01

Describes several chemistry projects, including solubility, formula for magnesium oxide, dissociation of dinitrogen tetroxide, use of 1-chloro-2, 4-dinitrobenzene, migration of ions, heats of neutralizations, use of pocket calculators, sonic cleaning, oxidation states of manganese, and cell potentials. Includes an extract from Chemical Age on…
Nitrated metalloporphyrins as catalysts for alkane oxidation

DOEpatents

Ellis, Jr., Paul E.; Lyons, James E.

1994-01-01

Compositions of matter comprising nitro-substituted metal complexes of porphyrins are catalysts for the oxidation of alkanes. The metal is iron, chromium, manganese, ruthenium, copper or cobalt. The porphyrin ring has nitro groups attached thereto in meso and/or .beta.-pyrrolic positions.
Stability and transport of commercial metal oxide nanoparticles in aquatic systems

EPA Science Inventory

The use of nano-technology and the application of products containing nano-scale particles have been increasing. When nano-scale particles are released to the environment, their stability, transport properties and interaction with other pollutants and natural organic matter play ...
Detection of different oxidation states of individual manganese porphyrins during their reaction with oxygen at a solid/liquid interface.

PubMed

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.
Interrogation of bimetallic particle oxidation in three dimensions at the nanoscale

DOE PAGES

Han, Lili; Meng, Qingping; Wang, Deli; ...

2016-12-08

An understanding of bimetallic alloy oxidation is key to the design of hollow-structured binary oxides and the optimization of their catalytic performance. However, one roadblock encountered in studying these binary oxide systems is the difficulty in describing the heterogeneities that occur in both structure and chemistry as a function of reaction coordinate. This is due to the complexity of the three-dimensional mosaic patterns that occur in these heterogeneous binary systems. By combining real-time imaging and chemical-sensitive electron tomography, we show that it is possible to characterize these systems with simultaneous nanoscale and chemical detail. We find that there is oxidation-inducedmore » chemical segregation occurring on both external and internal surfaces. Additionally, there is another layer of complexity that occurs during the oxidation, namely that the morphology of the initial oxide surface can change the oxidation modality. As a result, this work characterizes the pathways that can control the morphology in binary oxide materials.« less
Recent progress on elaboration of undoped and doped Y2O3, Gd2O3 rare-earth nano-oxide.

PubMed

Lebbou, K; Perriat, P; Tillement, O

2005-09-01

Some selected materials with small sizes in the nanometer region are reviewed. Different methods for synthesis of nanoscale materials are classified and discussed. Basic prerequisites for successful use of the materials for nanotechnology application are their synthesis with specific and homogeneous composition and geometry. This review summarizes recent results on nanoscale materials containing optically active lanthanide ion especially focused on Y2O3 and Gd2O3 oxide.
Review of the U.S. Department of Energy's "Deep Dive" Effort to Understand Voltage Fade in Li- and Mn-rich Cathodes

DOE PAGES

Croy, Jason R.; Balasubramanian, Mahalingam; Gallagher, Kevin G.; ...

2015-11-01

With roughly two-thirds of daily oil consumption in the United States allotted for transportation, the possibility of efficient and affordable electric vehicles suggests a way to substantially alleviate the Country’s dependence on oil and mitigate the rise of greenhouse gases. Although commercialized Li-ion batteries do not currently meet the stringent demands of a would-be, economically competitive, electrified vehicle fleet, significant efforts are being focused on promising new materials for the next generation of Li-ion batteries. The leading class of materials most suitable for the challenge is the Li- and manganese-rich class of oxides. Denoted as LMR-NMC (Li-manganese-rich, nickel, manganese, cobalt),more » these materials could significantly improve energy densities, cost, and safety, relative to state-of-the-art Ni- and Co-rich Li-ion cells, if successfully developed.1 The success or failure of such a development relies heavily on understanding two defining characteristics of LMR-NMC cathodes. The first is a mechanism whereby the average voltage of cells continuously decreases with each successive charge and discharge cycle. This phenomenon, known as voltage fade, decreases the energy output of cells to unacceptable levels too early in cycling. The second characteristic is a pronounced hysteresis, or voltage difference, between charge and discharge cycles. The hysteresis represents not only an energy inefficiency (i.e., energy in vs energy out) but may also complicate the state of charge/depth of discharge management of larger systems, especially when accompanied by voltage fade. n 2012, the United States Department of Energy’s Office of Vehicle Technologies, well aware of the inherent potential of LMR-NMC materials for improving the energy density of automotive energy storage systems, tasked a team of scientists across the National Laboratory Complex to investigate the phenomenon of voltage fade. Unique studies using synchrotron X-ray absorption (XAS) and high-resolution diffraction (HR-XRD) were coupled with nuclear magnetic resonance spectroscopy (NMR), neutron diffraction, high-resolution transmission electron microscopy (HR-TEM), first-principles calculations, molecular dynamics simulations, and detailed electrochemical analyses. These studies demonstrated for the first time the atomic-scale, structure–property relationships that exist between nanoscale inhomogeneities and defects, and the macroscale, electrochemical performance of these layered oxides. These inhomogeneities and defects have been directly correlated with voltage fade and hysteresis, and a model describing these mechanisms has been proposed. This Account gives a brief summary of the findings of this recently concluded, approximately three-year investigation. Lastly, the interested reader is directed to the extensive body of work cited in the given references for a more comprehensive review of the subject.« less
Volatilization of oxides during oxidation of some superalloys at 1200 C

NASA Technical Reports Server (NTRS)

Zaplatynsky, I.

1977-01-01

Volatilization of oxides during cyclic oxidation of commercial Nichrome, Inconel 750, Rene 41, Stellite 6B, and GE-1541 was studied at 1200 C in static air. Quantitative analysis of oxide vapor deposits revealed that oxides of tungsten, molybdenum, niobium, manganese, and chromium volatilized preferentially from the oxide scales. Aluminum and silicon were not detected in vapor deposits. For all the alloys except GE-1541 chromium was found to be the main metallic element in the oxide scales.
Volatilization of oxides during oxidation of some superalloys at 1200 C

NASA Technical Reports Server (NTRS)

Zaplatynsky, I.

1977-01-01

Volatilization of oxides during cyclic oxidation of commercial Nichrome, Inconel 750, Rene 41, Stellite 6B, and GE-1541 was studied at 1200 C in static air. Quantitative analysis of oxide vapor deposits revealed that oxides of tungsten, molybdenum, niobium, manganese, and chromium volatilized preferentially from the oxide scales. Aluminum and silicon were not detected in vapor deposits. For all the alloys except GE-1541, chromium was found to be the main metallic element in the oxide scales.
Using neutrons, X-rays and nuclear magnetism to determine the role of transition metal oxide inclusions on both glass structure and stability in automotive glass enamels.

PubMed

Bowron, Daniel T; Booth, Jonathan; Barrow, Nathan S; Sutton, Patricia; Johnson, Simon R

2018-05-23

Low levels of transition metal oxides in alkali borosilicate glass systems can drastically influence crystallisation and phase separation properties. We investigated the non-monotonic effect of manganese doping on suppressing crystallisation, and the influence on optical properties by iron oxide doping, in terms of local atomic structure. Structural models based on empirical potential structure refinement were generated from neutron and X-ray scattering data, and compared against multinuclear solid-state NMR. This revealed that a 2.5% manganese doping had a disruptive effect on the entire glass network, supressing crystallisation of an undesired bismuth silicate phase, and that iron species preferentially locate near borate tetrahedra. Preventing phase separation and controlling crystallisation behaviour of glass are critical to the ultimate properties of automotive glass enamels.
Simultaneous reduction and carburization of ilmenite

NASA Astrophysics Data System (ADS)

Coley, K. S.; Terry, B. S.; Grieveson, P.

1995-05-01

Western Australian ilmenite was reduced using “Collie” coal at temperatures in the range 1587 to 1790 K to form carbon-saturated iron and titanium oxycarbide. The oxycarbide phase formed from Ti3O5 at temperatures below 1686 K and from Ti2O3 at temperatures above 1686 K. At 1686 K, both mechanisms occurred. The reaction rate was controlled by oxidation of carbon by carbon dioxide generated by reduction of the oxide phase. The final product at temperatures up to 1686 K was a fine dispersion of titanium oxycarbide in iron. At 1790 K, the reducing oxide tended to remain intact and formed a coarser distribution. In general, manganese impurities from the ilmenite were confined to the iron phase in the product, although some of the coarser oxycarbide particles formed at 1790 K contained trapped manganese at the internal pores.
[The industrial environment in the electric-furnace steel smelting, converter and open-hearth furnace methods of manufacturing manganese-alloyed steels].

PubMed

Karnaukh, N G; Petrov, G A; Gapon, V A; Poslednichenko, I P; Shmidt, S E

1992-01-01

Inspection of the environment in manganese-alloyed steel production showed inadequate hygienic conditions of the technological processes employed. Air was more polluted by manganese oxides during the oxygen-converter process though their highest concentrations, 38 times exceeding the MAS, appeared during the casting of steel. An electric furnace coated by dust-noise-proof material and gas cleaning is preferable from a hygienic point of view. The influence of unfavourable microclimate, intensive infrared irradiation and loud noise on workers necessitates automation and mechanization of the process in order to improve the working conditions.
Ternary manganese ferrite/graphene/polyaniline nanostructure with enhanced electrochemical capacitance performance

NASA Astrophysics Data System (ADS)

Xiong, Pan; Hu, Chenyao; Fan, Ye; Zhang, Wenyao; Zhu, Junwu; Wang, Xin

2014-11-01

A ternary manganese ferrite/graphene/polyaniline (MGP) nanostructure is designed and synthesized via a facile two-step approach. This nanostructure exhibits outstanding electrochemical performances, such as high specific capacitance (454.8 F g-1 at 0.2 A g-1), excellent rate capability (75.8% capacity retention at 5 A g-1), and good cycling stability (76.4% capacity retention after 5000 cycles at 2 A g-1), which are superior to those of its individual components (manganese ferrite, reduced-graphene oxide, polyaniline) and corresponding binary hybrids (manganese ferrite/graphene (MG), manganese ferrite/polyaniline (MP), and graphene/polyaniline (GP)). A symmetric supercapacitor device using the as-obtained hybrid has been fabricated and tested. The device exhibits a high specific capacitance of 307.2 F g-1 at 0.1 A g-1 with a maximum energy density of 13.5 W h kg-1. The high electrochemical performance of ternary MGP can be attributed to its well-designed nanostructure and the synergistic effect of the individual components.
Chemically activated manganese dioxide for dry batteries

NASA Astrophysics Data System (ADS)

Askar, M.; Abbas, H.

1994-10-01

The present investigation has enabled us to convert inactive beta-manganese dioxide to high electrochemically active types by chemical processes. Natural and chemically prepared beta-manganese dioxides were roasted at 1050 C to form Mn3O4. This compound was subjected to activation treatment using hydrochloric and sulfuric acid under various reaction conditions. The manganese dioxide so obtained was examined by x-ray diffraction, thermogravimetric, differential thermal, and chemical analyses. The structure of the dioxide obtained was found to be greatly dependent on the origin of MnO2 and type of acid used. Treatment with hydrochloric acid yielded the so-called gamma-variety while sulfuric acid tended to produce gamma- or alpha-MnO2. In addition, waste manganese sulfate obtained as by-product from sulfuric acid digestion treatment was recycled and electrolytically oxidized to gamma-MnO2. The discharge performance of the above-mentioned MnO2 samples as battery cathodic active material was evaluated and compared with the ordinary battery grade.
Anti-sigma factor YlaD regulates transcriptional activity of sigma factor YlaC and sporulation via manganese-dependent redox-sensing molecular switch in Bacillus subtilis.

PubMed

Kwak, Min-Kyu; Ryu, Han-Bong; Song, Sung-Hyun; Lee, Jin-Won; Kang, Sa-Ouk

2018-05-14

YlaD, a membrane-anchored anti-sigma factor of Bacillus subtilis , contains a HX 3 CXXC motif that functions as a redox-sensing domain and belongs to one of the zinc-coordinated anti-sigma factor families. Despite previously showing that the YlaC transcription is controlled by YlaD, experimental evidence of how the YlaC-YlaD interaction is affected by active cysteines and/or metal ions is lacking. Here, we showed that the P yla promoter is autoregulated solely by YlaC. Moreover, reduced YlaD contained zinc and iron, while oxidized YlaD did not. Cysteine substitution in YlaD led to changes in its secondary structure; Cys3 had important structural functions in YlaD, and its mutation caused dissociation from YlaC, indicating the essential requirement of a HX 3 CXXC motif for regulating interactions of YlaC with YlaD. Analyses of the far-UV CD spectrum and metal content revealed that the addition of Mn ions to Zn-YlaD changed its secondary structure and that iron was substituted for manganese. The ylaC gene expression using βGlu activity from P yla : gusA was observed at the late-exponential and early-stationary phase and the ylaC -overexpressing mutant constitutively expressed gene transcripts of clpP and sigH , an important alternative sigma factor regulated by ClpXP. Collectively, our data demonstrated that YlaD senses redox changes and elicits increase in manganese ion concentrations and that, in turn, YlaD-mediated transcriptional activity of YlaC regulates sporulation initiation under oxidative stress and manganese-substituted conditions by regulating clpP gene transcripts. This is the first report of the involvement of oxidative stress-responsive B. subtilis extracytoplasmic function sigma factors during sporulation via a manganese-dependent redox-sensing molecular switch. ©2018 The Author(s).
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.
Effective recycling of manganese oxide cathodes for lithium based batteries

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

Poyraz, Altug S.; Huang, Jianping; Cheng, Shaobo

Rechargeable lithium ion batteries (LIBs) occupy a prominent consumer presence due to their high cell potential and gravimetric energy density, there are also limited opportunities for electrode recycling. Currently used or proposed cathode recycling processes are multistep procedures which involve sequences of mechanical, thermal, and chemical leaching, where only the base material is recovered and significant processing is required to generate a recycled electrode structure. Another significant issue facing lithium based batteries is capacity fade due to structural degradation of the electroactive material upon extending cycling. Herein, inspired by heterogeneous catalyst thermal regeneration strategies, we present a new facile cathodemore » recycling process, where previously used cathodes are removed from a cell, heat treated, and then inserted into a new cell restoring the delivered capacity and cycle life. An environmentally sustainable manganese based material is employed, where binder-free self-supporting (BFSS) electrodes are prepared using a fibrous, high aspect ratio manganese oxide active material. After 200 discharge–charge cycles, the recycled BFSS electrodes display restored crystallinity and oxidation state of the manganese centers with the resulting electrochemistry (capacity and coulombic efficiency) reminiscent of freshly prepared BFSS cathodes. Of note, the BFSS electrode structure is robust with no degradation during the cell disassembly, electrode recovery, washing, and heat treatment steps; thus no post-processing is required for the recycled electrode. Furthermore, this work shows for the first time that a thermal regeneration method previously employed in catalyst systems can fully restore battery electrochemical performance, demonstrating a novel electrode recycling process which could open up new possibilities for energy storage devices with extended electrode lifecycles.« less
Effective recycling of manganese oxide cathodes for lithium based batteries

DOE PAGES

Poyraz, Altug S.; Huang, Jianping; Cheng, Shaobo; ...

2016-02-29

Rechargeable lithium ion batteries (LIBs) occupy a prominent consumer presence due to their high cell potential and gravimetric energy density, there are also limited opportunities for electrode recycling. Currently used or proposed cathode recycling processes are multistep procedures which involve sequences of mechanical, thermal, and chemical leaching, where only the base material is recovered and significant processing is required to generate a recycled electrode structure. Another significant issue facing lithium based batteries is capacity fade due to structural degradation of the electroactive material upon extending cycling. Herein, inspired by heterogeneous catalyst thermal regeneration strategies, we present a new facile cathodemore » recycling process, where previously used cathodes are removed from a cell, heat treated, and then inserted into a new cell restoring the delivered capacity and cycle life. An environmentally sustainable manganese based material is employed, where binder-free self-supporting (BFSS) electrodes are prepared using a fibrous, high aspect ratio manganese oxide active material. After 200 discharge–charge cycles, the recycled BFSS electrodes display restored crystallinity and oxidation state of the manganese centers with the resulting electrochemistry (capacity and coulombic efficiency) reminiscent of freshly prepared BFSS cathodes. Of note, the BFSS electrode structure is robust with no degradation during the cell disassembly, electrode recovery, washing, and heat treatment steps; thus no post-processing is required for the recycled electrode. Furthermore, this work shows for the first time that a thermal regeneration method previously employed in catalyst systems can fully restore battery electrochemical performance, demonstrating a novel electrode recycling process which could open up new possibilities for energy storage devices with extended electrode lifecycles.« less

Evaluation of Vacuum Blasting and Heat Guns as Methods for Abating Lead- Based Paint on Buildings

DTIC Science & Technology

1993-09-01

INCOMPATIBILITY - Contact with powerful oxidizing agents such as FLUORINE, CHLORINE TRIFLUORIDE , MANGANESE TRIOXIDE, OXYGEN DIFLUORIDE, MANGANESE...investigating new technologies for lead-based paint abatement. This research evaluates the effectiveness , safety, LEC1L•.T• and cost of vacuum abrasive...paint abatement. This research evaluates the effectiveness , safety, and cost of vacuum abrasive units and heat guns as methods of removing lead-based
REFRACTORY DIE FOR EXTRUDING URANIUM

DOEpatents

Creutz, E.C.

1959-08-11

A die is presented for the extrusion of metals, said die being formed of a refractory complex oxide having the composition M/sub n/O/sub m/R/sub x/O/sub y/ where M is magnesium, zinc, manganese, or iron, R is aluminum, chromic chromium, ferric iron, or manganic manganese, and m, n, x, and y are whole numbers. Specific examples are spinel, magnesium aluminate, magnetite, magnesioferrite, chromite, and franklinite.
Indirect Manganese Removal by Stenotrophomonas sp. and Lysinibacillus sp. Isolated from Brazilian Mine Water.

PubMed

Barboza, Natália Rocha; Amorim, Soraya Sander; Santos, Pricila Almeida; Reis, Flávia Donária; Cordeiro, Mônica Mendes; Guerra-Sá, Renata; Leão, Versiane Albis

2015-01-01

Manganese is a contaminant in the wastewaters produced by Brazilian mining operations, and the removal of the metal is notoriously difficult because of the high stability of the Mn(II) ion in aqueous solutions. To explore a biological approach for removing excessive amounts of aqueous Mn(II), we investigated the potential of Mn(II) oxidation by both consortium and bacterial isolates from a Brazilian manganese mine. A bacterial consortium was able to remove 99.7% of the Mn(II). A phylogenetic analysis of isolates demonstrated that the predominant microorganisms were members of Stenotrophomonas, Bacillus, and Lysinibacillus genera. Mn(II) removal rates between 58.5% and 70.9% were observed for Bacillus sp. and Stenotrophomonas sp. while the Lysinibacillus isolate 13P removes 82.7%. The catalytic oxidation of Mn(II) mediated by multicopper oxidase was not properly detected; however, in all of the experiments, a significant increase in the pH of the culture medium was detected. No aggregates inside the cells grown for a week were found by electronic microscopy. Nevertheless, an energy-dispersive X-ray spectroscopy of the isolates revealed the presence of manganese in Stenotrophomonas sp. and Lysinibacillus sp. grown in K medium. These results suggest that members of Stenotrophomonas and Lysinibacillus genera were able to remove Mn(II) by a nonenzymatic pathway.
Temperature Dependence Discontinuity in the Stability of Manganese doped Ceria Nanocrystals

DOE PAGES

Wu, Longjia; Dholabhai, Pratik; Uberuaga, Blas P.; ...

2017-01-05

CeO 2 has strong potential for chemical-looping water splitting. It has been shown that manganese doping decreases interface energies of CeO 2, allowing increased stability of high surface areas in this oxygen carrier oxide. The phenomenon is related to the segregation of Mn3+ at interfaces, which causes a measurable decrease in excess energy. Here in the present work, it is shown that, despite the stability of nanocrystals of manganese-doped CeO 2 with relation to undoped CeO 2, the effect is strongly dependent on the oxidation state of manganese, i.e., on the temperature. At temperatures below 800 °C, Mn is inmore » the 3+ valence state, and coarsening is hindered by the reduced interface energetics, showing smaller crystal sizes with increasing Mn content. At temperatures above 800 °C, Mn is reduced to its 2+ valence state, and coarsening is enhanced with increasing Mn content. Atomistic simulations show the segregation of Mn to grain boundaries is relatively insensitive to the charge state of the dopant. However, point defect modeling finds that the reduced state causes a decrease in cation vacancy concentration and an increase in cation interstitials, reducing drag forces for grain boundary mobility and increasing growth rates.« less
Assigning Oxidation States to Some Metal Dioxygen Complexes of Biological Interest.

ERIC Educational Resources Information Center

Summerville, David A.; And Others

1979-01-01

The bonding of dioxygen in metal-dioxygen complexes is discussed, paying particular attention to the problems encountered in assigning conventional oxidation numbers to both the metal center and coordinated dioxygen. Complexes of iron, cobalt, chromium, and manganese are considered. (BB)
Manganese complex-catalyzed oxidation and oxidative kinetic resolution of secondary alcohols by hydrogen peroxide† †Electronic supplementary information (ESI) available: Tables S1–S4 and additional data: NMR spectra of the products, GC and HPLC chromatograms in the OKR of secondary alcohols, key geometric information for DFT, etc. See DOI: 10.1039/c7sc00891k Click here for additional data file.

PubMed Central

Miao, Chengxia; Li, Xiao-Xi; Lee, Yong-Min; Xia, Chungu; Wang, Yong

2017-01-01

The highly efficient catalytic oxidation and oxidative kinetic resolution (OKR) of secondary alcohols has been achieved using a synthetic manganese catalyst with low loading and hydrogen peroxide as an environmentally benign oxidant in the presence of a small amount of sulfuric acid as an additive. The product yields were high (up to 93%) for alcohol oxidation and the enantioselectivity was excellent (>90% ee) for the OKR of secondary alcohols. Mechanistic studies revealed that alcohol oxidation occurs via hydrogen atom (H-atom) abstraction from an α-CH bond of the alcohol substrate and a two-electron process by an electrophilic Mn–oxo species. Density functional theory calculations revealed the difference in reaction energy barriers for H-atom abstraction from the α-CH bonds of R- and S-enantiomers by a chiral high-valent manganese–oxo complex, supporting the experimental result from the OKR of secondary alcohols. PMID:29163900
Identification of Manganese Superoxide Dismutase from Sphingobacterium sp. T2 as a Novel Bacterial Enzyme for Lignin Oxidation.

PubMed

Rashid, Goran M M; Taylor, Charles R; Liu, Yangqingxue; Zhang, Xiaoyang; Rea, Dean; Fülöp, Vilmos; Bugg, Timothy D H

2015-10-16

The valorization of aromatic heteropolymer lignin is an important unsolved problem in the development of a biomass-based biorefinery, for which novel high-activity biocatalysts are needed. Sequencing of the genomic DNA of lignin-degrading bacterial strain Sphingobacterium sp. T2 revealed no matches to known lignin-degrading genes. Proteomic matches for two manganese superoxide dismutase proteins were found in partially purified extracellular fractions. Recombinant MnSOD1 and MnSOD2 were both found to show high activity for oxidation of Organosolv and Kraft lignin, and lignin model compounds, generating multiple oxidation products. Structure determination revealed that the products result from aryl-Cα and Cα-Cβ bond oxidative cleavage and O-demethylation. The crystal structure of MnSOD1 was determined to 1.35 Å resolution, revealing a typical MnSOD homodimer harboring a five-coordinate trigonal bipyramidal Mn(II) center ligated by three His, one Asp, and a water/hydroxide in each active site. We propose that the lignin oxidation reactivity of these enzymes is due to the production of a hydroxyl radical, a highly reactive oxidant. This is the first demonstration that MnSOD is a microbial lignin-oxidizing enzyme.
Localized temperature and chemical reaction control in nanoscale space by nanowire array.

PubMed

Jin, C Yan; Li, Zhiyong; Williams, R Stanley; Lee, K-Cheol; Park, Inkyu

2011-11-09

We introduce a novel method for chemical reaction control with nanoscale spatial resolution based on localized heating by using a well-aligned nanowire array. Numerical and experimental analysis shows that each individual nanowire could be selectively and rapidly Joule heated for local and ultrafast temperature modulation in nanoscale space (e.g., maximum temperature gradient 2.2 K/nm at the nanowire edge; heating/cooling time < 2 μs). By taking advantage of this capability, several nanoscale chemical reactions such as polymer decomposition/cross-linking and direct and localized hydrothermal synthesis of metal oxide nanowires were demonstrated.
A comparison study of the start-up of a MnOx filter for catalytic oxidative removal of ammonium from groundwater and surface water.

PubMed

Cheng, Ya; Li, Ye; Huang, Tinglin; Sun, Yuankui; Shi, Xinxin; Shao, Yuezong

2018-03-01

As an efficient method for ammonium (NH 4 + ) removal, contact catalytic oxidation technology has drawn much attention recently, due to its good low temperature resistance and short start-up period. Two identical filters were employed to compare the process for ammonium removal during the start-up period for ammonium removal in groundwater (Filter-N) and surface water (Filter-S) treatment. Two types of source water (groundwater and surface water) were used as the feed waters for the filtration trials. Although the same initiating method was used, Filter-N exhibited much better ammonium removal performance than Filter-S. The differences in catalytic activity among these two filters were probed using X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and compositional analysis. XRD results indicated that different manganese oxide species were formed in Filter-N and Filter-S. Furthermore, the Mn3p XPS spectra taken on the surface of the filter films revealed that the average manganese valence of the inactive manganese oxide film collected from Filter-S (FS-MnO x ) was higher than in the film collected from Filter-N (FN-MnO x ). Mn(IV) was identified as the predominant oxidation state in FS-MnO x and Mn(III) was identified as the predominant oxidation state in FN-MnO x . The results of compositional analyses suggested that polyaluminum ferric chloride (PAFC) used during the surface water treatment was an important factor in the mineralogy and reactivity of MnO x . This study provides the theoretical basis for promoting the wide application of the technology and has great practical significance. Copyright © 2017. Published by Elsevier B.V.
Effect of the Mn oxidation state and lattice oxygen in Mn-based TiO2 catalysts on the low-temperature selective catalytic reduction of NO by NH3.

PubMed

Lee, Sang Moon; Park, Kwang Hee; Kim, Sung Su; Kwon, Dong Wook; Hong, Sung Chang

2012-09-01

TiO2-supported manganese oxide catalysts formed using different calcination temperatures were prepared by using the wet-impregnation method and were investigated for their activity in the low-temperature selective catalytic reduction (SCR) of NO by NH3 with respect to the Mn valence and lattice oxygen behavior. The surface and bulk properties of these catalysts were examined using Brunauer-Emmett-Teller (BET) surface area, X-ray diffraction (XRD), temperature-programmed reduction (TPR), and temperature-programmed desorption (TPD). Catalysts prepared using lower calcination temperatures, which contained Mn4+ displayed high SCR activity at low temperatures and possessed several acid sites and active oxygen. The TPD analysis determined that the Brönsted and Lewis acid sites in the Mn/TiO2 catalysts were important for the low-temperature SCR at 80-160 and 200-350 degrees C, respectively. In addition, the available lattice oxygen was important for attaining high NO to NO2 oxidation at low temperatures. Recently, various Mn catalysts have been evaluated as SCR catalysts. However, there have been no studies on the relationship of adsorption and desorption properties and behavior of lattice oxygen according to the valence state for manganese oxides (MnO(x)). Therefore, in this study, the catalysts were prepared by the wet-impregnation method at different calcination temperatures in order to show the difference of manganese oxidation state. These catalysts were then characterized using various physicochemical techniques, including BET, XRD, TPR, and TPD, to understand the structure, oxidation state, redox properties, and adsorption and desorption properties of the Mn/TiO2 catalysts.
Formation of Manganese Oxide Coatings onto Sand for Adsorption of Trace Metals from Groundwater.

PubMed

Tilak, A S; Ojewole, S; Williford, C W; Fox, G A; Sobecki, T M; Larson, S L

2013-11-01

Manganese oxide (MnO) occurs naturally in soil and has a high affinity for trace metals adsorption. In this work, we quantified the factors (pH; flow rate; use of oxidants such as bleach, HO, and O; initial Mn(II) concentrations; and two types of geologic media) affecting MnO coatings onto Ottawa and aquifer sand using batch and column experiments. The batch experiments consisted of manual and automated titration, and the column experiments mimicked natural MnO adsorption and oxidation cycles as a strategy for in situ adsorption. A Pb solution of 50 mg L was passed through MnO-coated sand at a flow rate of 4 mL min to determine its adsorption capacity. Batch experimental results showed that MnO coatings increased from pH 6 to 8, with maximum MnO coating occurring at pH 8. Regarding MnO coatings, bleach and O were highly effective compared with HO. The Ottawa sand had approximately twice the MnO coating of aquifer sand. The sequential increase in initial Mn(II) concentrations on both sands resulted in incremental buildup of MnO. The automated procedure enhanced MnO coatings by 3.5 times compared with manual batch experiments. Column results showed that MnO coatings were highly dependent on initial Mn(II) and oxidant concentrations, pH, flow rate, number of cycles (h), and the type of geologic media used. Manganese oxide coating exceeded 1700 mg kg for Ottawa sand and 130 mg kg for aquifer sand. The Pb adsorption exceeded 2200 mg kg for the Ottawa sand and 300 mg kg for the aquifer sand. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.
Spectroscopic characterization and reactivity studies of a mononuclear nonheme Mn(III)-hydroperoxo complex.

PubMed

So, Hee; Park, Young Jun; Cho, Kyung-Bin; Lee, Yong-Min; Seo, Mi Sook; Cho, Jaeheung; Sarangi, Ritimukta; Nam, Wonwoo

2014-09-03

We report the first example of a mononuclear nonheme manganese(III)-hydroperoxo complex derived from protonation of an isolated manganese(III)-peroxo complex bearing an N-tetramethylated cyclam (TMC) ligand, [Mn(III)(TMC)(OOH)](2+). The Mn(III)-hydroperoxo intermediate is characterized with various spectroscopic methods as well as with density functional theory (DFT) calculations, showing the binding of a hydroperoxide ligand in an end-on fashion. The Mn(III)-hydroperoxo species is a competent oxidant in oxygen atom transfer (OAT) reactions, such as the oxidation of sulfides. The electrophilic character of the Mn(III)-hydroperoxo complex is demonstrated unambiguously in the sulfoxidation of para-substituted thioanisoles.
Oxidation of iodide and iodine on birnessite (delta-MnO2) in the pH range 4-8.

PubMed

Allard, Sébastien; von Gunten, Urs; Sahli, Elisabeth; Nicolau, Rudy; Gallard, Hervé

2009-08-01

The oxidation of iodide by synthetic birnessite (delta-MnO(2)) was studied in perchlorate media in the pH range 4-8. Iodine (I(2)) was detected as an oxidation product that was subsequently further oxidized to iodate (IO(3)(-)). The third order rate constants, second order on iodide and first order on manganese oxide, determined by extraction of iodine in benzene decreased with increasing pH (6.3-7.5) from 1790 to 3.1M(-2) s(-1). Both iodine and iodate were found to adsorb significantly on birnessite with an adsorption capacity of 12.7 microM/g for iodate at pH 5.7. The rate of iodine oxidation by birnessite decreased with increasing ionic strength, which resulted in a lower rate of iodate formation. The production of iodine in iodide-containing waters in contact with manganese oxides may result in the formation of undesired iodinated organic compounds (taste and odor, toxicity) in natural and technical systems. The probability of the formation of such compounds is highest in the pH range 5-7.5. For pH <5 iodine is quickly oxidized to iodate, a non-toxic and stable sink for iodine. At pH >7.5, iodide is not oxidized to a significant extent.
Transformation of Cerium Oxide Nanoparticles from a Diesel Fuel Additive during Combustion in a Diesel Engine.

PubMed

Dale, James G; Cox, Steven S; Vance, Marina E; Marr, Linsey C; Hochella, Michael F

2017-02-21

Nanoscale cerium oxide is used as a diesel fuel additive to reduce particulate matter emissions and increase fuel economy, but its fate in the environment has not been established. Cerium oxide released as a result of the combustion of diesel fuel containing the additive Envirox, which utilizes suspended nanoscale cerium oxide to reduce particulate matter emissions and increase fuel economy, was captured from the exhaust stream of a diesel engine and was characterized using a combination of bulk analytical techniques and high resolution transmission electron microscopy. The combustion process induced significant changes in the size and morphology of the particles; ∼15 nm aggregates consisting of 5-7 nm faceted crystals in the fuel additive became 50-300 nm, near-spherical, single crystals in the exhaust. Electron diffraction identified the original cerium oxide particles as cerium(IV) oxide (CeO 2 , standard FCC structure) with no detectable quantities of Ce(III), whereas in the exhaust the ceria particles had additional electron diffraction reflections indicative of a CeO 2 superstructure containing ordered oxygen vacancies. The surfactant coating present on the cerium oxide particles in the additive was lost during combustion, but in roughly 30% of the observed particles in the exhaust, a new surface coating formed, approximately 2-5 nm thick. The results of this study suggest that pristine, laboratory-produced, nanoscale cerium oxide is not a good substitute for the cerium oxide released from fuel-borne catalyst applications and that future toxicity experiments and modeling will require the use/consideration of more realistic materials.
Nanostructured manganese oxide/carbon nanotubes, graphene and graphene oxide as water-oxidizing composites in artificial photosynthesis.

PubMed

Najafpour, Mohammad Mahdi; Rahimi, Fahime; Fathollahzadeh, Maryam; Haghighi, Behzad; Hołyńska, Małgorzata; Tomo, Tatsuya; Allakhverdiev, Suleyman I

2014-07-28

Herein, we report on nano-sized Mn oxide/carbon nanotubes, graphene and graphene oxide as water-oxidizing compounds in artificial photosynthesis. The composites are synthesized by different and simple procedures and characterized by a number of methods. The water-oxidizing activities of these composites are also considered in the presence of cerium(IV) ammonium nitrate. Some composites are efficient Mn-based catalysts with TOF (mmol O2 per mol Mn per second) ~ 2.6.
Manganese micro-nodules on ancient brick walls.

PubMed

López-Arce, P; García-Guinea, J; Fierro, J L G

2003-01-20

Romans, Jews, Arabs and Christians built the ancient city of Toledo (Spain) with bricks as the main construction material. Manganese micro-nodules (circa 2 microm in diameter) have grown under the external bio-film surface of the bricks. Recent anthropogenic activities such as industrial emissions, foundries, or traffic and housing pollution have further altered these old bricks. The energy-dispersive X-ray microanalyses (XPS) of micro-nodules show Al, Si, Ca, K, Fe and Mn, with some carbon species. Manganese atoms are present only as Mn(4+) and iron as Fe(3+) (FeOOH-Fe(2)O(3) mixtures). The large concentration of alga biomass of the River Tagus and the Torcón and Guajaraz reservoirs suggest manganese micro-nodules are formed either from water solutions rich in anthropogenic MnO(4)K in a reduction environment (from Mn(7+) to Mn(4+)) or by oxidation mechanisms from dissolved Mn(2+) (from Mn(2+) to Mn(4+)) linked to algae biofilm onto the ancient brick surfaces. Ancient wall surfaces were also studied by scanning electron microscopy (SEM-EDS) and X-ray diffraction (XRD). Chemical and biological analyses of the waters around Toledo are also analysed for possible sources of manganese. Manganese micro-nodules on ancient brick walls are good indicators of manganese pollution. Copyright 2002 Elsevier Science B.V.
Exploring Lithium-Cobalt-Nickel Oxide Spinel Electrodes for ≥3.5 V Li-Ion Cells

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

Lee, Eungje; Blauwkamp, Joel; Castro, Fernando C.

2016-10-19

Recent reports have indicated that a manganese oxide spinel component, when embedded in a relatively small concentration in layered xLi2MnO3(1-x)LiMO2 (M=Ni, Mn, Co) electrode systems, can act as a stabilizer that increases their capacity, rate capability, cycle life, and first-cycle efficiency. These findings prompted us to explore the possibility of exploiting lithiated cobalt oxide spinel stabilizers by taking advantage of (1) the low mobility of cobalt ions relative to manganese and nickel ions in close-packed oxides and (2) their higher potential (~3.6 V vs. Li0) relative to manganese oxide spinels (~2.9 V vs. Li0) for the spinel-to-lithiated spinel electrochemical reaction.more » In particular, we have revisited the structural and electrochemical properties of lithiated spinels in the LiCo1-xNixO2 (0x0.2) system, first reported almost 25 years ago, by means of high-resolution (synchrotron) X-ray diffraction, transmission electron microscopy, nuclear magnetic resonance spectroscopy, electrochemical cell tests, and theoretical calculations. The results provide a deeper understanding of the complexity of intergrown layered/lithiated spinel LiCo1-xNixO2 structures, when prepared in air between 400 and 800 C, and the impact of structural variations on their electrochemical behavior. These structures, when used in low concentration, offer the possibility of improving the cycling stability, energy, and power of high energy (≥3.5 V) lithium-ion cells.« less
Effects of manganese oxide-modified biochar composites on arsenic speciation and accumulation in an indica rice (Oryza sativa L.) cultivar.

PubMed

Yu, Zhihong; Qiu, Weiwen; Wang, Fei; Lei, Ming; Wang, Di; Song, Zhengguo

2017-02-01

A pot experiment was used to investigate arsenic (As) speciation and accumulation in rice, as well as its concentration in both heavily contaminated and moderately contaminated soils amended with manganese oxide-modified biochar composites (MBC) and biochar alone (BC). In heavily As-contaminated soil, application of BC and MBC improved the weight of above-ground part and rice root, whereas in moderately As-contaminated soil, the application of MBC and low rate BC amendment increased rice root, grain weight and the biomass of the plant. Arsenic reduction in different parts of rice grown in MBC-amended soils was greater than that in plants cultivated in BC-amended soils. Such reduction can be attributed to the oxidation of arsenite, As(III), to arsenate, As(V), by Mn-oxides, which also had a strong adsorptive capacity for As(V). MBC amended to As-contaminated soil had a positive effect on amino acids. The Fe and Mn levels in the iron-manganese plaque that formed on the rice root surface differed among the treatments. MBC addition significantly increased Mn content (p < 0.05); the application of 2.0% MBC increased Mn content 36- and 10-fold compared to the control in heavily and moderately As-contaminated soils, respectively. The results indicate that application of Mn oxide-modified biochar to As-contaminated paddy soil could effectively remediate contaminated soil and reduce As accumulation in edible parts of rice. Copyright © 2016 Elsevier Ltd. All rights reserved.
EXAFS and XANES analysis of oxides at the nanoscale.

PubMed

Kuzmin, Alexei; Chaboy, Jesús

2014-11-01

Worldwide research activity at the nanoscale is triggering the appearance of new, and frequently surprising, materials properties in which the increasing importance of surface and interface effects plays a fundamental role. This opens further possibilities in the development of new multifunctional materials with tuned physical properties that do not arise together at the bulk scale. Unfortunately, the standard methods currently available for solving the atomic structure of bulk crystals fail for nanomaterials due to nanoscale effects (very small crystallite sizes, large surface-to-volume ratio, near-surface relaxation, local lattice distortions etc.). As a consequence, a critical reexamination of the available local-structure characterization methods is needed. This work discusses the real possibilities and limits of X-ray absorption spectroscopy (XAS) analysis at the nanoscale. To this end, the present state of the art for the interpretation of extended X-ray absorption fine structure (EXAFS) is described, including an advanced approach based on the use of classical molecular dynamics and its application to nickel oxide nanoparticles. The limits and possibilities of X-ray absorption near-edge spectroscopy (XANES) to determine several effects associated with the nanocrystalline nature of materials are discussed in connection with the development of ZnO-based dilute magnetic semiconductors (DMSs) and iron oxide nanoparticles.
Magnetic iron oxide and manganese-doped iron oxide nanoparticles for the collection of alpha-emitting radionuclides from aqueous solutions

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

O'Hara, Matthew J.; Carter, Jennifer C.; Warner, Cynthia L.

Magnetic nanoparticles are well known to possess chemically active surfaces and high surface areas that can be employed to extract a range of ions from aqueous solutions. Additionally, their paramagnetic property provides a convenient means for bulk collection of the material from solution after the targeted ions have been adsorbed. Herein, two nanoscale amphoteric metal oxides, each possessing useful magnetic attributes, were evaluated for their ability to collect both naturally occurring radioactive isotopes (polonium (Po), radium (Ra), and uranium (U)) as well as the transuranic element americium (Am) from a suite of naturally occurring aqueous matrices. The nanomaterials include commerciallymore » available paramagnetic magnetite (Fe3O4) and magnetite that was modified to incorporate manganese (Mn) into the crystal structure. The chemical stability of these nanomaterials was evaluated in Hanford Site, WA ground water between the natural pH (~8) and pH 1 (acidified with HCl). Whereas the magnetite was observed to have good stability over the pH range, the Mn-doped material was observed to leach Mn at low pH. The materials were evaluated in parallel to characterize their uptake performance of the aforementioned alpha-emitting radionuclide spikes from Hanford Site ground water across a range of pH (from ~8 down to 2). In addition, radiotracer uptake experiments were performed on Columbia River water, seawater, and human urine at their natural pH and at pH 2. Despite the observed leaching of Mn from the Mn-doped nanomaterial in the lower pH range, it exhibited generally superior analyte extraction performance compared to the magnetite, and analyte uptake was observed across a broader pH range. The uptake behavior of the various radiotracers on these two materials at different pH levels can generally be explained by the amphoteric nature of the nanoparticle surfaces. Finally, the rate of sorption of the radiotracers on the two materials in unacidified groundwater was evaluated. The uptake curves generally indicate that equilibrium is obtained within a few minutes, which is attributed to the high surface areas of the nanomaterials and the high level of dispersion in the liquids. Overall, the results indicate that these nanomaterials may have the potential to be employed for a range of applications to extract radionuclides from aqueous solutions. These applications may include analytical chemistry, waste water treatment and remediation, mining, and in vitro radiobioassay.« less

Cyano- and polycyanometallo-porphyrins as catalysts for alkane oxidation

DOEpatents

Ellis, P.E. Jr.; Lyons, J.E.

1995-01-17

New compositions of matter comprising cyano-substituted metal complexes of porphyrins are catalysts for the oxidation of alkanes. The metal is iron, chromium, manganese, ruthenium, copper or cobalt. The porphyrin ring has cyano groups attached thereto in meso and/or [beta]-pyrrolic positions.
Cyano- and polycyanometallo-porphyrins as catalysts for alkane oxidation

DOEpatents

Ellis, P.E. Jr.; Lyons, J.E.

1993-05-18

New compositions of matter comprising cyano-substituted metal complexes of porphyrins are catalysts for the oxidation of alkanes. The metal is iron, chromium, manganese, ruthenium, copper or cobalt. The porphyrin ring has cyano groups attached thereto in meso- and/or [beta]-pyrrolic positions.
Cyano- and polycyanometallo-porphyrins as catalysts for alkane oxidation

DOEpatents

Ellis, Jr., Paul E.; Lyons, James E.

1993-01-01

New compositions of matter comprising cyano-substituted metal complexes of porphyrins are catalysts for the oxidation of alkanes. The metal is iron, chromium, manganese, ruthenium, copper or cobalt. The porphyrin ring has cyano groups attached thereto in meso and/or .beta.-pyrrolic positions.
Cyano- and polycyanometallo-porphyrins as catalysts for alkane oxidation

DOEpatents

Ellis, Jr., Paul E.; Lyons, James E.

1995-01-01

New compositions of matter comprising cyano-substituted metal complexes of porphyrins are catalysts for the oxidation of alkanes. The metal is iron, chromium, manganese, ruthenium, copper or cobalt. The porphyrin ring has cyano groups attached thereto in meso and/or .beta.-pyrrolic positions.
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 oxidizing fungi.
Microbial Manganese and Sulfate Reduction in Black Sea Shelf Sediments

PubMed Central

Thamdrup, Bo; Rosselló-Mora, Ramón; Amann, Rudolf

2000-01-01

The microbial ecology of anaerobic carbon oxidation processes was investigated in Black Sea shelf sediments from mid-shelf with well-oxygenated bottom water to the oxic-anoxic chemocline at the shelf-break. At all stations, organic carbon (Corg) oxidation rates were rapidly attenuated with depth in anoxically incubated sediment. Dissimilatory Mn reduction was the most important terminal electron-accepting process in the active surface layer to a depth of ∼1 cm, while SO42− reduction accounted for the entire Corg oxidation below. Manganese reduction was supported by moderately high Mn oxide concentrations. A contribution from microbial Fe reduction could not be discerned, and the process was not stimulated by addition of ferrihydrite. Manganese reduction resulted in carbonate precipitation, which complicated the quantification of Corg oxidation rates. The relative contribution of Mn reduction to Corg oxidation in the anaerobic incubations was 25 to 73% at the stations with oxic bottom water. In situ, where Mn reduction must compete with oxygen respiration, the contribution of the process will vary in response to fluctuations in bottom water oxygen concentrations. Total bacterial numbers as well as the detection frequency of bacteria with fluorescent in situ hybridization scaled to the mineralization rates. Most-probable-number enumerations yielded up to 105 cells of acetate-oxidizing Mn-reducing bacteria (MnRB) cm−3, while counts of Fe reducers were <102 cm−3. At two stations, organisms affiliated with Arcobacter were the only types identified from 16S rRNA clone libraries from the highest positive MPN dilutions for MnRB. At the third station, a clone type affiliated with Pelobacter was also observed. Our results delineate a niche for dissimilatory Mn-reducing bacteria in sediments with Mn oxide concentrations greater than ∼10 μmol cm−3 and indicate that bacteria that are specialized in Mn reduction, rather than known Mn and Fe reducers, are important in this niche. PMID:10877783
Accumulation of iron and arsenic in the Chandina alluvium of the lower delta plain, Southeastern Bangladesh

USGS Publications Warehouse

Zahid, A.; Hassan, M.Q.; Breit, G.N.; Balke, K.-D.; Flegr, M.

2009-01-01

Accumulations of iron, manganese, and arsenic occur in the Chandina alluvium of southeastern Bangladesh within 2.5 m of the ground surface. These distinctive orange-brown horizons are subhorizontal and consistently occur within 1 m of the contact of the aerated (yellow-brown) and water-saturated (gray) sediment. Ferric oxyhydroxide precipitates that define the horizons form by oxidation of reduced iron in pore waters near the top of the saturated zone when exposed to air in the unsaturated sediment. Hydrous Fe-oxide has a high specific surface area and thus a high adsorption capacity that absorbs the bulk of arsenic also present in the reduced pore water, resulting in accumulations containing as much as 280 ppm arsenic. The steep redox gradient that characterizes the transition of saturated and unsaturated sediment also favors accumulation of manganese oxides in the oxidized sediment. Anomalous concentrations of phosphate and molybdenum also detected in the ferric oxyhydroxide-enriched sediment are attributed to sorption processes. ?? Springer Science+Business Media B.V. 2008.
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
Timing the oxidation of Earth's crust: Evidence from big data records of manganese mineralization

NASA Astrophysics Data System (ADS)

Hummer, D. R.; Golden, J. J.; Hystad, G.; Downs, R. T.; Eleish, A.; Liu, C.; Ralph, J.; Morrison, S.; Meyer, M.; Hazen, R. M.

2017-12-01

A great deal of work has focused on unravelling the oxygenation of Earth's early atmosphere and oceans, which took place during and after the Great Oxidation Event (1). Recently, field and experimental methods have also been used to examine the timing of mantle oxidation, especially near subduction zones (2). However, very little information is available on the timing of crustal oxidation. To examine the oxidation of Earth's shallow crust, we analyzed records of manganese (Mn) mineral occurrences across geologic time from a database of 2666 mineral-locality data pairs (mindat.org as of 20 Nov. 2015) that had associated geologic ages in the literature. Manganese is a redox-sensitive transition element with oxidation states of +2, +3, and +4, whose average oxidation state in the geologic record can be used as a proxy for the oxygenation of the shallow crust, where Mn mineralization typically occurs. Analysis revealed that Mn mineralization older than 600 Ma contained mostly Mn2+ mineral species, with isolated localities containing Mn3+ and Mn4+ species. During the Phanerozoic, the average oxidation state of Mn follows the same trend as reconstructions of atmospheric oxygen (3), but on a 66+1 Myr delay (as calculated using a least squares fitting procedure). This contrasts with a delay of hundreds of millions of years for the oxidation of molybdenum, which forms much deeper in the crust (4). We interpret these time lags as the time necessary to equilibrate various crustal depths to atmospheric oxygen fugacity through infiltration of oxidizing fluids and tectonic mixing processes. Analysis of other redox-sensitive transition metals (such as Cr, V, and Fe) using big data techniques may reveal a strategy for timing the oxidation of different portions of Earth's crust. (1) T.W. Lyons, C.T. Reinhard, N.J. Planavsky, Nature 506, 307-315 (2014). (2) M. Brounce, et al. Geology 43, 775-778 (2015). (3) N.M. Bergman, T.M. Lenton, A.J. Watson, Am. J. Sci. 304, 397-437 (2004). (4) J.J. Golden, et al. EPSL 366, 1-5 (2013).
Biogeochemical Gradients in Wetland Sediments and their Effect on the Fate Trace Metals

NASA Astrophysics Data System (ADS)

Jaffe, P. R.; Choi, J.; Xu, S.

2005-12-01

The interactions between sediment biogeochemistry processes and higher plants play a major role on trace metal mobility in wetlands. Most wetland sediments are characterized by steep redox gradients, resulting from the sequential utilization of different electron acceptors during the degradation of organic matter provided by leaf litter and root turnover. Metals in wetland sediments may be immobilized due to precipitation or adsorption to different organic and inorganic sediment constituents. Adsorption onto iron, and manganese oxides, are important in the rhizosphere where iron oxyhydroxide plaques may form on the surface of roots. As the sediments becomes more reduced, bioavailable iron and manganese oxides are used as electron acceptor and are gradually depleted, resulting in the mobilization of some adsorbed species (i.e., As(V), phosphate, etc.), the reduction of some trace metals such as Cr(VI) (which is then immobilized as Cr(III)), and for more reduced conditions the immobilization of trace metals (i.e., Cd, Pb, Zn) as sulfides. Results from numerical simulations, laboratory experiments, and field measurements will be presented, showing how redox gradients and hence, trace-metal immobilization, in wetlands respond to external forcing functions such as changes in nutrient loading, plant distribution, seasonal and diurnal plant activity (specifically evapotranspiration and oxygen release), and temporal or spatial changes in the profile of iron and manganese oxides.
Mechanisms and chemistry of dye adsorption on manganese oxides-modified diatomite.

PubMed

Al-Ghouti, Mohammad A; Al-Degs, Yehya S; Khraisheh, Majeda A M; Ahmad, Mohammad N; Allen, Stephen J

2009-08-01

The investigations into structural changes which occur during adsorbent modification and the adsorption mechanisms are essential for an effective design of adsorption systems. Manganese oxides were impregnated onto diatomite to form the type known as delta-birnessite. Initial investigations established the effectiveness of manganese oxides-modified diatomite (MOMD) to remove basic and reactive dyes from aqueous solution. The adsorption capacity of MOMD for methylene blue (MB), hydrolysed reactive black (RB) and hydrolysed reactive yellow (RY) was 320, 419, and 204mg/g, respectively. Various analytical techniques were used to characterise the structure and the mechanisms of the dye adsorption process onto MOMD such as Fourier transform infrared (FTIR), X-ray diffraction (XRD) and atomic absorption spectrometry (A.A.). A small shift to higher values of the d-spacing of dye/MOMD was observed indicating that a small amount of the dye molecules were intercalated in the MOMD structure and other molecules were adsorbed on the external surface of MOMD. Two mechanisms of dye adsorption onto MOMD were proposed; intercalation of the dye in the octahedral layers and adsorption of the dye on the MOMD external surface. Moreover, the results demonstrated that the MOMD structure was changed upon insertion of MB and RY with an obvious decrease in the intensity of the second main peak of the MOMD X-ray pattern.
Post-test characterization of a solid oxide fuel cell stack operated for more than 30,000 hours: The cell

NASA Astrophysics Data System (ADS)

Menzler, Norbert H.; Sebold, Doris; Guillon, Olivier

2018-01-01

A four-layer solid oxide fuel cell stack with planar anode-supported cells was operated galvanostatically at 700 °C and 0.5Acm-2 for nearly 35,000 h. One of the four planes started to degrade more rapidly after ∼28,000 h and finally more progressively after ∼33,000 h. The stack was then shut down and a post-test analysis was carefully performed. The cell was characterized with respect to cathodic impurities and clarification of the reason(s) for failure. Wet chemical analysis revealed very low chromium incorporation into the cathode. However, SEM and TEM observations on polished and fractured surfaces showed catastrophic failure in the degraded layer. The cathode-barrier-electrolyte cell layer system delaminated from the entire cell over large areas. The source of delamination was the formation of a porous, sponge-like secondary phase consisting of zirconia, yttria and manganese (oxide). Large secondary phase islands grew from the electrolyte-anode interface towards the anode and cracked the bonding between both layers. The manganese originated from the contact or protection layers used on the air side. This stack result shows that volatile species - in this case manganese - should be avoided, especially when long-term applications are envisaged.
Submarine basalt from the Revillagigedo Islands region, Mexico

USGS Publications Warehouse

Moore, J.G.

1970-01-01

Ocean-floor dredging and submarine photography in the Revillagigedo region off the west coast of Mexico reveal that the dominant exposed rock of the submarine part of the large island-forming volcanoes (Roca Partida and San Benedicto) is a uniform alkali pillow basalt; more siliceous rocks are exposed on the upper, subaerial parts of the volcanoes. Basalts dredged from smaller seamounts along the Clarion fracture zone south of the Revillagigedo Islands are tholeiitic pillow basalts. Pillows of alkali basalts are more vesicular than Hawaiian tholeiitic pillows collected from the same depths. This difference probably reflects a higher original volatile content of the alkali basalts. Manganese-iron oxide nodules common in several dredge hauls generally contain nucleii of rhyolitic pumice or basalt pillow fragments. The pumice floated to its present site from subaerial eruptions, became waterlogged and sank, and was then coated with manganese-iron oxides. The thickness of palagonite rinds on the glassy pillow fragments is proportional to the thickness of manganese-iron oxide layers, and both are a measure of the age of the nodule. Both oldest basalts (10-100 m.y.) and youngest (less than 1 m.y.) are along the Clarion fracture zone, whereas basalts from Roca Partida and San Benedicto volcanoes are of intermediate age. ?? 1970.
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. Copyright © 2016 Elsevier Ltd. All rights reserved.
Preparation and evaluation of aminopropyl-functionalized manganese-loaded SBA-15 for copper removal from aqueous solution.

PubMed

Lei, Di; Zheng, Qianwen; Wang, Yili; Wang, Hongjie

2015-02-01

A novel material, aminopropyl-functionalized manganese-loaded SBA-15 (NH2-Mn-SBA-15), was synthesized by bonding 3-aminopropyl trimethoxysilane (APTMS) onto manganese-loaded SBA-15 (Mn-SBA-15) and used as a Cu2+ adsorbent in aqueous solution. Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction spectra (XRD), N2 adsorption/desorption isotherms, high resolution field emission scanning electron microscopy (FESEM) and X-ray photoelectron spectroscopy (XPS) were used to characterize the NH2-Mn-SBA-15. The ordered mesoporous structure of SBA-15 was remained after modification. The manganese oxides were mainly loaded on the internal surface of the pore channels while the aminopropyl groups were mainly anchored on the external surface of SBA-15. The adsorption of Cu2+ on NH2-Mn-SBA-15 was fitted well by the Langmuir equation and the maximum adsorption capacity of NH2-Mn-SBA-15 for Cu2+ was over two times higher than that of Mn-SBA-15 under the same conditions. The Elovich equation gave a good fit for the adsorption process of Cu2+ by NH2-Mn-SBA-15 and Mn-SBA-15. Both the loaded manganese oxides and the anchored aminopropyl groups were found to contribute to the uptake of Cu2+. The NH2-Mn-SBA-15 showed high selectivity for copper ions. Consecutive adsorption-desorption experiments showed that the NH2-Mn-SBA-15 could be regenerated by acid treatment without altering its properties. Copyright © 2014. Published by Elsevier B.V.
Microbial Nitrogen Cycling Associated with the Early Diagenesis of Organic Matter in Subseafloor Sediments

NASA Astrophysics Data System (ADS)

Zhao, R.

2015-12-01

The early diagenesis of organic matter is the major energy source of marine sedimentary biosphere and thus controls its population size; however, the vertical distribution of any functional groups along with the diagenesis of organic matter is remained unclear, especially for those microbes involved in nitrogen transformation which serve as a major control on the nitrogen flux between reservoirs. Here we investigated the vertical distributions of various functional groups in five sediment cores retrieved from Arctic Mid-Ocean Ridge (AMOR), with emphasis on the nitrifiers, denitrifiers and anaerobic ammonium oxidizing bacteria (anammox). We observed the clear geochemical zonation associated with organic matter diagenesis in the sediments based on the pore water profiles of oxygen, nitrate, ammonium, manganese and sulfate, with distinct geochemical transition zones at the boundaries of geochemical zones, including oxic-anoxic transition zone (OATZ) and nitrate-manganese reduction zone (NMTZ). Nitrate was produced in surface oxygenated sediments and nitrate consumption mainly took place at the NMTZ, splitted between re-oxidation of ammonium and manganese (II). Abundances of ammonia oxidizers, nitrite oxidizers, and denitrifiers, estimated through quantitative PCR targeting their respective functional genes, generally decrease with depth, but constantly elevated around the OATZ, NMTZ, and manganese-reduction zone as well. Anammox bacteria were only detected around the NMTZ where both nitrate/nitrite and ammonium are available. These depth profiles of functional groups were also confirmed by the community structure profiling by prokaryotic 16S rRNA gene tag pyrosequencing. Cell-specific rates of nitrification and denitrification, calculated from the bulk net reaction rates divided by functional group abundances, were similar to those values from oligotrophic sediments like North Pond and thus suggested that nitrifiers and denitirifiers populations were in maintenance state. This study illustrated the microbial nitrogen transformation accompanying the early diagenesis of organic matter in marine sediments, which scenario might be occurring in a wide range of stratified environments on Earth.
Mineralogy and autoradiography of selected mineral-spring precipitates in the Western United States

USGS Publications Warehouse

Bove, Dana; Felmlee, J.K.

1982-01-01

X-ray diffaction analysis of 236 precipitate or sediment samples from 97 mineral-spring sites in nine Western States showed the presence of 25 minerals, some precipitated and some detrital. Calcite and (or) aragonite are the most common of all the precipitated minerals. Gypsum and (or) anhydrite, as well as barite and native sulfur, are less common but are also believed to be precipitated minerals. Precipitated manganese and iron oxides, including romanechite, manganite, pyrolusite, goethite, and hematite, were found in some of the samples. Various salts of sodium, including halite and thenardite, were also identified. Dolomite and an unknown type of siliceous material are present in some of the samples and were possibly precipitated at the spring sites. Quartz, feldspar, and mica are present in many of the samples and are believed to be detrital contaminants. An autoradiographic and thin section study of 11 samples from nine of the most radioactive spring sites showed the radioactivity, which is due primarily to radium, to be directly associated with mineral phases containing barium, manganese, iron, and (or) calcium as major constituents. Furthermore, the radioactivity has an exclusive affinity for the manganese-bearing minerals, which in these samples contain a substantial amount of barium, even if calcite or iron oxides are present. Where calcite predominates and manganese- and barium-bearing minerals are absent, the radioactivity shows a close association with the iron oxides present, especially hematite, but also shows a moderate association with the calcite and (or) aragonite cementing phases. In other samples composed predominantly of calcite but lacking iron oxides, the radioactivity is preferentially associated with an early stage of calcite development and is considerably lower in the later cementing stages. The radioactivity observed in all these samples is believed to be caused by radium substituting for barium in mineral lattices, filling irregularities in other crystal structures, or adsorbing on the surfaces of precipitated molecules.
Oxidation Catalysts in the Dark and the Light

DTIC Science & Technology

2010-01-01

TiO2 with added silver, chromium, vanadium, manganese, carbon, and/or sulfur (selected transition metal ions and selected non- metals ) are very...Ranjit, Koodali T.; Klabunde, Kenneth J.; “ Catalysis by Metal Oxides,” Surface and Nanomolecular Catalysis , ed. Ryan Richards, CRC Press, NY, Ch. 2, pgs...REPORT Oxidation Catalysts in the Dark and the Light--Final Report 14. ABSTRACT 16. SECURITY CLASSIFICATION OF: Extensive research on mixed metal oxide
Effect of Nanoparticles on Complement System in Cell Culture Model

DTIC Science & Technology

2006-09-15

case complement activation considerably differs between nanoparticles , being the highest in case of fullerene, ferric oxide and aluminium oxide ... oxide (CdO; 1 µm), manganese oxide (MnO2; 1-2 µm), and tungsten (W; 27 µm) were assessed. Additionally the effects of nanoparticles coated with...using in vitro system. Obtained results indicate that: 1. Nanoparticles toxicity in vitro can’t be measured using methods which were designed
Effect of drinking water treatment process parameters on biological removal of manganese from surface water.

PubMed

Hoyland, Victoria W; Knocke, William R; Falkinham, Joseph O; Pruden, Amy; Singh, Gargi

2014-12-01

Soluble manganese (Mn) presents a significant treatment challenge to many water utilities, causing aesthetic and operational concerns. While application of free chlorine to oxidize Mn prior to filtration can be effective, this is not feasible for surface water treatment plants using ozonation followed by biofiltration because it inhibits biological removal of organics. Manganese-oxidizing bacteria (MOB) readily oxidize Mn in groundwater treatment applications, which normally involve pH > 7.0. The purpose of this study was to evaluate the potential for biological Mn removal at the lower pH conditions (6.2-6.3) often employed in enhanced coagulation to optimize organics removal. Four laboratory-scale biofilters were operated over a pH range of 6.3-7.3. The biofilters were able to oxidize Mn at a pH as low as pH 6.3 with greater than 98% Mn removal. Removal of simulated organic ozonation by-products was also greater than 90% in all columns. Stress studies indicated that well-acclimated MOB can withstand variations in Mn concentration (e.g., 0.1-0.2 mg/L), hydraulic loading rate (e.g., 2-4 gpm/ft(2); 1.36 × 10(-3)-2.72 × 10(-3) m/s), and temperature (e.g., 7-22 °C) typically found at surface water treatment plants at least for relatively short (1-2 days) periods of time. Copyright © 2014 Elsevier Ltd. All rights reserved.

[Lead adsorption and arsenite oxidation by cobalt doped birnessite].

PubMed

Yin, Hui; Feng, Xiong-Han; Qiu, Guo-Hong; Tan, Wen-Feng; Liu, Fan

2011-07-01

In order to study the effects of transition metal ions on the physic-chemical properties of manganese dioxides as environmental friendly materials, three-dimensional nano-microsphere cobalt-doped birnessite was synthesized by reduction of potassium permanganate by mixtures of concentrated hydrochloride and cobalt (II) chloride. Powder X-ray diffraction, chemical analysis, N2 physical adsorption, field emission scanning electron microscopy (FE-SEM) and X-ray photoelectron spectra (XPS) were used to characterize the crystal structure, chemical composition and micro-morphologies of products. In the range of molar ratios from 0.05 to 0.20, birnessite was fabricated exclusively. It was observed that cobalt incorporated into the layers of birnessite and had little effect on the crystal structure and micromorpholgy, but crystallinity decreased after cobalt doping. Both chemical analysis and XPS results showed that manganese average oxidation state decreased after cobalt doping, and the percentage of Mn3+ increased. Co(III) OOH existed mainly in the structure. With the increase of cobalt, hydroxide oxygen percentage in molar increased from 12.79% for undoped birnessite to 13.05%, 17.69% and 17.79% for doped samples respectively. Adsorption capacity for lead and oxidation of arsenite of birnessite were enhanced by cobalt doping. The maximum capacity of Pb2+ adsorption increased in the order HB (2 538 mmol/kg) < CoB5 (2798 mmol/kg) < CoB10 (2932 mmol/kg) < CoB20 (3 146 mmol/kg). Oxidation percentage of arsenite in simulated waste water by undoped birnessite was 76.5%, those of doped ones increased by 2.0%, 12.8% and 18.9% respectively. Partial of Co3+ substitution for Mn4+ results in the increase of negative charge of the layer and the content of hydroxyl group, which could account for the improved adsorption capacity of Pb2+. After substitution of manganese by cobalt, oxidation capacity of arsenite by birnessite increases likely due to the higher standard redox potential of Co3+/Co2+ than those of Mn4+/Mn3+/Mn2+. Therefore, Co-doped birnessite is more applicable for the remediation of water polluted with heavy metal ions, implying new methods of modification of manganese dioxides in practice.
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 3.1 x 10(-2) g/min mg. It is concluded that AOMO is a highly promising adsorbent for the removal of excess fluoride from drinking water.
Maternal dietary manganese protects chick embryos against maternal heat stress via epigenetic-activated antioxidant and anti-apoptotic abilities.

PubMed

Zhu, Yongwen; Lu, Lin; Liao, Xiudong; Li, Wenxiang; Zhang, Liyang; Ji, Cheng; Lin, Xi; Liu, Hsiao-Ching; Odle, Jack; Luo, Xugang

2017-10-27

Maternal heat stress induced the aberrant epigenetic patterns resulting in the abnormal development of offspring embryos. It is unclear whether maternal dietary manganese supplementation as an epigenetic modifier could protect the chick embryonic development against maternal heat stress via epigenetic mechanisms. To test this hypothesis using an avian model, a completely randomized design with a 2 (maternal normal and high environmental temperatures of 21 and 32°C, respectively) × 3 (maternal dietary manganese sources, the control diet without manganese supplementation and the control diet + 120 mg/kg as either inorganic or organic manganese) factorial arrangement was adopted. Maternal environmental hyperthermia increased mRNA expressions of heat shock proteins 90 and 70, cyclin-dependent kinase 6 and B-cell CLL/lymphoma 2-associated X protein displaying oxidative damage and apoptosis in the embryonic heart. Maternal environmental hyperthermia impaired the embryonic development associated with the alteration of epigenetic status, as evidenced by global DNA hypomethylation and histone 3 lysine 9 hypoacetylation in the embryonic heart. Maternal dietary manganese supplementation increased the heart anti-apoptotic gene B-cell CLL/lymphoma 2 expressions under maternal environmental hyperthermia and manganese superoxide dismutase enzyme activity in the embryonic heart. Maternal dietary organic Mn supplementation effectively eliminated the impairment of maternal environmental hyperthermia on the embryonic development. Maternal dietary manganese supplementation up-regulated manganese superoxide dismutase mRNA expression by reducing DNA methylation and increasing histone 3 lysine 9 acetylation of its promoter. It is suggested that maternal dietary manganese addition could protect the chick embryonic development against maternal heat stress via enhancing epigenetic-activated antioxidant and anti-apoptotic abilities.
Photochemically assisted fast abiotic oxidation of manganese and formation of δ-MnO 2 nanosheets in nitrate solution

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

Jung, Haesung; Chadha, Tandeep S.; Kim, Doyoon

This study introduces a new and previously unconsidered fast abiotic formation of Mn(IV) oxides. We report photochemically assisted fast abiotic oxidation of Mn 2+ (aq) to Mn(IV) (s) by superoxide radicals generated from nitrate photolysis. This photochemical pathway generates randomly stacked layered birnessite (δ-MnO 2) nanosheets.
Study of electrochemical reduced graphene oxide and MnO2 heterostructure for supercapacitor application

NASA Astrophysics Data System (ADS)

Jana, S. K.; Rao, V. P.; Banerjee, S.

2013-02-01

In this paper we have shown enhanced supercapacitive property of electrochemically reduced graphene oxide (ERGO) and manganese dioxide (MnO2) based heterostructure over single MnO2 thin film grown by electrochemical deposition on indium tin oxide (ITO). ERGO improves the electrical conduction leading to decrease of the internal resistance of the heterostructure.
Molten salt extraction process for the recovery of valued transition metals from land-based and deep-sea minerals

DOEpatents

Maroni, V.A.; von Winbush, S.

1987-05-01

A process for extracting transition metals and particularly cobalt and manganese together with iron, copper and nickel from low grade ores (including ocean-floor nodules) by converting the metal oxides or other compositions to chlorides in a molten salt, and subsequently using a combination of selective distillation at temperatures below about 500/degree/C, electrolysis at a voltage not more negative that about /minus/1.5 volt versus Ag/AgCl, and precipitation to separate the desired manganese and cobalt salts from other metals and provide cobalt and manganese in metallic forms or compositions from which these metals may be more easily recovered.
Molten salt extraction process for the recovery of valued transition metals from land-based and deep-sea minerals

DOEpatents

Maroni, Victor A.; von Winbush, Samuel

1988-01-01

A process for extracting transition metals and particularly cobalt and manganese together with iron, copper and nickel from low grade ores (including ocean-floor nodules) by converting the metal oxides or other compositions to chlorides in a molten salt, and subsequently using a combination of selective distillation at temperatures below about 500.degree. C., electrolysis at a voltage not more negative than about -1.5 volt versus Ag/AgCl, and precipitation to separate the desired manganese and cobalt salts from other metals and provide cobalt and manganese in metallic forms or compositions from which these metals may be more easily recovered.
Grains of Nonferrous and Noble Metals in Iron-Manganese Formations and Igneous Rocks of Submarine Elevations of the Sea of Japan

NASA Astrophysics Data System (ADS)

Kolesnik, O. N.; Astakhova, N. V.

2018-01-01

Iron-manganese formations and igneous rocks of submarine elevations in the Sea of Japan contain overlapping mineral phases (grains) with quite identical morphology, localization, and chemical composition. Most of the grains conform to oxides, intermetallic compounds, native elements, sulfides, and sulfates in terms of the set of nonferrous, noble, and certain other metals (Cu, Zn, Sn, Pb, Ni, Mo, Ag, Pd, and Pt). The main conclusion that postvolcanic hydrothermal fluids are the key sources of metals is based upon a comparison of the data of electron microprobe analysis of iron-manganese formations and igneous rocks dredged at the same submarine elevations in the Sea of Japan.
Using Iron-Manganese Co-Oxide Filter Film to Remove Ammonium from Surface Water

PubMed Central

Zhang, Ruifeng; Huang, Tinglin; Wen, Gang; Chen, Yongpan; Cao, Xin; Zhang, Beibei

2017-01-01

An iron-manganese co-oxide filter film (MeOx) has been proven to be a good catalyst for the chemical catalytic oxidation of ammonium in groundwater. Compared with groundwater, surface water is generally used more widely and has characteristics that make ammonium removal more difficult. In this study, MeOx was used to remove ammonium from surface water. It indicated that the average ammonium removal efficiency of MeOx was greater than 90%, even though the water quality changed dramatically and the water temperature was reduced to about 6–8 °C. Then, through inactivating microorganisms, it showed that the removal capability of MeOx included both biological (accounted for about 41.05%) and chemical catalytic oxidation and chemical catalytic oxidation (accounted for about 58.95%). The investigation of the characterizations suggested that MeOx was formed by abiotic ways and the main elements on the surface of MeOx were distributed homogenously. The analysis of the catalytic oxidation process indicated that ammonia nitrogen may interact with MeOx as both ammonia molecules and ammonium ions and the active species of O2 were possibly •O and O2−. PMID:28753939
Using Iron-Manganese Co-Oxide Filter Film to Remove Ammonium from Surface Water.

PubMed

Zhang, Ruifeng; Huang, Tinglin; Wen, Gang; Chen, Yongpan; Cao, Xin; Zhang, Beibei

2017-07-19

An iron-manganese co-oxide filter film (MeO x ) has been proven to be a good catalyst for the chemical catalytic oxidation of ammonium in groundwater. Compared with groundwater, surface water is generally used more widely and has characteristics that make ammonium removal more difficult. In this study, MeO x was used to remove ammonium from surface water. It indicated that the average ammonium removal efficiency of MeO x was greater than 90%, even though the water quality changed dramatically and the water temperature was reduced to about 6-8 °C. Then, through inactivating microorganisms, it showed that the removal capability of MeO x included both biological (accounted for about 41.05%) and chemical catalytic oxidation and chemical catalytic oxidation (accounted for about 58.95%). The investigation of the characterizations suggested that MeO x was formed by abiotic ways and the main elements on the surface of MeO x were distributed homogenously. The analysis of the catalytic oxidation process indicated that ammonia nitrogen may interact with MeO x as both ammonia molecules and ammonium ions and the active species of O₂ were possibly • O and O₂ - .
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, causes a rapid second-stage rearrangement and facilitates disproportionation of the Mn3+ ions. The Mn2+ ions thus released provide a positive feedback mechanism that couples the two steps of the conversion of Mn2+ to Mn4+ more closely than is possible when other metal ions besides manganese are not present. During aging of precipitates in contact with solutions, proportions of Cd2Mn3O8 and MnO2 increased at the expense of other precipitate components. ?? 1991.
Preliminary study of sources and processes of enrichment of manganese in water from University of Rhode Island supply wells

USGS Publications Warehouse

Silvey, William Dudley; Johnston, Herbert E.

1977-01-01

Concentrations of dissolved manganese have increased from 0.0 to as much as 3.3 mg/liter over a period of years in closely spaced University of Rhode Island supply wells. The wells tap stratified glacial deposits and derive part of their water from infiltration from a nearby river-pond system. The principal sources of the manganese seem to be coatings of oxides and other forms of manganese on granular aquifer materials and organic-rich sediments on the bottom of the pond and river. Chemical analyses of water from an observation well screened from 3 to 5 feet below the pond bottom indicate that infiltration of water through organic-rich sediments on the pond bottom is the likely cause of manganese enrichment in the well supplies. After passing through the organic layer, the water contains concentrations of manganese as high as 1.2 mg/liter. Manganese in water in concentrations that do not cause unpleasant taste is not regarded to be toxicologically significant. However, concentrations in excess of a few tenths of a milligram per liter are undesirable in public supplies and in many industrial supplies. Brown and others (21970) note that waters containing manganese in concentrations less than 0.1 mg/liter seldom prove troublesome, but that those containing more than 0.5 mg/liter may form objectionable deposits on cooked food, laundry, and plumbing fixtures. The U.S. Public health Service (1962) recommends that the concentrations of manganese in drinking and culinary water not exceed 0.05 mg/liter. (Woodard-USGS)
Manganese activates the mitochondrial apoptotic pathway in rat astrocytes by modulating the expression of proteins of the Bcl-2 family.

PubMed

Gonzalez, Laura E; Juknat, A Ana; Venosa, Andrea J; Verrengia, Noemi; Kotler, Mónica L

2008-12-01

Manganese induces the central nervous system injury leading to manganism, by mechanisms not completely understood. Chronic exposure to manganese generates oxidative stress and induces the mitochondrial permeability transition. In the present study, we characterized apoptotic cell death mechanisms associated with manganese toxicity in rat cortical astrocytes and demonstrated that (i) Mn treatment targets the mitochondria and induces mitochondrial membrane depolarization followed by cytochrome c release to the cytoplasm, (ii) Mn induces both effector caspases 3/7 and 6 as well as PARP-1 cleavage and (iii) Mn shifts the balance of cell death/survival of Bcl-2 family proteins to favor the apoptotic demise of astrocytes. Our model system using cortical rat astrocytes treated with Mn would emerge as a good tool for investigations aimed to elucidate the role of apoptosis in manganism.
Surface Reactivity of Li2MnO3: First-Principles and Experimental Study.

PubMed

Quesne-Turin, Ambroise; Flahaut, Delphine; Croguennec, Laurence; Vallverdu, Germain; Allouche, Joachim; Charles-Blin, Youn; Chotard, Jean-Noël; Ménétrier, Michel; Baraille, Isabelle

2017-12-20

This article deals with the surface reactivity of (001)-oriented Li 2 MnO 3 crystals investigated from a multitechnique approach combining material synthesis, X-ray photoemission spectroscopy (XPS), scanning electron microscopy, Auger electron spectroscopy, and first-principles calculations. Li 2 MnO 3 is considered as a model compound suitable to go further in the understanding of the role of tetravalent manganese atoms in the surface reactivity of layered lithium oxides. The knowledge of the surface properties of such materials is essential to understand the mechanisms involved in parasitic phenomena responsible for early aging or poor storage performances of lithium-ion batteries. The surface reactivity was probed through the adsorption of SO 2 gas molecules on large Li 2 MnO 3 crystals to be able to focus the XPS beam on the top of the (001) surface. A chemical mapping and XPS characterization of the material before and after SO 2 adsorption show in particular that the adsorption is homogeneous at the micro- and nanoscale and involves Mn reduction, whereas first-principles calculations on a slab model of the surface allow us to conclude that the most energetically favorable species formed is a sulfate with charge transfer implying reduction of Mn.
Water soluble nano-scale transient material germanium oxide for zero toxic waste based environmentally benign nano-manufacturing

NASA Astrophysics Data System (ADS)

Almuslem, A. S.; Hanna, A. N.; Yapici, T.; Wehbe, N.; Diallo, E. M.; Kutbee, A. T.; Bahabry, R. R.; Hussain, M. M.

2017-02-01

In the recent past, with the advent of transient electronics for mostly implantable and secured electronic applications, the whole field effect transistor structure has been dissolved in a variety of chemicals. Here, we show simple water soluble nano-scale (sub-10 nm) germanium oxide (GeO2) as the dissolvable component to remove the functional structures of metal oxide semiconductor devices and then reuse the expensive germanium substrate again for functional device fabrication. This way, in addition to transiency, we also show an environmentally friendly manufacturing process for a complementary metal oxide semiconductor (CMOS) technology. Every year, trillions of complementary metal oxide semiconductor (CMOS) electronics are manufactured and billions are disposed, which extend the harmful impact to our environment. Therefore, this is a key study to show a pragmatic approach for water soluble high performance electronics for environmentally friendly manufacturing and bioresorbable electronic applications.
Removal of Waste Anesthetics Exhaust.

DTIC Science & Technology

1995-12-01

Filter 580 ST manufactured by Auer (MSA) in Germany. This filter contains Hopcalite (a mixture of MnO2, CuO, C0203 and Ag20) which oxidizes carbon...exhaust of dental patients. A C2 canister coupled downstream to the Hopcalite -containing filter may be used to remove the oxidation products such as nitric...components of this Hopcalite - type catalyst consist of 60-75% manganese oxide, 11-14% copper oxide and 15-16% aluminum oxide. f. Penetrant-Protective
Nanoscale Ge fin etching using F- and Cl-based etchants for Ge-based multi-gate devices

NASA Astrophysics Data System (ADS)

Zhang, Bingxin; An, Xia; Li, Ming; Hao, Peilin; Zhang, Xing; Huang, Ru

2018-04-01

In this paper, nanoscale germanium (Ge) fin etching with inductively coupled plasma equipment with SF6/CHF3/Ar and Cl2/BCl3/Ar gas mixes are experimentally demonstrated. The impact of the gas ratio on etching induced Ge surface flatness, etch rate and sidewall steepness are comprehensively investigated and compared for these two kinds of etchants and the optimized gas ratio is provided. By using silicon oxide as a hard mask, nanoscale Ge fin with a flat surface and sharp sidewall is experimentally illustrated, which indicates great potential for use in nanoscale Ge-based multi-gate MOSFETs.
Kinetics of sorption and abiotic oxidation of arsenic(III) by aquifer materials

USGS Publications Warehouse

Amirbahman, A.; Kent, D.B.; Curtis, G.P.; Davis, J.A.

2006-01-01

The fate of arsenic in groundwater depends largely on its interaction with mineral surfaces. We investigated the kinetics of As(III) oxidation by aquifer materials collected from the USGS research site at Cape Cod, MA, USA, by conducting laboratory experiments. Five different solid samples with similar specific surface areas (0.6-0.9 m2 g-1) and reductively extractable iron contents (18-26 ??mol m-2), but with varying total manganese contents (0.5-3.5 ??mol m-2) were used. Both dissolved and adsorbed As(III) and As(V) concentrations were measured with time up to 250 h. The As(III) removal rate from solution increased with increasing solid manganese content, suggesting that manganese oxide is responsible for the oxidation of As(III). Under all conditions, dissolved As(V) concentrations were very low. A quantitative model was developed to simulate the extent and kinetics of arsenic transformation by aquifer materials. The model included: (1) reversible rate-limited adsorption of As(III) onto both oxidative and non-oxidative (adsorptive) sites, (2) irreversible rate-limited oxidation of As(III), and (3) equilibrium adsorption of As(V) onto adsorptive sites. Rate constants for these processes, as well as the total oxidative site densities were used as the fitting parameters. The total adsorptive site densities were estimated based on the measured specific surface area of each material. The best fit was provided by considering one fast and one slow site for each adsorptive and oxidative site. The fitting parameters were obtained using the kinetic data for the most reactive aquifer material at different initial As(III) concentrations. Using the same parameters to simulate As(III) and As(V) surface reactions, the model predictions were compared to observations for aquifer materials with different manganese contents. The model simulated the experimental data very well for all materials at all initial As(III) concentrations. The As(V) production rate was related to the concentrations of the free oxidative surface sites and dissolved As(III), as r As(V) = k???ox [Mn(IV) OH3][AsO3] with apparent second-order rate constants of koxf??? = 6.28 ?? 10-1 and koxs??? = 1.25 ?? 10-2 M-1 s-1 for the fast and the slow oxidative sites, respectively. The As(III) removal rate decreased approximately by half for a pH increase from 4 to 7. The pH dependence was explained using the acid-base behavior of the surface oxidative sites by considering a surface pKa = 6.2 (I = 0). In the presence of excess surface adsorptive and oxidative sites, phosphate diminished the rate of As(III) removal and As(V) production only slightly due to its interaction with the oxidative sites. The observed As(III) oxidation rate here is consistent with previous observations of As(III) oxidation over short transport distances during field-scale transport experiments. The model developed here may be incorporated into groundwater transport models to predict arsenic speciation and transport in chemically heterogeneous systems. ?? 2005 Elsevier Inc. All rights reserved.
High Manganese Tolerance and Biooxidation Ability of Serratia marcescens Isolated from Manganese Mine Water in Minas Gerais, Brazil.

PubMed

Barboza, Natália R; Morais, Mônica M C A; Queiroz, Pollyana S; Amorim, Soraya S; Guerra-Sá, Renata; Leão, Versiane A

2017-01-01

Manganese is an important metal for the maintenance of several biological functions, but it can be toxic in high concentrations. One of the main forms of human exposure to metals, such as manganese (Mn), is the consumption of solar salt contaminated. Mn-tolerant bacteria could be used to decrease the concentration of this metal from contaminated sites through safer environmental-friendly alternative technology in the future. Therefore, this study was undertaken to isolate and identify Mn resistant bacteria from water samples collected from a Mn mine in the Iron Quadrangle region (Minas Gerais, Brazil). Two bacterial isolates were identified as Serratia marcescens based on morphological, biochemical, 16S rDNA gene sequencing and phylogeny analysis. Maximum resistance of the selected isolates against increasing concentrations of Mn(II), up to 1200 mg L -1 was determined in solid media. A batch assay was developed to analyze and quantify the Mn removal capacities of the isolates. Biological Mn removal capacities of over 55% were detected for both isolates. Whereas that mechanism like biosorption, precipitation and oxidation could be explaining the Mn removal, we seek to give an insight into some of the molecular mechanisms adopted by S. marcescens isolates. For this purpose, the following approaches were adopted: leucoberbelin blue I assay, Mn(II) oxidation by cell-free filtrate and electron microscopy and energy-dispersive X-ray spectroscopy analyses. Overall, these results indicate that S. marcescens promotes Mn removal in an indirect mechanism by the formation of Mn oxides precipitates around the cells, which should be further explored for potential biotechnological applications for water recycling both in hydrometallurgical and mineral processing operations.
The influence of curcumin and manganese complex of curcumin on cadmium-induced oxidative damage and trace elements status in tissues of mice.

PubMed

Eybl, Vladislav; Kotyzová, Dana; Lesetický, Ladislav; Bludovská, Monika; Koutenský, Jaroslav

2006-01-01

Curcumin (diferuoyl methane) from turmeric is a well-known biologically active compound. It has been shown to ameliorate oxidative stress and it is considered to be a potent cancer chemopreventive agent. In our previous study the antioxidative effects of curcumin in cadmium exposed animals were demonstrated. Also manganese exerts protective effects in experimental cadmium intoxication. The present study examined the ability of the manganese complex of curcumin (Mn-curcumin) and curcumin to protect against oxidative damage and changes in trace element status in cadmium-intoxicated male mice. Curcumin or Mn-curcumin were administered at equimolar doses (0.14 mmol/kg b.w.) for 3 days, by gastric gavages, dispersed in methylcellulose. One hour after the last dose of antioxidants, cadmium chloride (33 micromol/kg) was administered subcutaneously. Both curcumin and Mn-curcumin prevented the increase of hepatic lipid peroxidation -- expressed as MDA level, induced by cadmium intoxication and attenuated the Cd-induced decrease of hepatic GSH level. No change in hepatic glutathione peroxidase or catalase activities was found in Cd-exposed mice. A decreased GSH-Px activity was measured in curcumin and Mn-curcumin alone treated mice. Neither curcumin nor Mn-curcumin treatment influenced cadmium distribution in the tissues and did not correct the changes in the balance of essential elements caused by Cd-treatment. The treatment with Mn-curcumin increased the Fe and Mn content in the kidneys of both control and Cd-treated mice and Fe and Cu content in the brain of control mice. In conclusion, regarding the antioxidative action, introducing manganese into the curcumin molecule does not potentiate the studied effects of curcumin. Copyright 2006 John Wiley & Sons, Ltd.

Kinetics of the solid-state carbothermic reduction of wessel manganese ores

NASA Astrophysics Data System (ADS)

Akdogan, Guven; Eric, R. Hurman

1995-02-01

Reduction of manganese ores from the Wessel mine of South Africa has been investigated in the temperature range 1100 °C to 1350 °C with pure graphite as the reductant under argon atmosphere. The rate and degree of reduction were found to increase with increasing temperature and decreasing particle sizes of both the ore and the graphite. The reduction was found to occur in two stages: (1) The first stage includes the rapid reduction of higher oxides of manganese and iron to MnO and FeO. The rate control appears to be mixed, both inward diffusion of CO and outward diffusion of CO2 across the porous product layer, and the reaction of carbon monoxide on the pore walls of the oxide phase play important roles. The values of effective CO-CO2 diffusivities generated by the mathematical model are in the range from 2.15 x 10-5 to 6.17 X 10-5 cm2.s-1 for different ores at 1300 °C. Apparent activation energies range from 81. 3 to 94.6 kJ/kg/mol. (2) The second stage is slower during which MnO and FeO are reduced to mixed carbide of iron and manganese. The chemical reaction between the manganous oxide and carbon dissolved in the metal phase or metal carbide seems to be the rate-controlling process The rate constant of chemical reaction between MnO and carbide on the surface of the impervious core was found to lie in the range from 1.53 x 10-8 to 1.32 x 10-7 mol . s-1 . cm-2. Apparent activation energies calculated are in the range from 102.1 to 141.7 kJ/kg/mol.
High Manganese Tolerance and Biooxidation Ability of Serratia marcescens Isolated from Manganese Mine Water in Minas Gerais, Brazil

PubMed Central

Barboza, Natália R.; Morais, Mônica M. C. A.; Queiroz, Pollyana S.; Amorim, Soraya S.; Guerra-Sá, Renata; Leão, Versiane A.

2017-01-01

Manganese is an important metal for the maintenance of several biological functions, but it can be toxic in high concentrations. One of the main forms of human exposure to metals, such as manganese (Mn), is the consumption of solar salt contaminated. Mn-tolerant bacteria could be used to decrease the concentration of this metal from contaminated sites through safer environmental-friendly alternative technology in the future. Therefore, this study was undertaken to isolate and identify Mn resistant bacteria from water samples collected from a Mn mine in the Iron Quadrangle region (Minas Gerais, Brazil). Two bacterial isolates were identified as Serratia marcescens based on morphological, biochemical, 16S rDNA gene sequencing and phylogeny analysis. Maximum resistance of the selected isolates against increasing concentrations of Mn(II), up to 1200 mg L-1 was determined in solid media. A batch assay was developed to analyze and quantify the Mn removal capacities of the isolates. Biological Mn removal capacities of over 55% were detected for both isolates. Whereas that mechanism like biosorption, precipitation and oxidation could be explaining the Mn removal, we seek to give an insight into some of the molecular mechanisms adopted by S. marcescens isolates. For this purpose, the following approaches were adopted: leucoberbelin blue I assay, Mn(II) oxidation by cell-free filtrate and electron microscopy and energy-dispersive X-ray spectroscopy analyses. Overall, these results indicate that S. marcescens promotes Mn removal in an indirect mechanism by the formation of Mn oxides precipitates around the cells, which should be further explored for potential biotechnological applications for water recycling both in hydrometallurgical and mineral processing operations. PMID:29062307
Accelerated evaporation of water on graphene oxide.

PubMed

Wan, Rongzheng; Shi, Guosheng

2017-03-29

Using molecular dynamics simulations, we show that the evaporation of nanoscale volumes of water on patterned graphene oxide is faster than that on homogeneous graphene oxide. The evaporation rate of water is insensitive to variation in the oxidation degree of the oxidized regions, so long as the water film is only distributed on the oxidized regions. The evaporation rate drops when the water film spreads onto the unoxidized regions. Further analysis showed that varying the oxidation degree observably changed the interaction between the outmost water molecules and the solid surface, but the total interaction for the outmost water molecules only changed a very limited amount due to the correspondingly regulated water-water interaction when the water film is only distributed on the oxidized regions. When the oxidation degree is too low and some unoxidized regions are also covered by the water film, the thickness of the water film decreases, which extends the lifetime of the hydrogen bonds for the outmost water molecules and lowers the evaporation rate of the water. The insensitivity of water evaporation to the oxidation degree indicates that we only need to control the scale of the unoxidized and oxidized regions for graphene oxide to regulate the evaporation of nanoscale volumes of water.
Fast degradation of dyes in water using manganese-oxide-coated diatomite for environmental remediation

NASA Astrophysics Data System (ADS)

Dang, Trung-Dung; Banerjee, Arghya Narayan; Tran, Quang-Tung; Roy, Sudipta

2016-11-01

By a simple wet-chemical procedure using a permanganate in the acidic medium, diatomite coated with amorphous manganese oxide nanoparticles was synthesized. The structural, microstructural and morphological characterizations of the as-synthesized catalysts confirmed the nanostructure of MnO2 and its stabilization on the support - diatomite. The highly efficient and rapid degradation of methylene blue and methyl orange over synthesized MnO2 coated Diatomite has been carried out. The results revealed considerably faster degradation of the dyes against the previously reported data. The proposed mechanism of the dye-degradation is considered to be a combinatorial effect of chemical, physicochemical and physical processes. Therefore, the fabricated catalysts have potential application in waste water treatment, and pollution degradation for environmental remediation.
Preliminary neutron diffraction analysis of challenging human manganese superoxide dismutase crystals

DOE PAGES

Azadmanesh, Jahaun; Trickel, Scott R.; Weiss, Kevin L.; ...

2017-03-29

Superoxide dismutases (SODs) are enzymes that protect against oxidative stress by dismutation of superoxide into oxygen and hydrogen peroxide through cyclic reduction and oxidation of the active-site metal. The complete enzymatic mechanisms of SODs are unknown since data on the positions of hydrogen are limited. Here, we present, methods for large crystal growth and neutron data collection of human manganese SOD (MnSOD) using perdeuteration and the MaNDi beamline at Oak Ridge National Laboratory. Furthermore, The crystal from which the human MnSOD data set was obtained is the crystal with the largest unit-cell edge (240 Å) from which data have beenmore » collectedvianeutron diffraction to sufficient resolution (2.30 Å) where hydrogen positions can be observed.« less
Preliminary neutron diffraction analysis of challenging human manganese superoxide dismutase crystals

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

Azadmanesh, Jahaun; Trickel, Scott R.; Weiss, Kevin L.

Superoxide dismutases (SODs) are enzymes that protect against oxidative stress by dismutation of superoxide into oxygen and hydrogen peroxide through cyclic reduction and oxidation of the active-site metal. The complete enzymatic mechanisms of SODs are unknown since data on the positions of hydrogen are limited. Here, we present, methods for large crystal growth and neutron data collection of human manganese SOD (MnSOD) using perdeuteration and the MaNDi beamline at Oak Ridge National Laboratory. Furthermore, The crystal from which the human MnSOD data set was obtained is the crystal with the largest unit-cell edge (240 Å) from which data have beenmore » collectedvianeutron diffraction to sufficient resolution (2.30 Å) where hydrogen positions can be observed.« less
Structural, optical, and magnetic studies of manganese-doped zinc oxide hierarchical microspheres by self-assembly of nanoparticles.

PubMed

Hao, Yao-Ming; Lou, Shi-Yun; Zhou, Shao-Min; Yuan, Rui-Jian; Zhu, Gong-Yu; Li, Ning

2012-02-02

In this study, a series of manganese [Mn]-doped zinc oxide [ZnO] hierarchical microspheres [HMSs] are prepared by hydrothermal method only using zinc acetate and manganese acetate as precursors and ethylene glycol as solvent. X-ray diffraction indicates that all of the as-obtained samples including the highest Mn (7 mol%) in the crystal lattice of ZnO have a pure phase (hexagonal wurtzite structure). A broad Raman spectrum from as-synthesized doping samples ranges from 500 to 600 cm-1, revealing the successful doping of paramagnetic Mn2+ ions in the host ZnO. Optical absorption analysis of the samples exhibits a blueshift in the absorption band edge with increasing dopant concentration, and corresponding photoluminescence spectra show that Mn doping suppresses both near-band edge UV emission and defect-related blue emission. In particular, magnetic measurements confirm robust room-temperature ferromagnetic behavior with a high Curie temperature exceeding 400 K, signifying that the as-formed Mn-doped ZnO HMSs will have immense potential in spintronic devices and spin-based electronic technologies.
Single molecule magnets with protective ligand shells on gold and titanium dioxide surfaces: In situ electrospray deposition and x-ray absorption spectroscopy

NASA Astrophysics Data System (ADS)

Handrup, Karsten; Richards, Victoria J.; Weston, Matthew; Champness, Neil R.; O'Shea, James N.

2013-10-01

Two single molecule magnets based on the dodecamanganese (III, IV) cluster with either benzoate or terphenyl-4-carboxylate ligands, have been studied on the Au(111) and rutile TiO2(110) surfaces. We have used in situ electrospray deposition to produce a series of surface coverages from a fraction of a monolayer to multilayer films in both cases. X-ray absorption spectroscopy measured at the Mn L-edge (Mn 2p) has been used to study the effect of adsorption on the oxidation states of the manganese atoms in the core. In the case of the benzoate-functionalised complex reduction of the manganese metal centres is observed due to the interaction of the manganese core with the underlying surface. In the case of terphenyl-4-carboxylate, the presence of this much larger ligand prevents the magnetic core from interacting with either the gold or the titanium dioxide surfaces and the characteristic Mn3+ and Mn4+ oxidation states necessary for magnetic behaviour are preserved.
Stable Water Oxidation in Acid Using Manganese-Modified TiO2 Protective Coatings.

PubMed

Siddiqi, Georges; Luo, Zhenya; Xie, Yujun; Pan, Zhenhua; Zhu, Qianhong; Röhr, Jason A; Cha, Judy J; Hu, Shu

2018-06-06

Accomplishing acid-stable water oxidation is a critical matter for achieving both long-lasting water-splitting devices and other fuel-forming electro- and photocatalytic processes. Because water oxidation releases protons into the local electrolytic environment, it becomes increasingly acidic during device operation, which leads to corrosion of the photoactive component and hence loss in device performance and lifetime. In this work, we show that thin films of manganese-modified titania, (Ti,Mn)O x , topped with an iridium catalyst, can be used in a coating stabilization scheme for acid-stable water oxidation. We achieved a device lifetime of more than 100 h in pH = 0 acid. We successfully grew (Ti,Mn)O x coatings with uniform elemental distributions over a wide range of manganese compositions using atomic layer deposition (ALD), and using X-ray photoelectron spectroscopy, we show that (Ti,Mn)O x films grown in this manner give rise to closer-to-valence-band Fermi levels, which can be further tuned with annealing. In contrast to the normally n-type or intrinsic TiO 2 coatings, annealed (Ti,Mn)O x films can make direct charge transfer to a Fe(CN) 6 3-/4- redox couple dissolved in aqueous electrolytes. Using the Fe(CN) 6 3-/4- redox, we further demonstrated anodic charge transfer through the (Ti,Mn)O x films to high work function metals, such as iridium and gold, which is not previously possible with ALD-grown TiO 2 . We correlated changes in the crystallinity (amorphous to rutile TiO 2 ) and oxidation state (2+ to 3+) of the annealed (Ti,Mn)O x films to their hole conductivity and electrochemical stability in acid. Finally, by combining (Ti,Mn)O x coatings with iridium, an acid-stable water-oxidation anode, using acid-sensitive conductive fluorine-doped tin oxides, was achieved.
Carbon Nanotube/Graphene Supercapacitors Containing Manganese Oxide Nanoparticles

DTIC Science & Technology

2012-12-01

for the carbon source since the GO is actually in solution and not merely suspended as the MWCNTs above were. Next, 2 mg of GO and 3.3 mg of MnAc...Results 2 2.1 GO /Manganese Acetate Solution Preparation .................................................................2 2.2 G/MnOx NP Synthesis...Figure 2. SEM image of ball milled MnAc (3 mole %) with multi-wall carbon nanotubes ( MWCNTs ) annealed at 370 °C. The resulting material is rather
Indirect Manganese Removal by Stenotrophomonas sp. and Lysinibacillus sp. Isolated from Brazilian Mine Water

PubMed Central

Barboza, Natália Rocha; Amorim, Soraya Sander; Santos, Pricila Almeida; Reis, Flávia Donária; Cordeiro, Mônica Mendes; Guerra-Sá, Renata; Leão, Versiane Albis

2015-01-01

Manganese is a contaminant in the wastewaters produced by Brazilian mining operations, and the removal of the metal is notoriously difficult because of the high stability of the Mn(II) ion in aqueous solutions. To explore a biological approach for removing excessive amounts of aqueous Mn(II), we investigated the potential of Mn(II) oxidation by both consortium and bacterial isolates from a Brazilian manganese mine. A bacterial consortium was able to remove 99.7% of the Mn(II). A phylogenetic analysis of isolates demonstrated that the predominant microorganisms were members of Stenotrophomonas, Bacillus, and Lysinibacillus genera. Mn(II) removal rates between 58.5% and 70.9% were observed for Bacillus sp. and Stenotrophomonas sp. while the Lysinibacillus isolate 13P removes 82.7%. The catalytic oxidation of Mn(II) mediated by multicopper oxidase was not properly detected; however, in all of the experiments, a significant increase in the pH of the culture medium was detected. No aggregates inside the cells grown for a week were found by electronic microscopy. Nevertheless, an energy-dispersive X-ray spectroscopy of the isolates revealed the presence of manganese in Stenotrophomonas sp. and Lysinibacillus sp. grown in K medium. These results suggest that members of Stenotrophomonas and Lysinibacillus genera were able to remove Mn(II) by a nonenzymatic pathway. PMID:26697496
Microemulsion based approach for nanospheres assembly into anisotropic nanostructures of NiMnO3 and their magnetic properties

NASA Astrophysics Data System (ADS)

Jha, Menaka; Kumar, Sandeep; Garg, Neha; Ramanujachary, Kandalam V.; Lofland, Samuel E.; Ganguli, Ashok K.

2018-02-01

The present study focuses on synthesis of anisotropic nanostructures of nickel manganese oxide (NiMnO3) obtained by thermal decomposition of nanocrystalline nickel manganese oxalate precursor, Ni0.5Mn0.5(C2O4)·2H2O which crystallized as nanorods. The synthesis of the oxalate precursor has been carried out via microemulsion-mediated process with cationic and non-ionic surfactants. The microemulsion led to reverse micelles, and the film flexibility of the micelle in presence of non-ionic surfactant (Tergitol) was reduced by increasing the chain length of the co-surfactant (1-butanol, 1-hexanol and 1-octanol) which led to the increase in reaction rate and hence increase in the aspect ratio of the nickel manganese oxalate by up to four times. However, in the presence of cationic surfactant, highly uniform nickel manganese oxalate nanorods were obtained. Further, the decomposition of the oxalate precursor was optimized to maintain the anisotropy of the rods of ternary metal oxide (NiMnO3). An electron microscopy study showed that the rods were made up of an assembly of ultrafine nanospheres. The NiMnO3 nanostructures were all ferrimagnetic with Curie temperature ranging between 437 and 467 K showing increasing saturation magnetization with increase in aspect ratio of the nanorods.
Spectroscopic Studies of the Iron and Manganese Reconstituted Tyrosyl Radical in Bacillus Cereus Ribonucleotide Reductase R2 Protein

PubMed Central

Tomter, Ane B.; Zoppellaro, Giorgio; Bell, Caleb B.; Barra, Anne-Laure; Andersen, Niels H.; Solomon, Edward I.; Andersson, K. Kristoffer

2012-01-01

Ribonucleotide reductase (RNR) catalyzes the rate limiting step in DNA synthesis where ribonucleotides are reduced to the corresponding deoxyribonucleotides. Class Ib RNRs consist of two homodimeric subunits: R1E, which houses the active site; and R2F, which contains a metallo cofactor and a tyrosyl radical that initiates the ribonucleotide reduction reaction. We studied the R2F subunit of B. cereus reconstituted with iron or alternatively with manganese ions, then subsequently reacted with molecular oxygen to generate two tyrosyl-radicals. The two similar X-band EPR spectra did not change significantly over 4 to 50 K. From the 285 GHz EPR spectrum of the iron form, a g 1-value of 2.0090 for the tyrosyl radical was extracted. This g 1-value is similar to that observed in class Ia E. coli R2 and class Ib R2Fs with iron-oxygen cluster, suggesting the absence of hydrogen bond to the phenoxyl group. This was confirmed by resonance Raman spectroscopy, where the stretching vibration associated to the radical (C-O, ν7a = 1500 cm−1) was found to be insensitive to deuterium-oxide exchange. Additionally, the 18O-sensitive Fe-O-Fe symmetric stretching (483 cm−1) of the metallo-cofactor was also insensitive to deuterium-oxide exchange indicating no hydrogen bonding to the di-iron-oxygen cluster, and thus, different from mouse R2 with a hydrogen bonded cluster. The HF-EPR spectrum of the manganese reconstituted RNR R2F gave a g 1-value of ∼2.0094. The tyrosyl radical microwave power saturation behavior of the iron-oxygen cluster form was as observed in class Ia R2, with diamagnetic di-ferric cluster ground state, while the properties of the manganese reconstituted form indicated a magnetic ground state of the manganese-cluster. The recent activity measurements (Crona et al., (2011) J Biol Chem 286: 33053–33060) indicates that both the manganese and iron reconstituted RNR R2F could be functional. The manganese form might be very important, as it has 8 times higher activity. PMID:22432022
Characterization of Nano-scale Aluminum Oxide Transport through Porous Media

NASA Astrophysics Data System (ADS)

Norwood, S.; Reynolds, M.; Miao, Z.; Brusseau, M. L.; Johnson, G. R.

2011-12-01

Colloidal material (including that in the nanoparticle size range) is naturally present in most subsurface environments. Mobilization of these colloidal materials via particle disaggregation may occur through abrupt changes in flow rate and/or via chemical perturbations, such as rapid changes in ionic strength or solution pH. While concentrations of natural colloidal materials in the subsurface are typically small, those concentrations may be greatly increased at contaminated sites such as following the application of metal oxides for groundwater remediation efforts. Additionally, while land application of biosolids has become common practice in the United States as an alternative to industrial fertilizers, biosolids have been shown to contain a significant fraction of organic and inorganic nano-scale colloidal materials such as oxides of iron, titanium, and aluminum. Given their reactivity and small size, there are many questions concerning the potential migration of nano-scale colloidal materials through the soil column and their potential participation in the facilitated transport of contaminants, such as heavy metals and emerging pollutants. The purpose of this study was to investigate the transport behavior of aluminum oxide (Al2O3) nanoparticles through porous media. The impacts of pH, ionic strength, pore-water velocity (i.e., residence time), and aqueous-phase concentration on transport was investigated. All experiments were conducted with large injection pulses to fully characterize the impact of long-term retention and transport behavior relevant for natural systems wherein multiple retention processes may be operative. The results indicate that the observed nonideal transport behavior of the nano-scale colloids is influenced by multiple retention mechanisms/processes. Given the ubiquitous nature of these nano-scale colloids in the environment, a clear understanding of their transport and fate is necessary in further resolving the potential for facilitated transport of toxins through the subsurface and into our surface and groundwater bodies.
NiAl Oxidation Reaction Processes Studied In Situ Using MEMS-Based Closed-Cell Gas Reaction Transmission Electron Microscopy

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

Unocic, Kinga A.; Shin, Dongwon; Unocic, Raymond R.

The nanoscale oxidation mechanisms and kinetics of a model β-NiAl system were investigated using in situ closed-cell gas reaction scanning transmission electron microscopy (STEM). Here, we directly visualize the dynamic structural and chemical changes that occur during high-temperature oxidation at a high spatial resolution of 50.3Ni–49.7Al (at.%) nanoparticles under static air conditions at 730 Torr with heating up to 750 °C at 5 °C/s. A MEMS-based gas cell system, with microfabricated heater devices and a gas delivery system, was used to reveal site-specific oxidation initiation sites. Through time-resolved annular dark-field STEM imaging, we tracked the nanoscale oxidation kinetics of Almore » 2O 3. After oxidation at 750 °C, nucleation of voids at the Ni/Al 2O 3 interface was observed along a NiAl grain boundary, followed by the formation of faceted NiO crystals. Small faceted cubic crystals of NiO were formed at the initial stage of oxidation at high PO 2 due to the outward self-diffusion of Ni 2+ ions, followed by the formation of a mixture of metastable and stable α-Al 2O 3 at the oxide/metal interface that is attributed to a PO 2 decrease with oxidation time, which agreed with thermodynamic modeling calculations. Furthermore, the results from these in situ oxidation experiments in the β-NiAl system are in agreement with the established oxidation mechanisms; however, with in situ closed-cell gas microscopy it is now feasible to investigate nanoscale oxidation mechanisms and kinetics in real time and at high spatial resolution and can be broadly applied to understand the basic high-temperature oxidation mechanisms for a wide range of alloy compositions.« less
NiAl Oxidation Reaction Processes Studied In Situ Using MEMS-Based Closed-Cell Gas Reaction Transmission Electron Microscopy

DOE PAGES

Unocic, Kinga A.; Shin, Dongwon; Unocic, Raymond R.; ...

2017-02-07

The nanoscale oxidation mechanisms and kinetics of a model β-NiAl system were investigated using in situ closed-cell gas reaction scanning transmission electron microscopy (STEM). Here, we directly visualize the dynamic structural and chemical changes that occur during high-temperature oxidation at a high spatial resolution of 50.3Ni–49.7Al (at.%) nanoparticles under static air conditions at 730 Torr with heating up to 750 °C at 5 °C/s. A MEMS-based gas cell system, with microfabricated heater devices and a gas delivery system, was used to reveal site-specific oxidation initiation sites. Through time-resolved annular dark-field STEM imaging, we tracked the nanoscale oxidation kinetics of Almore » 2O 3. After oxidation at 750 °C, nucleation of voids at the Ni/Al 2O 3 interface was observed along a NiAl grain boundary, followed by the formation of faceted NiO crystals. Small faceted cubic crystals of NiO were formed at the initial stage of oxidation at high PO 2 due to the outward self-diffusion of Ni 2+ ions, followed by the formation of a mixture of metastable and stable α-Al 2O 3 at the oxide/metal interface that is attributed to a PO 2 decrease with oxidation time, which agreed with thermodynamic modeling calculations. Furthermore, the results from these in situ oxidation experiments in the β-NiAl system are in agreement with the established oxidation mechanisms; however, with in situ closed-cell gas microscopy it is now feasible to investigate nanoscale oxidation mechanisms and kinetics in real time and at high spatial resolution and can be broadly applied to understand the basic high-temperature oxidation mechanisms for a wide range of alloy compositions.« less
Influence of the Typha community on mine drainage

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

Snyder, C.D.; Aharrah, E.C.

1984-12-01

This study investigated potential positive influences of the Typha community on mine drainage. The pH increased as the water flowed through two, two-pond systems, and the iron and manganese concentrations decreased. The water quality remained constant or deteriorated in non-vegetated ponds. Typha from the ponds and a non-mined site were assayed for iron and manganese. Roots/rhizomes concentrated the most iron, while the exterior stem layers contained more iron than the remaining stems or leaves. Manganese concentrations were similar in the roots/rhizomes, the leaves, and the exterior stem layers, while stems contained less. Iron concentrations in the Typha from June andmore » September were similar, but manganese concentrations in these Typha were different. Typha from mined sites accumulated more iron and manganese in the roots/rhizomes than Typha from non-mined sites. Bacteria and algae were identified and numerous species which function as oxidizers were recorded. These microbes play an important role in the Typha community and should also be considered in future studies as agents in the removal of metallic ions.« less
Green synthesis of Fe0 and bimetallic Fe0 for oxidative catalysis and reduction applications

EPA Science Inventory

A single-step green approach to the synthesis of nanoscale zero valent iron (nZVI) and nanoscale bimetallic (Fe0/Pd) particles using tea (Camellia sinensis) polyphenols is described. The expedient reaction between polyphenols and ferric chloride (FeCl3) occurs within a minute at ...
Novel synthesis of manganese and vanadium mixed oxide (V{sub 2}O{sub 5}/OMS-2) as an efficient and selective catalyst for the oxidation of alcohols in liquid phase

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

Mahdavi, Vahid, E-mail: v-mahdavi@araku.ac.ir; Soleimani, Shima

2014-03-01

Graphical abstract: Oxidation of various alcohols is studied in the liquid phase over new composite mixed oxide (V{sub 2}O{sub 5}/OMS-2) catalyst using tert-butyl hydroperoxide (TBHP). The activity of V{sub 2}O{sub 5}/OMS-2 samples was considerably increased with respect to OMS-2 catalyst and these samples are found to be suitable for the selective oxidation of alcohols. - Highlights: • V{sub 2}O{sub 5}/K-OMS-2 with different V/Mn molar ratios prepared by the impregnation method. • Oxidation of alcohols was studied in the liquid phase over V{sub 2}O{sub 5}/K-OMS-2 catalyst. • V{sub 2}O{sub 5}/K-OMS-2 catalyst had excellent activity for alcohol oxidation. • Benzyl alcohol oxidationmore » using excess TBHP followed a pseudo-first order kinetic. • The selected catalyst was reused without significant loss of activity. - Abstract: This work reports the synthesis and characterization of mixed oxide vanadium–manganese V{sub 2}O{sub 5}/K-OMS-2 at various V/Mn molar ratios and prepared by the impregnation method. Characterization of these new composite materials was made by elemental analysis, BET, XRD, FT-IR, SEM and TEM techniques. Results of these analyses showed that vanadium impregnated samples contained mixed phases of cryptomelane and crystalline V{sub 2}O{sub 5} species. Oxidation of various alcohols was studied in the liquid phase over the V{sub 2}O{sub 5}/K-OMS-2 catalyst using tert-butyl hydroperoxide (TBHP) and H{sub 2}O{sub 2} as the oxidant. Activity of the V{sub 2}O{sub 5}/K-OMS-2 samples was increased considerably with respect to K-OMS-2 catalyst due to the interaction of manganese oxide and V{sub 2}O{sub 5}. The kinetic of benzyl alcohol oxidation using excess TBHP over V{sub 2}O{sub 5}/K-OMS-2 catalyst was investigated at different temperatures and a pseudo-first order reaction was determined with respect to benzyl alcohol. The effects of reaction time, oxidant/alcohol molar ratio, reaction temperature, solvents, catalyst recycling potential and leaching were investigated.« less
Oxidative degradation of organic acids conjugated with sulfite oxidation in flue gas desulfurization

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

Lee, Y.I.

Organic acid degradation conjugated with sulfite oxidation has been studied under flue gas desulfurization (EGD) conditions. The oxidative degradation constant, k/sub 12/, is defined as the ratio of organic acid degradation rate and sulfite oxidation rate after being normalized by the concentrations of organic acid and dissolved S(IV). K/sub 12/, not significantly affected by pH or dissolved oxygen, is around 10/sup -3/ in the absence of manganese or iron. However, k/sub 12/ is increased by certain transition metals such as Co, Ni, and Fe and is decreased by Mn and halides. Lower dissolved S(IV) magnified these effects. No k/sub 12/more » greater than 4 x 10/sup -3/ or smaller than 0.1 x 10/sup -3/ has been observed. A free radical mechanism was proposed to describe the kinetics: (1) sulfate free radical is the major radical responsible to the degradation of organic acid; (2) ferrous generates sulfate radical by reacting with monoxypersulfate to enhance k/sub 12/; (3) manganous consumes sulfate radical to decrease k/sub 12/; (4) dissolved S(IV) competes with ferrous for monoxypersulfate and with manganous for sulfate radical to demonstrate the effects of dissolved S(IV) on k/sub 12/. Hydroxy and sulfonated carboxylic acids degrade approximately three times slower than saturated dicarboxylic acids; while maleic acid, an unsaturated dicarboxylic acid, degraded an order of magnitude faster. A wide spectrum of degradation products of adipic acid were found, including carbon dioxide - the major product, glutaric semialdehyde - the major retained product with low manganese, glutaric acid and valeric acids - the major retained product with high manganese, lower molecular weight mono- and dicarboxylic acids, other carbonyl compounds, and hydrocarbons.« less

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Sample records for nanoscale manganese oxide

Abstract