Sample records for nano-sized manganese oxides

  1. 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

  2. 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.

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. Sediment toxicity and bioaccumulation of nano and micron-sized aluminum oxide.

    PubMed

    Stanley, Jacob K; Coleman, Jessica G; Weiss, Charles A; Steevens, Jeffery A

    2010-02-01

    Nano-aluminum oxide (Al(2)O(3)) is used commercially in coatings and abrasives. Nano-Al(2)O(3) can also be generated through the oxidation of nano-aluminum in military propellants and energetics. The purpose of the present study was to assess toxicity and bioaccumulation of nano-Al(2)O(3) to a variety of sediment organisms (Tubifex tubifex, Hyalella azteca, Lumbriculus variegatus, and Corbicula fluminea). The bioaccumulation and toxicity of nano-Al(2)O(3) was compared with that of micron-sized Al(2)O(3) to investigate potential size-related effects. Results of the present study show species-specific differences in relative bioaccumulation of nano and micron-sized Al(2)O(3). Significant toxic effects (survival and growth) were observed in H. azteca testing, but only at high concentrations unlikely to be found in the environment. Nano-Al(2)O(3) was found to be more toxic than micron-sized Al(2)O(3) to H. azteca survival in a 14-d study in which organisms were in direct contact with a thin layer of 625 or 2,500 mg of Al(2)O(3) dispersed on the surface of either sediment or sand. A significant growth effect was also observed for nano but not micron-sized Al(2)O(3) at the highest treatment level tested (100 g/kg Al(2)O(3)) in a 10-d H. azteca bioassay in which Al(2)O(3) was homogenized with sediment. However, differences in measured sediment Al concentrations (micron-sized = 55.1 [+/-0.6] g/kg Al; nano-sized = 66.2 [+/-0.6] g/kg Al) in the nano and micron-sized Al(2)O(3) preclude direct comparison of the toxicity of these two treatments based on particle size. Copyright 2009 SETAC.

  8. Characterization of nano-sized oxides in Fe-12Cr oxide-dispersion-strengthened ferritic steel using small-angle neutron scattering

    NASA Astrophysics Data System (ADS)

    Han, Young-Soo; Mao, Xiaodong; Jang, Jinsung; Kim, Tae-Kyu

    2015-04-01

    The ferritic ODS steel was manufactured by hot isostatic pressing and heat treatment. The nano-sized microstructures such as yttrium oxides and Cr oxides were quantitatively analyzed by small-angle neutron scattering (SANS). The effects of the fabrication conditions on the nano-sized microstructure were investigated in relation to the quantitative analysis results obtained by SANS. The ratio between magnetic and nuclear scattering components was calculated, and the characteristics of the nano-sized yttrium oxides are discussed based on the SANS analysis results.

  9. 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.

  10. 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.

  11. Synthesis and LPG sensing properties of nano-sized cadmium oxide.

    PubMed

    Waghulade, R B; Patil, P P; Pasricha, Renu

    2007-04-30

    This paper reports the synthesis and liquid petroleum gas (LPG) sensing properties of nano-sized cadmium oxide (CdO). The nano-sized CdO powder was successfully synthesized by using a chemical co-precipitation method using cadmium acetate and the ammonium hydroxide, as starting materials and water as a carrier. The resulting nano-sized powder was characterized by X-ray diffraction (XRD) measurements and the transmission electron microscopy (TEM). The LPG sensing properties of the synthesized nano-sized CdO were investigated at different operating temperatures and LPG concentrations. It was found that the calcination temperature and the operating temperature significantly affect the sensitivity of the nano-sized CdO powder to the LPG. The sensitivity is found to be maximum when the calcination temperature was 400 degrees C. The sensitivity to 75ppm of LPG is maximum at an operating temperature 450 degrees C and it was found to be approximately 341%. The response and recovery times were found to be nearly 3-5s and 8-10s, respectively. The synthesized nano-sized CdO powder is able to detect up to 25ppm for LPG with reasonable sensitivity at an operating temperature 450 degrees C and it can be reliably used to monitor the concentration of LPG over the range (25-75ppm). The experimental results of the LPG sensing studies reveal that the nano-sized CdO powder synthesized by a simple co-precipitation method is a suitable material for the fabrication of the LPG sensor.

  12. 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.

  13. 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.

  14. Size-controlled synthesis and formation mechanism of manganese oxide OMS-2 nanowires under reflux conditions with KMnO4 and inorganic acids

    NASA Astrophysics Data System (ADS)

    Zhang, Qin; Cheng, Xiaodi; Qiu, Guohong; Liu, Fan; Feng, Xionghan

    2016-05-01

    This study presents a simplified approach for size-controlled synthesis of manganese oxide octahedral molecular sieve (OMS-2) nanowires using potassium permanganate (KMnO4) and different inorganic acids (HCl, HNO3, and H2SO4) under reflux conditions. The morphology and nanostructure of the synthesized products are characterized by X-ray diffraction, Ar adsorption, and electron microscopy analysis, in order to elucidate the controlling effects of acid concentration and type as well as the formation mechanism of OMS-2 nanowires. The concentration of inorganic acid is a crucial factor controlling the phase of the synthesized products. OMS-2 nanowires are obtained with HCl at the concentration ≥0.96 mol/L or with HNO3 and H2SO4 at the concentrations ≥0.72 mol/L. Differently, the type of inorganic acid effectively determines the particle size of OMS-2 nanowires. When the acid is changed from HCl to HNO3 and H2SO4 in the reflux system, the average length of OMS-2 declines significantly by 60-70% (1104-442 and 339 nm), with minor decreased in the average width (43-39 and 34 nm). The formation of OMS-2 nanowires under reflux conditions with KMnO4 and inorganic acids involves a two-step process, i.e., the initial formation of layered manganese oxides, and subsequent transformation to OMS-2 via a dissolution-recrystallization process under acidic conditions. The proposed reflux route provides an alternative approach for synthesizing OMS-2 nanowires as well as other porous nano-crystalline OMS materials.

  15. 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

  16. Morphology and phase identification of micron to nanosized manganese oxide (MnO) with variations in sintering time

    NASA Astrophysics Data System (ADS)

    Sasongko, Muhammad Ilman Nur; Puspitasari, Poppy; Yazirin, Cepi; Tsamroh, Dewi Izzatus; Risdanareni, Puput

    2017-09-01

    Manganese oxide (MnO) occurs in many rock types and may take the form of minerals. MnO has its drawbacks, namely highly reactive oxidizing species classified as dangerous and explosive at temperatures above 55 °C. Despite this,MnO has excellent magnetic, electrochemical, and conductivity properties, which should be reduced to nano-size to maximize their use and improve the properties of MnO. Phase and morphology characterization of powder this research aims to reduce the grain size of the MnO from micro to nano using the sol-gel method with various sintering times. Sol-gel is a simple synthesis method that has been proven capable of synthesizing a wide variety of micro-sized oxide materials into nano. Sintering time is a technique performed in the synthesis process to dry the material to a temperature above the normal temperature. The temperature used for sintering starting from 600 °C to 1000 °C. Characterizations were done using XRD, SEM, EDX, and FTIR machines. The sintering processes in this study used a temperature of 600 °C with different sintering periods of 30, 60 and 90 minutes. The XRD characterization with a 30-minute sintering time resulted in the smallest MnO in the form crystalline powder of 47.3 nm. The highest intensity (degree of crystallinity) found in MnO sintered for 90 minutes. The results of the morphological characterization of SEM showed a morphological change in MnO from micro-sized triangular to nano-sized spherical shape. The EDX characterization results indicated that the 30-minute sintering caused the lowest change in Mn and the highest change in O. The results of FTIR characterization showed a shift in C-H and Mn-O followed by an increase in the group of N-H, C=O and Mn-O.

  17. 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

  18. 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.

  19. Self-aligned periodic Ni nano dots embedded in nano-oxide layer

    NASA Astrophysics Data System (ADS)

    Doi, M.; Izumi, M.; Kawasaki, S.; Miyake, K.; Sahashi, M.

    The Ni nano constriction dots embedded in the Ta-nano-oxide layer (NOL) was prepared by the ion beam sputtering (IBS) method. After the various conditions of the oxidations, the structural analyses of the NOL were performed by RHEED, AES and in situ STM/AFM observations. From the current image of the conductive AFM for NOL, the periodically aligned metallic dots with the size around 5-10 nm were successfully observed. The mechanism of the formation of the self-organized aligned Ni nano constriction dots is discussed from the standpoint of the grain size, the crystal orientation, the preferred oxidation of Ta at the diffused interface.

  20. In vitro toxicity test of nano-sized magnesium oxide synthesized via solid-phase transformation

    NASA Astrophysics Data System (ADS)

    Zheng, Jun; Zhou, Wei

    2018-04-01

    Nano-sized magnesium oxide (MgO) has been a promising potential material for biomedical pharmaceuticals. In the present investigation, MgO nanoparticles synthesized through in-situ solid-phase transformation based on the previous work (nano-Mg(OH)2 prepared by precipitation technique) using magnesium nitrate and sodium hydroxide. The phase structure and morphology of the MgO nanoparticles are characterized by X-ray powder diffraction (XRD), selected area electronic diffraction (SAED) and transmission electron microscopy (TEM) respectively. In vitro hemolysis tests are adopted to evaluate the toxicity of the synthesized nano-MgO. The results evident that nano-MgO with lower concentration is slightly hemolytic, and with concentration increasing nano-MgO exhibit dose-responsive hemolysis.

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

    PubMed

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

    2014-08-01

    We present a facile synthesis of bioinspired manganese oxides for chemical and photocatalytic water oxidation, starting from a reliable and versatile manganese(II) oxalate single-source precursor (SSP) accessible through an inverse micellar molecular approach. Strikingly, thermal decomposition of the latter precursor in various environments (air, nitrogen, and vacuum) led to the three different mineral phases of bixbyite (Mn2 O3 ), hausmannite (Mn3 O4 ), and manganosite (MnO). Initial chemical water oxidation experiments using ceric ammonium nitrate (CAN) gave the maximum catalytic activity for Mn2 O3 and MnO whereas Mn3 O4 had a limited activity. The substantial increase in the catalytic activity of MnO in chemical water oxidation was demonstrated by the fact that a phase transformation occurs at the surface from nanocrystalline MnO into an amorphous MnOx (1oxidizing agent. Photocatalytic water oxidation in the presence of [Ru(bpy)3 ](2+) (bpy=2,2'-bipyridine) as a sensitizer and peroxodisulfate as an electron acceptor was carried out for all three manganese oxides including the newly formed amorphous MnOx . Both Mn2 O3 and the amorphous MnOx exhibit tremendous enhancement in oxygen evolution during photocatalysis and are much higher in comparison to so far known bioinspired manganese oxides and calcium-manganese oxides. Also, for the first time, a new approach for the representation of activities of water oxidation catalysts has been proposed by determining the amount of accessible manganese centers. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. 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

  3. 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.

  4. 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.

  5. Prediction Surface Morphology of Nanostructure Fabricated by Nano-Oxidation Technology.

    PubMed

    Huang, Jen-Ching; Chang, Ho; Kuo, Chin-Guo; Li, Jeen-Fong; You, Yong-Chin

    2015-12-04

    Atomic force microscopy (AFM) was used for visualization of a nano-oxidation technique performed on diamond-like carbon (DLC) thin film. Experiments of the nano-oxidation technique of the DLC thin film include those on nano-oxidation points and nano-oxidation lines. The feature sizes of the DLC thin film, including surface morphology, depth, and width, were explored after application of a nano-oxidation technique to the DLC thin film under different process parameters. A databank for process parameters and feature sizes of thin films was then established, and multiple regression analysis (MRA) and a back-propagation neural network (BPN) were used to carry out the algorithm. The algorithmic results are compared with the feature sizes acquired from experiments, thus obtaining a prediction model of the nano-oxidation technique of the DLC thin film. The comparative results show that the prediction accuracy of BPN is superior to that of MRA. When the BPN algorithm is used to predict nano-point machining, the mean absolute percentage errors (MAPE) of depth, left side, and right side are 8.02%, 9.68%, and 7.34%, respectively. When nano-line machining is being predicted, the MAPEs of depth, left side, and right side are 4.96%, 8.09%, and 6.77%, respectively. The obtained data can also be used to predict cross-sectional morphology in the DLC thin film treated with a nano-oxidation process.

  6. 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.

  7. Thermal annealing behavior of nano-size metal-oxide particles synthesized by ion implantation in Fe-Cr alloy

    NASA Astrophysics Data System (ADS)

    Zheng, C.; Gentils, A.; Ribis, J.; Borodin, V. A.; Descoins, M.; Mangelinck, D.; Dalle, F.; Arnal, B.; Delauche, L.

    2017-05-01

    Oxide dispersion strengthened (ODS) steels are promising structural materials for the next generation nuclear reactors, as well as fusion facilities. The detailed understanding of the mechanisms involved in the precipitation of nano-oxides during ODS steel production would strongly contribute to the improvement of the mechanical properties and the optimization of manufacturing of ODS steels, with a potentially strong economic impact for their industrialization. A useful tool for the experimental study of nano-oxide precipitation is ion implantation, a technique that is widely used to synthesize precipitate nanostructures in well-controlled conditions. Earlier, we have demonstrated the feasibility of synthesizing aluminum-oxide particles in the high purity Fe-10Cr alloy by consecutive implantation with Al and O ions at room temperature. This paper describes the effects of high-temperature annealing after the ion implantation stage on the development of the aluminum based oxide nanoparticle system. Using transmission electron microscopy and atom probe tomography experiments, we demonstrate that post-implantation heat treatment induces the growth of the nano-sized oxides in the implanted region and nucleation of new oxide precipitates behind the implantation zone as a result of the diffusion driven broadening of implant profiles. A tentative scenario for the development of metal-oxide nano-particles at both ion implantation and heat treatment stages is suggested based on the experimental observations.

  8. The role of particle size of particulate nano-zinc oxide wood preservatives on termite mortality and leach resistance

    NASA Astrophysics Data System (ADS)

    Clausen, Carol A.; Kartal, S. Nami; Arango, Rachel A.; Green, Frederick

    2011-06-01

    Historically most residential wood preservatives were aqueous soluble metal formulations, but recently metals ground to submicron size and dispersed in water to give particulate formulations have gained importance. In this study, the specific role nano-zinc oxide (ZnO) particle size and leach resistance plays in termite mortality resulting from exposure to particulate ZnO-treated wood was investigated. Southern yellow pine (SYP) sapwood impregnated with three concentrations of two particle sizes (30 and 70 nm) of ZnO were compared to wood treated with soluble zinc sulphate (ZnSO4) preservative for leach resistance and termite resistance. Less than four percent leached from the particulate nano-ZnO-treated specimens, while 13 to 25% of the zinc sulphate leached from the soluble treated wood. Nano-ZnO was essentially non-leachable from wood treated with 5% formulation for the 30-nm particle size. In a no-choice laboratory test, eastern subterranean termites ( Reticulitermes flavipes) consumed less than 10% of the leached nano-ZnO-treated wood with 93 to 100% mortality in all treatment concentrations. In contrast, termites consumed 10 to 12% of the leached ZnSO4-treated wood, but with lower mortality: 29% in the 1% treatment group and less than 10% (5 and 8%, respectively) in the group of wood blocks treated with 2.5 and 5.0% ZnSO4. We conclude that termites were repelled from consuming wood treated with nano-ZnO, but when consumed it was more toxic to eastern subterranean termites than wood treated with the soluble metal oxide formulation. There were no differences in leaching or termite mortality between the two particle sizes of nano-ZnO.

  9. Spatially confined synthesis of SiOx nano-rod with size-controlled Si quantum dots in nano-porous anodic aluminum oxide membrane.

    PubMed

    Pai, Yi-Hao; Lin, Gong-Ru

    2011-01-17

    By depositing Si-rich SiOx nano-rod in nano-porous anodic aluminum oxide (AAO) membrane using PECVD, the spatially confined synthesis of Si quantum-dots (Si-QDs) with ultra-bright photoluminescence spectra are demonstrated after low-temperature annealing. Spatially confined SiOx nano-rod in nano-porous AAO membrane greatly increases the density of nucleated positions for Si-QD precursors, which essentially impedes the route of thermally diffused Si atoms and confines the degree of atomic self-aggregation. The diffusion controlled growth mechanism is employed to determine the activation energy of 6.284 kJ mole(-1) and diffusion length of 2.84 nm for SiO1.5 nano-rod in nano-porous AAO membrane. HRTEM results verify that the reduced geometric dimension of the SiOx host matrix effectively constrain the buried Si-QD size at even lower annealing temperature. The spatially confined synthesis of Si-QD essentially contributes the intense PL with its spectral linewidth shrinking from 210 to 140 nm and its peak intensity enhancing by two orders of magnitude, corresponding to the reduction on both the average Si-QD size and its standard deviation from 2.6 to 2.0 nm and from 25% to 12.5%, respectively. The red-shifted PL wavelength of the Si-QD reveals an inverse exponential trend with increasing temperature of annealing, which is in good agree with the Si-QD size simulation via the atomic diffusion theory.

  10. 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

  11. Enhanced sun protection of nano-sized metal oxide particles over conventional metal oxide particles: an in vitro comparative study.

    PubMed

    Singh, P; Nanda, A

    2014-06-01

    A systematic and detailed study has been designed and conducted, taking into account some of the proposed benefits such as increased efficiency, transparency, unique texture, protection of active ingredient and higher consumer compliance of cosmetics containing nano-sized metal oxides. This study also presents an in vitro method to determine sun protection factor of the investigational sunscreen cream samples containing zinc oxide and titanium dioxide with a varied range of particle size. Finally, a comparative study has been conducted between metal oxide particles, conventional as well as nanoparticles. All the skin cosmetics formulated were thermally stable with a pH ranging from 7.9 to 8.2. Moreover, the fatty acid substance content and residue were found to be analogous to the standard values in each skin cosmetic. The skin cosmetics containing the titanium or zinc oxide nanoparticles were found to have improved spreadability as compared to skin cosmetics containing conventional titanium or zinc oxide particles, respectively. All skin cosmetics were found to have uniform distribution of the particles. The sunscreen creams containing zinc oxide nanoparticles and titanium dioxide nanoparticles were found to have higher in vitro sun protection factor (SPF of 3.65 for ZnO nanoparticles and 4.93 for TiO2 nanoparticles) as compared to that of sunscreen creams containing conventional zinc oxide particles (SPF = 2.90) and conventional titanium dioxide (SPF = 1.29), clearly indicating the effect of reduction in particles size, from micro to nano, on the sun protection factor. Good texture, better spreadability and enhanced in vitro SPF proved the advantageous role of nanoparticles in cosmetics. © 2014 Society of Cosmetic Scientists and the Société Française de Cosmétologie.

  12. 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.

  13. 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).

  14. 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.

  15. Oxidative stress, cytoxicity, and cell mortality induced by nano-sized lead in aqueous suspensions.

    PubMed

    Cornejo-Garrido, Hilda; Kibanova, Daria; Nieto-Camacho, Antonio; Guzmán, José; Ramírez-Apan, Teresa; Fernández-Lomelín, Pilar; Garduño, Maria Laura; Cervini-Silva, Javiera

    2011-09-01

    This paper reports on the effect of aqueous and nano-particulated Pb on oxidative stress (lipid peroxidation), cytoxicity, and cell mortality. As determined by the Thiobarbituric Acid Reactive Substances (TBARS) method, only 6h after incubation aqueous suspensions bearing nano-sized PbO(2), soluble Pb(II), and brain-homogenate only suspensions, were determined to contain as much as ca. 7, 5, and 1 nmol TBARS mg protein(-1), respectively. Exposure of human cells (central nervous system, prostate, leukemia, colon, breast, lung cells) to nano-PbO(2) led to cell-growth inhibition values (%) ca. ≤18.7%. Finally, as estimated by the Artemia salina test, cell mortality values were found to show high-survival larvae rates. Microscopic observations revealed that Pb particles were swallowed, but caused no mortality, however. Copyright © 2011 Elsevier Ltd. All rights reserved.

  16. Manganese oxide nanoparticle-assisted laser desorption/ionization mass spectrometry for medical applications

    NASA Astrophysics Data System (ADS)

    Taira, Shu; Kitajima, Kenji; Katayanagi, Hikaru; Ichiishi, Eiichiro; Ichiyanagi, Yuko

    2009-06-01

    We prepared and characterized manganese oxide magnetic nanoparticles (d =5.6 nm) and developed nanoparticle-assited laser desorption/ionization (nano-PALDI) mass spectrometry. The nanoparticles had MnO2 and Mn2O3 cores conjugated with hydroxyl and amino groups, and showed paramagnetism at room temperature. The nanoparticles worked as an ionization assisting reagent in mass spectroscopy. The mass spectra showed no background in the low m/z. The nanoparticles could ionize samples of peptide, drug and proteins (approx. 5000 Da) without using matrix, i.e., 2,5-dihydroxybenzoic acid (DHB), 4-hydroxy-α-cinnamic acid (CHCA) and liquid matrix, as conventional ionization assisting reagents. Post source decay spectra by nano-PALDI mass spectrometry will yield information of the chemical structure of analytes.

  17. 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.

  18. 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

  19. 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

  20. 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...

  1. 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...

  2. 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...

  3. 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...

  4. 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...

  5. 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...

  6. 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.

  7. Reactive oxygen species-related activities of nano-iron metal and nano-iron oxides.

    PubMed

    Wu, Haohao; Yin, Jun-Jie; Wamer, Wayne G; Zeng, Mingyong; Lo, Y Martin

    2014-03-01

    Nano-iron metal and nano-iron oxides are among the most widely used engineered and naturally occurring nanostructures, and the increasing incidence of biological exposure to these nanostructures has raised concerns about their biotoxicity. Reactive oxygen species (ROS)-induced oxidative stress is one of the most accepted toxic mechanisms and, in the past decades, considerable efforts have been made to investigate the ROS-related activities of iron nanostructures. In this review, we summarize activities of nano-iron metal and nano-iron oxides in ROS-related redox processes, addressing in detail the known homogeneous and heterogeneous redox mechanisms involved in these processes, intrinsic ROS-related properties of iron nanostructures (chemical composition, particle size, and crystalline phase), and ROS-related bio-microenvironmental factors, including physiological pH and buffers, biogenic reducing agents, and other organic substances. Copyright © 2014. Published by Elsevier B.V.

  8. Exposure to nano-size titanium dioxide causes oxidative damages in human mesothelial cells: The crystal form rather than size of particle contributes to cytotoxicity.

    PubMed

    Hattori, Kenji; Nakadate, Kazuhiko; Morii, Akane; Noguchi, Takumi; Ogasawara, Yuki; Ishii, Kazuyuki

    2017-10-14

    Exposure to nanoparticles such as carbon nanotubes has been shown to cause pleural mesothelioma similar to that caused by asbestos, and has become an environmental health issue. Not only is the percutaneous absorption of nano-size titanium dioxide particles frequently considered problematic, but the possibility of absorption into the body through the pulmonary route is also a concern. Nevertheless, there are few reports of nano-size titanium dioxide particles on respiratory organ exposure and dynamics or on the mechanism of toxicity. In this study, we focused on the morphology as well as the size of titanium dioxide particles. In comparing the effects between nano-size anatase and rutile titanium dioxide on human-derived pleural mesothelial cells, the anatase form was shown to be actively absorbed into cells, producing reactive oxygen species and causing oxidative damage to DNA. In contrast, we showed for the first time that the rutile form is not easily absorbed by cells and, therefore, does not cause oxidative DNA damage and is significantly less damaging to cells. These results suggest that with respect to the toxicity of titanium dioxide particles on human-derived mesothelial cells, the crystal form rather than the particle size has a greater effect on cellular absorption. Also, it was indicated that the difference in absorption is the primary cause of the difference in the toxicity against mesothelial cells. Copyright © 2017 Elsevier Inc. All rights reserved.

  9. 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

  10. 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.

  11. 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.

  12. Comparison of nano-sized Mn oxides with the Mn cluster of photosystem II as catalysts for water oxidation.

    PubMed

    Najafpour, Mohammad Mahdi; Ghobadi, Mohadeseh Zarei; Haghighi, Behzad; Tomo, Tatsuya; Shen, Jian-Ren; Allakhverdiev, Suleyman I

    2015-02-01

    "Back to Nature" is a promising way to solve the problems that we face today, such as air pollution and shortage of energy supply based on conventional fossil fuels. A Mn cluster inside photosystem II catalyzes light-induced water-splitting leading to the generation of protons, electrons and oxygen in photosynthetic organisms, and has been considered as a good model for the synthesis of new artificial water-oxidizing catalysts. Herein, we surveyed the structural and functional details of this cluster and its surrounding environment. Then, we review the mechanistic findings concerning the cluster and compare this biological catalyst with nano-sized Mn oxides, which are among the best artificial Mn-based water-oxidizing catalysts. Copyright © 2014 Elsevier B.V. All rights reserved.

  13. 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.

  14. 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.

  15. The Effects of Natural Clinoptilolite and Nano-Sized Clinoptilolite Supplementation on Glucose Levels and Oxidative Stress in Rats With Type 1 Diabetes.

    PubMed

    Hossein Nia, Behnoosh; Khorram, Sirous; Rezazadeh, Hassan; Safaiyan, Abdolrasol; Tarighat-Esfanjani, Ali

    2018-02-01

    Oxidative stress has a major role in development of diabetic complications. In this study we investigated whether clinoptilolite and nano-sized clinoptilolite could reduce hyperglycemia and oxidative stress in streptozotocin-induced diabetic rats and attempted to determine which intervention was more effective. Thirty-six rats were randomly allocated to 2 groups; 1 group was randomly chosen as a diabetic group and injected with streptozotocin (60 mg/kg body weight in 0.1 mol/L sodium citrate buffer, pH 4.5) to induce diabetes. Three days after diabetes induction, each group (diabetic group and nondiabetic group) was randomly divided into 3 subgroups of 6 animals each ([1] control, [2] 1% clinoptilolite/food, [3] 1% nano-sized clinoptilolite/food). Supplementation was continued for 28 days. Blood glucose was measured 3 times, at the beginning of the study and on the 14th and 28th days. Activity of antioxidant enzymes, including glutathione peroxidase and superoxide dismutase, and levels of total antioxidant capacity, as well as malondialdehyde, were evaluated. Blood glucose and malondialdehyde were significantly elevated, but there were no statistically significant changes in superoxide dismutase, glutathione peroxidase or total antioxidant capacity in diabetic rats. In diabetic rats treated with nano-sized clinoptilolite, blood glucose decreased to near normal levels (12.4 vs. 27.5 mmol/L). No significant changes were found in the other groups. None of the oxidative stress indices showed significant changes in either the treated or untreated rats. Nano-sized clinoptilolite exerted a hypoglycemic effect in streptozotocin-induced diabetic rats but had no significant influence on oxidative stress markers. Copyright © 2018. Published by Elsevier Inc.

  16. 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.

  17. 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.

  18. 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.

  19. 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.

  20. 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...

  1. 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...

  2. 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...

  3. 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...

  4. 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...

  5. 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...

  6. 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...

  7. 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...

  8. 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...

  9. 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...

  10. Silver manganese oxide electrodes for lithium batteries

    DOEpatents

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

    2006-05-09

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

  11. 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.

  12. 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

  13. 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.

  14. 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

  15. 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...

  16. 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...

  17. 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...

  18. 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...

  19. 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...

  20. 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.

  1. 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

  2. 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.

  3. 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

  4. 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.

  5. 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.

  6. 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...

  7. 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.

  8. 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.

  9. 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.

  10. 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

  11. 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.

  12. 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...

  13. 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.

  14. Effect of CTAB concentration on synthesis of nickel doped manganese oxide nanoparticles

    NASA Astrophysics Data System (ADS)

    Shobana, R.; Saravanakumar, B.; Ravi, G.; Yuvakkumar, R.

    2018-05-01

    In this work the effect of concentration of cetyltrimethylammonium bromide (CTAB) in the synthesis of Nickel doped Manganese oxide (Ni-MnO2) nanoparticles have been carried out by adopting the sol-gel process. The synthesized products were characterized by XRD, Infra- Red (FTIR) and SEM analysis. The XRD confirms the formation of Ni-MnO2 nanoparticles illustrate peak at 31.4° with lattice plane (-231). The IR spectra correspond to the peak at 592 and 846 cm-1 attributed to the characteristics peak for Ni-MnO2 nanoparticles. The SEM images for all three Ni-MnO2 nanoparticles for different concentration of CTAB allows us to assess the formation route of nano tentacles from 10 mM, 30 mM and 50 mM. The configured nano tentacles of Ni-MnO2 nanoparticles presumably leads to more significantly change its properties, particularly in its electrochemical properties show the ways to be suitable candidates for supercapacitor, battery, photo catalytic and fuel cell applications.

  15. 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

  16. 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...

  17. 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.

  18. 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

  19. 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.

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

    Code of Federal Regulations, 2011 CFR

    2011-07-01

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

  1. 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...

  2. Assessing the fate and effects of nano aluminum oxide in the terrestrial earthworm, Eisenia fetida.

    PubMed

    Coleman, Jessica G; Johnson, David R; Stanley, Jacob K; Bednar, Anthony J; Weiss, Charles A; Boyd, Robert E; Steevens, Jeffery A

    2010-07-01

    Nano-sized aluminum is currently being used by the military and commercial industries in many applications including coatings, thermites, and propellants. Due to the potential for wide dispersal in soil systems, we chose to investigate the fate and effects of nano-sized aluminum oxide (Al2O3), the oxidized form of nano aluminum, in a terrestrial organism. The toxicity and bioaccumulation potential of micron-sized (50-200 microm, nominal) and nano-sized (11 nm, nominal) Al2O3 was comparatively assessed through acute and subchronic bioassays using the terrestrial earthworm, Eisenia fetida. Subchronic (28-d) studies were performed exposing E. fetida to nano- and micron-sized Al2O3-spiked soils to assess the effects of long-term exposure. No mortality occurred in subchronic exposures, although reproduction decreased at >or=3,000 mg/kg nano-sized Al2O3 treatments, with higher aluminum body burdens observed at 100 and 300 mg/kg; no reproductive effects were observed in the micron-sized Al2O3 treatments. In addition to toxicity and bioaccumulation bioassays, an acute (48-h) behavioral bioassay was conducted utilizing a soil avoidance wheel in which E. fetida were given a choice of habitat between control, nano-, or micron-sized Al2O3 amended soils. In the soil avoidance bioassays, E. fetida exhibited avoidance behavior toward the highest concentrations of micron- and nano-sized Al2O3 (>5,000 mg/kg) relative to control soils. Results of the present study indicate that nano-sized Al2O3 may impact reproduction and behavior of E. fetida, although at high levels unlikely to be found in the environment. Copyright (c) 2010 SETAC.

  3. CO oxidation on Alsbnd Au nano-composite systems

    NASA Astrophysics Data System (ADS)

    Rajesh, C.; Majumder, C.

    2018-03-01

    Using first principles method we report the CO oxidation behaviour of Alsbnd Au nano-composites in three different size ranges: Al6Au8, Al13Au42 and a periodic slab of Alsbnd Au(1 1 1) surface. The clusters prefer enclosed structures with alternating arrangement of Al and Au atoms, maximising Auδ-sbnd Alδ+ bonds. Charge distribution analysis suggests the charge transfer from Al to Au atoms, corroborated by the red shift in the density of states spectrum. Further, CO oxidation on these nano-composite systems was investigated through both Eley - Rideal and Langmuir Hinshelwood mechanism. While, these clusters interact with O2 non-dissociatively with an elongation of the Osbnd O bond, further interaction with CO led to formation of CO2 spontaneously. On contrary, the CO2 evolution by co-adsorption of O2 and CO molecules has a transition state barrier. On the basis of the results it is inferred that nano-composite material of Alsbnd Au shows significant promise toward effective oxidative catalysis.

  4. Nano-size metallic oxide particle synthesis in Fe-Cr alloys by ion implantation

    NASA Astrophysics Data System (ADS)

    Zheng, C.; Gentils, A.; Ribis, J.; Borodin, V. A.; Delauche, L.; Arnal, B.

    2017-10-01

    Oxide Dispersion Strengthened (ODS) steels reinforced with metal oxide nanoparticles are advanced structural materials for nuclear and thermonuclear reactors. The understanding of the mechanisms involved in the precipitation of nano-oxides can help in improving mechanical properties of ODS steels, with a strong impact for their commercialization. A perfect tool to study these mechanisms is ion implantation, where various precipitate synthesis parameters are under control. In the framework of this approach, high-purity Fe-10Cr alloy samples were consecutively implanted with Al and O ions at room temperature and demonstrated a number of unexpected features. For example, oxide particles of a few nm in diameter could be identified in the samples already after ion implantation at room temperature. This is very unusual for ion beam synthesis, which commonly requires post-implantation high-temperature annealing to launch precipitation. The observed particles were composed of aluminium and oxygen, but additionally contained one of the matrix elements (chromium). The crystal structure of aluminium oxide compound corresponds to non-equilibrium cubic γ-Al2O3 phase rather than to more common corundum. The obtained experimental results together with the existing literature data give insight into the physical mechanisms involved in the precipitation of nano-oxides in ODS alloys.

  5. 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.

  6. 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.

  7. Nanostructured manganese oxide on silica aerogel: a new catalyst toward water oxidation.

    PubMed

    Najafpour, Mohammad Mahdi; Salimi, Saeideh; Madadkhani, Sepideh; Hołyńska, Małgorzata; Tomo, Tatsuya; Allakhverdiev, Suleyman I

    2016-12-01

    Herein we report on the synthesis and characterization of nano-sized Mn oxide/silica aerogel with low density as a good catalyst toward water oxidation. The composite was synthesized by a simple and low-cost hydrothermal procedure. In the next step, we studied the composite in the presence of cerium(IV) ammonium nitrate and photo-produced Ru(bpy) 3 3+ as a water-oxidizing catalyst. The low-density composite is a good Mn-based catalyst with turnover frequencies of ~0.3 and 0.5 (mmol O 2 /(mol Mn·s)) in the presence of Ru(bpy) 3 3+ and cerium(IV) ammonium nitrate, respectively. In addition to the water-oxidizing activities of the composite under different conditions, its self-healing reaction in the presence of cerium(IV) ammonium nitrate was also studied.

  8. 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.

  9. 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

  10. A submerged ceramic membrane reactor for the p-nitrophenol hydrogenation over nano-sized nickel catalysts.

    PubMed

    Chen, R Z; Sun, H L; Xing, W H; Jin, W Q; Xu, N P

    2009-02-01

    The catalytic hydrogenation of p-nitrophenol to p-aminophenol over nano-sized nickel catalysts was carried out in a submerged ceramic membrane reactor. It has been demonstrated that the submerged ceramic membrane reactor is more suitable for the p-nitrophenol hydrogenation over nano-sized nickel catalysts compared with the side-stream ceramic membrane reactor, and the membrane module configuration has a great influence on the reaction rate of p-nitrophenol hydrogenation and the membrane treating capacity. The deactivation of nano-sized nickel is mainly caused by the adsorption of impurity on the surface of nickel and the increase of oxidation degree of nickel.

  11. 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.

  12. 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

  13. Novel polyoxometalate silica nano-sized spheres: efficient catalysts for olefin oxidation and the deep desulfurization process.

    PubMed

    Nogueira, Lucie S; Ribeiro, Susana; Granadeiro, Carlos M; Pereira, Eulália; Feio, Gabriel; Cunha-Silva, Luís; Balula, Salete S

    2014-07-07

    A novel method to prepare silica nano-sized particles incorporating polyoxometalates was developed leading to a new efficient heterogeneous oxidative catalyst. Zinc-substituted polyoxotungstate [PW11Zn(H2O)O39](5-) (PW11Zn) was encapsulated into silica nanoparticles using a cross-linked organic-inorganic core, performed through successive spontaneous reactions in water. The potassium salt of PW11Zn and the composite formed, PW11Zn-APTES@SiO2, were characterized by a myriad of solid-state methods such as FT-IR, FT-Raman, (31)P and (13)C CP/MAS solid-state NMR, elemental analysis and SEM-EDS, confirming the integrity of the PW11Zn structure immobilized in the silica nanoparticles. The new composite has shown to be a versatile catalyst for the oxidation of olefins and also to catalyze the desulfurization of a model oil using H2O2 as the oxidant and acetonitrile as the solvent. The novel composite material was capable of being recycled without significant loss of activity and maintaining its structural stability for consecutive desulfurization and olefin oxidative cycles.

  14. Nano-fabricated size exclusion chromatograph

    NASA Technical Reports Server (NTRS)

    Svehla, D.; Feldman, S.; Feldman, J.; Grunthaner, F.; Shakkottai, P.; Castillo, L. del; White, V.

    2002-01-01

    This paper describes the development of a nano-fabricated size exclusion chromatograph (nSEC) based on the principle that molecules traveling through amicrocolumn containing nano-fabricated features will have characteristic elution times that directly correlate to molecular weight. Compared to conventional size exclusion chromatography, the nSEC offers greater control over the size exclusion process; mass fabrication; integration of the separation column with associated valves, pumps, and detectors; and dramatic reductions in instrument mass and power requirements.

  15. 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

  16. 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.

  17. Nano-sized Ni-doped carbon aerogel for supercapacitor.

    PubMed

    Lee, Yoon Jae; Jung, Ji Chul; Park, Sunyoung; Seo, Jeong Gil; Baeck, Sung-Hyeon; Yoon, Jung Rag; Yi, Jongheop; Song, In Kyu

    2011-07-01

    Carbon aerogel was prepared by polycondensation of resorcinol with formaldehyde using sodium carbonate as a catalyst in ambient conditions. Nano-sized Ni-doped carbon aerogel was then prepared by a precipitation method in an ethanol solvent. In order to elucidate the effect of nickel content on electrochemical properties, Ni-doped carbon aerogels (21, 35, 60, and 82 wt%) were prepared and their performance for supercapacitor electrode was investigated. Electrochemical properties of Ni-doped carbon aerogel electrodes were measured by cyclic voltammetry at a scan rate of 10 mV/sec and charge/discharge test at constant current of 1 A/g in 6 M KOH electrolyte. Among the samples prepared, 35 wt% Ni-doped carbon aerogel (Ni/CA-35) showed the highest capacitance (110 F/g) and excellent charge/discharge behavior. The enhanced capacitance of Ni-doped carbon aerogel was attributed to the faradaic redox reactions of nano-sized nickel oxide. Moreover, Ni-doped carbon aerogel exhibited quite stable cyclability, indicating long-term electrochemical stability.

  18. Nano-sized Mn3O4 and β-MnOOH from the decomposition of β-cyclodextrin-Mn: 2. The water-oxidizing activities.

    PubMed

    Najafpour, Mohammad Mahdi; Mostafalu, Ramin; Hołyńska, Małgorzata; Ebrahimi, Foad; Kaboudin, Babak

    2015-11-01

    Nano-sized Mn oxides contain Mn3O4, β-MnOOH and Mn2O3 have been prepared by a previously reported method using thermal decomposition of β-cyclodextrin-Mn complexes. In the next step, the water-oxidizing activities of these Mn oxides using cerium(IV) ammonium nitrate as a chemical oxidant are studied. The turnover frequencies for β-MnO(OH) and Mn3O4 are 0.24 and 0.01-0.17 (mmol O2/mol Mns), respectively. Subsequently, water-oxidizing activities of these compounds are compared to the other previously reported Mn oxides. Important factors affecting water oxidation by these Mn oxides are also discussed. Copyright © 2015 Elsevier B.V. All rights reserved.

  19. Twenty-Eight-Day Repeated Inhalation Toxicity Study of Nano-Sized Neodymium Oxide in Male Sprague-Dawley Rats

    PubMed Central

    Kim, Yong-Soon; Lim, Cheol-Hong; Shin, Seo-Ho; Kim, Jong-Choon

    2017-01-01

    Neodymium is a future-oriented material due to its unique properties, and its use is increasing in various industrial fields worldwide. However, the toxicity caused by repeated exposure to this metal has not been studied in detail thus far. The present study was carried out to investigate the potential inhalation toxicity of nano-sized neodymium oxide (Nd2O3) following a 28-day repeated inhalation exposure in male Sprague-Dawley rats. Male rats were exposed to nano-sized Nd2O3-containing aerosols via a nose-only inhalation system at doses of 0 mg/m3, 0.5 mg/m3, 2.5 mg/m3, and 10 mg/m3 for 6 hr/day, 5 days/week over a 28-day period, followed by a 28-day recovery period. During the experimental period, clinical signs, body weight, hematologic parameters, serum biochemical parameters, necropsy findings, organ weight, and histopathological findings were examined; neodymium distribution in the major organs and blood, bronchoalveolar lavage fluid (BALF), and oxidative stress in lung tissues were analyzed. Most of the neodymium was found to be deposited in lung tissues, showing a dose-dependent relationship. Infiltration of inflammatory cells and pulmonary alveolar proteinosis (PAP) were the main observations of lung histopathology. Infiltration of inflammatory cells was observed in the 2.5 mg/m3 and higher dose treatment groups. PAP was observed in all treatment groups accompanied by an increase in lung weight, but was observed to a lesser extent in the 0.5 mg/m3 treatment group. In BALF analysis, total cell counts, including macrophages and neutrophils, lactate dehydrogenase, albumin, interleukin-6, and tumor necrosis factor-alpha, increased significantly in all treatment groups. After a 4-week recovery period, these changes were generally reversed in the 0.5 mg/m3 group, but were exacerbated in the 10 mg/m3 group. The lowest-observed-adverse-effect concentration of nano-sized Nd2O3 was determined to be 0.5 mg/m3, and the target organ was determined to be the lung

  20. 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.

  1. 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.

  2. Gas sensing performance of nano zinc oxide sensors

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

    Sharma, Shiva, E-mail: shivasharmaau@gmail.com; Chauhan, Pratima, E-mail: mangu167@yahoo.co.in

    We report nano Zinc Oxide (ZnO) synthesized by sol-gel method possessing the crystallite size which varies from 25.17 nm to 47.27 nm. The Scanning electron microscope (SEM) image confirms the uniform distribution of nanograins with high porosity. The Energy dispersion X-ray (EDAX) spectrum gives the atomic composition of Zn and O in ZnO powders and confirms the formation of nano ZnO particles. These factors reveals that Nano ZnO based gas sensors are highly sensitive to Ammonia gas (NH{sub 3}) at room temperature, indicating the maximum response 86.8% at 800 ppm with fast response time and recovery time of 36 sec and 23 secmore » respectively.« less

  3. 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.

  4. Effects of micro-sized and nano-sized WO3 on mass attenauation coefficients of concrete by using MCNPX code.

    PubMed

    Tekin, H O; Singh, V P; Manici, T

    2017-03-01

    In the present work the effect of tungsten oxide (WO 3 ) nanoparticles on mass attenauation coefficients of concrete has been investigated by using MCNPX (version 2.4.0). The validation of generated MCNPX simulation geometry has been provided by comparing the results with standard XCOM data for mass attenuation coefficients of concrete. A very good agreement between XCOM and MCNPX have been obtained. The validated geometry has been used for definition of nano-WO 3 and micro-WO 3 into concrete sample. The mass attenuation coefficients of pure concrete and WO 3 added concrete with micro-sized and nano-sized have been compared. It was observed that shielding properties of concrete doped with WO 3 increased. The results of mass attenauation coefficients also showed that the concrete doped with nano-WO 3 significanlty improve shielding properties than micro-WO 3 . It can be concluded that addition of nano-sized particles can be considered as another mechanism to reduce radiation dose. Copyright © 2016 Elsevier Ltd. All rights reserved.

  5. 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.

  6. A Study on Formation and Thermal Stability of Nano-sized Oxide Clusters in Mechanically Alloyed Nickel Aluminum for High Temperature Applications

    NASA Astrophysics Data System (ADS)

    Kim, Yong-Deog

    The intermetallic compound, B2 NiAl, is a promising material for high temperature structural applications such as in aviation jet engines or gas turbines, provided that its high temperature mechanical properties can be improved. Although extensive efforts over the last several decades have been devoted toward enhancing ductility through alloying design and reducing impurities, as well as improving high temperature creep strength through precipitation and dispersion strengthening, these efforts have relied on traditional approaches, a combination of large grain size to limit diffusional creep and precipitation/dispersion (50 ˜ 100 nm size) strengthening to limit dislocation creep, for high temperature strengthening. While traditional approaches have shown a good improvement from a relatively high temperature strengthening point of view, the size and number density of dispersoids were not able to provide sufficient strength in the high temperature creep regime. Furthermore, details of the interaction mechanism between dislocations and dispersoids are not yet well understood. This study focuses on designing and developing advanced oxide dispersion strengthened (ODS) NiAl intermetallics with improved high temperature creep strength by incorporating a high number density (˜1024 m-3) of very thermally stable Y-Ti-O nano-clusters, akin to those recently observed to improve creep strength and radiation resistance in nano-structured ferritic alloys. Advanced ODS NiAl alloys have been produced by mechanical alloying of pre-alloyed Ni-50at%Al with Y2O3 and Ti elemental powders. The milled powders were subsequently consolidated by spark plasma sintering, with the objective of producing very high number densities of nano-sized Y-Ti-O precipitates, along with fine grain size. Advanced experimental characterization techniques, combined with microhardness strength measurement, were used to investigate the material microstructure and strength following processing and to evaluate

  7. Green chemistry synthesis of nano-cuprous oxide.

    PubMed

    Ceja-Romero, L R; Ortega-Arroyo, L; Ortega Rueda de León, J M; López-Andrade, X; Narayanan, J; Aguilar-Méndez, M A; Castaño, V M

    2016-04-01

    Green chemistry and a central composite design, to evaluate the effect of reducing agent, temperature and pH of the reaction, were employed to produce controlled cuprous oxide (Cu2O) nanoparticles. Response surface method of the ultraviolet-visible spectroscopy is allowed to determine the most relevant factors for the size distribution of the nanoCu2O. X-ray diffraction reflections correspond to a cubic structure, with sizes from 31.9 to 104.3 nm. High-resolution transmission electron microscopy reveals that the different shapes depend strongly on the conditions of the green synthesis.

  8. 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.

  9. 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 ).

  10. 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).

  11. 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.

  12. 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.

  13. Origin of Capacity Fading in Nano-Sized Co3O4 Electrodes: Electrochemical Impedance Spectroscopy Study

    NASA Astrophysics Data System (ADS)

    Kang, Jin-Gu; Ko, Young-Dae; Park, Jae-Gwan; Kim, Dong-Wan

    2008-10-01

    Transition metal oxides have been suggested as innovative, high-energy electrode materials for lithium-ion batteries because their electrochemical conversion reactions can transfer two to six electrons. However, nano-sized transition metal oxides, especially Co3O4, exhibit drastic capacity decay during discharge/charge cycling, which hinders their practical use in lithium-ion batteries. Herein, we prepared nano-sized Co3O4 with high crystallinity using a simple citrate-gel method and used electrochemical impedance spectroscopy method to examine the origin for the drastic capacity fading observed in the nano-sized Co3O4 anode system. During cycling, AC impedance responses were collected at the first discharged state and at every subsequent tenth discharged state until the 100th cycle. By examining the separable relaxation time of each electrochemical reaction and the goodness-of-fit results, a direct relation between the charge transfer process and cycling performance was clearly observed.

  14. 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.

  15. 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.

  16. Study on Locally Confined Deposition of Si Nanocrystals in High-Aspect-Ratio Si Nano-Pillar Arrays for Nano-Electronic and Nano-Photonic Applications II

    DTIC Science & Technology

    2010-12-03

    photoluminescence characteristics of equivalent-size controlled silicon quantum dots by employing a nano-porous aluminum oxide membrane as the template for growing...synthesis of Si quantum dots (Si-QDs) embedded in low-temperature (500oC) annealed Si-rich SiOx nano-rod deposited in nano-porous anodic aluminum oxide ...characteristics of the equivalent-size controlled Si-QDs by employing the nano-porous AAO membrane as the template for growing Si-rich SiOx nano-rods

  17. 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

  18. 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.

  19. 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

  20. 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.

  1. 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.

  2. Nano-Sized Structurally Disordered Metal Oxide Composite Aerogels as High-Power Anodes in Hybrid Supercapacitors.

    PubMed

    Huang, Haijian; Wang, Xing; Tervoort, Elena; Zeng, Guobo; Liu, Tian; Chen, Xi; Sologubenko, Alla; Niederberger, Markus

    2018-03-27

    A general method for preparing nano-sized metal oxide nanoparticles with highly disordered crystal structure and their processing into stable aqueous dispersions is presented. With these nanoparticles as building blocks, a series of nanoparticles@reduced graphene oxide (rGO) composite aerogels are fabricated and directly used as high-power anodes for lithium-ion hybrid supercapacitors (Li-HSCs). To clarify the effect of the degree of disorder, control samples of crystalline nanoparticles with similar particle size are prepared. The results indicate that the structurally disordered samples show a significantly enhanced electrochemical performance compared to the crystalline counterparts. In particular, structurally disordered Ni x Fe y O z @rGO delivers a capacity of 388 mAh g -1 at 5 A g -1 , which is 6 times that of the crystalline sample. Disordered Ni x Fe y O z @rGO is taken as an example to study the reasons for the enhanced performance. Compared with the crystalline sample, density functional theory calculations reveal a smaller volume expansion during Li + insertion for the structurally disordered Ni x Fe y O z nanoparticles, and they are found to exhibit larger pseudocapacitive effects. Combined with an activated carbon (AC) cathode, full-cell tests of the lithium-ion hybrid supercapacitors are performed, demonstrating that the structurally disordered metal oxide nanoparticles@rGO||AC hybrid systems deliver high energy and power densities within the voltage range of 1.0-4.0 V. These results indicate that structurally disordered nanomaterials might be interesting candidates for exploring high-power anodes for Li-HSCs.

  3. 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.

  4. 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.

  5. Urban runoff treatment using nano-sized iron oxide coated sand with and without magnetic field applying

    PubMed Central

    2013-01-01

    Increase of impervious surfaces in urban area followed with increases in runoff volume and peak flow, leads to increase in urban storm water pollution. The polluted runoff has many adverse impacts on human life and environment. For that reason, the aim of this study was to investigate the efficiency of nano iron oxide coated sand with and without magnetic field in treatment of urban runoff. In present work, synthetic urban runoff was treated in continuous separate columns system which was filled with nano iron oxide coated sand with and without magnetic field. Several experimental parameters such as heavy metals, turbidity, pH, nitrate and phosphate were controlled for investigate of system efficiency. The prepared column materials were characterized with Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray analysis (EDXA) instruments. SEM and EDXA analyses proved that the sand has been coated with nano iron oxide (Fe3O4) successfully. The results of SEM and EDXA instruments well demonstrate the formation of nano iron oxide (Fe3O4) on sand particle. Removal efficiency without magnetic field for turbidity; Pb, Zn, Cd and PO4 were observed to be 90.8%, 73.3%, 75.8%, 85.6% and 67.5%, respectively. When magnetic field was applied, the removal efficiency for turbidity, Pb, Zn, Cd and PO4 was increased to 95.7%, 89.5%, 79.9%, 91.5% and 75.6% respectively. In addition, it was observed that coated sand and magnetic field was not able to remove NO3 ions. Statistical analyses of data indicated that there was a significant difference between removals of pollutants in two tested columns. Results of this study well demonstrate the efficiency of nanosized iron oxide-coated sand in treatment of urban runoff quality; upon 75% of pollutants could be removed. In addition, in the case of magnetic field system efficiency can be improved significantly. PMID:24360061

  6. 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.

  7. 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

  8. 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

  9. 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.

  10. 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

  11. Characteristics of Sodium Polyacrylate/Nano-Sized Carbon Hydrogel for Biomedical Patch.

    PubMed

    Park, Jong-Kyu; Seo, Sun-Kyo; Cho, Seungkwan; Kim, Han-Sung; Lee, Chi-Hwan

    2018-03-01

    Conductive hydrogels were prepared for biomedical patch in order to improve the electrical conductivity. Sodium polyacrylate and nano-sized carbon were mixed and fabricated by aqueous solution gelation process in various contents of nano-sized carbon with 0.1, 0.5, 1.0 and 2.0 wt%. Sodium polyacrylate/nano-sized carbon conductive hydrogels were investigated by molecular structure, surface morphology and electrical conductivity. The conductivity of the hydrogel/nano-sized carbon conductive hydrogel proved to be 10% higher than conductive hydrogel without nano-sized carbon. However, it was founded that conductive hydrogels with nano-sized carbon content from 0.5 up to 2.0 wt% were remarkably decreased. This may be due to the non-uniform distribution of nano-sized carbon, resulting from agglomerates of nano-sized carbon. The developed hydrogel is intended for use in the medical and cosmetic fields that is applicable to supply micro-current from device to human body.

  12. 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.

  13. 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

  14. 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.

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. 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

  20. Characterization of Total and Size-Fractionated Manganese Exposure by Work Area in a Shipbuilding Yard.

    PubMed

    Jeong, Jee Yeon; Park, Jong Su; Kim, Pan Gyi

    2016-06-01

    Shipbuilding involves intensive welding activities, and welders are exposed to a variety of metal fumes, including manganese, that may be associated with neurological impairments. This study aimed to characterize total and size-fractionated manganese exposure resulting from welding operations in shipbuilding work areas. In this study, we characterized manganese-containing particulates with an emphasis on total mass (n = 86, closed-face 37-mm cassette samplers) and particle size-selective mass concentrations (n = 86, 8-stage cascade impactor samplers), particle size distributions, and a comparison of exposure levels determined using personal cassette and impactor samplers. Our results suggest that 67.4% of all samples were above the current American Conference of Governmental Industrial Hygienists manganese threshold limit value of 100 μg/m(3) as inhalable mass. Furthermore, most of the particles containing manganese in the welding process were of the size of respirable particulates, and 90.7% of all samples exceeded the American Conference of Governmental Industrial Hygienists threshold limit value of 20 μg/m(3) for respirable manganese. The concentrations measured with the two sampler types (cassette: total mass; impactor: inhalable mass) were significantly correlated (r = 0.964, p < 0.001), but the total concentration obtained using cassette samplers was lower than the inhalable concentration of impactor samplers.

  1. 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.

  2. 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.

  3. 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

  4. Effect of morphology and solvent on two-photon absorption of nano zinc oxide

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

    Kavitha, M.K.; Haripadmam, P.C.; Gopinath, Pramod

    Highlights: ► ZnO nanospheres and triangular structures synthesis by novel precipitation technique. ► The effect of precursor concentration on the size and shape of nano ZnO. ► Open aperture Z-scan measurements of the ZnO nanoparticle dispersions. ► Nanospheres exhibit higher two photon absorption coefficient than triangular nanostructures. ► Nanospheres dispersed in water exhibit higher two photon absorption coefficient than its dispersion in 2-propanol. - Abstract: In this paper, we report the effect of morphology and solvent on the two-photon absorption of nano zinc oxide. Zinc oxide nanoparticles in two different morphologies like nanospheres and triangular nanostructures are synthesized by novelmore » precipitation technique and their two-photon absorption coefficient is measured using open aperture Z-scan technique. Experimental results show that the zinc oxide nanospheres exhibit higher two-photon absorption coefficient than the zinc oxide triangular nanostructures. The zinc oxide nanospheres dispersed in water exhibit higher two-photon absorption coefficient than that of its dispersion in 2-propanol. The zinc oxide nanospheres dispersed in water shows a decrease in two-photon absorption coefficient with an increase in on-axis irradiance. The result confirms the dependence of shape and solvent on the two-photon absorption of nano zinc oxide.« less

  5. 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.

  6. 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

  7. Small angle neutron scattering study of nano sized microstructure in Fe-Cr ODS steels for gen IV in-core applications.

    PubMed

    Han, Young-Soo; Mao, Xiadong; Jang, Jinsung

    2013-11-01

    The nano-sized microstructures in Fe-Cr oxide dispersion strengthened steel for Gen IV in-core applications were studied using small angle neutron scattering. The oxide dispersion strengthened steel was manufactured through hot isostatic pressing with various chemical compositions and fabrication conditions. Small angle neutron scattering experiments were performed using a 40 m small angle neutron scattering instrument at HANARO. Nano sized microstructures, namely, yttrium oxides and Cr-oxides were quantitatively analyzed by small angle neutron scattering. The yttrium oxides and Cr-oxides were also observed by transmission electron microscopy. The microstructural analysis results from small angle neutron scattering were compared with those obtained by transmission electron microscopy. The effects of the chemical compositions and fabrication conditions on the microstructure were investigated in relation to the quantitative microstructural analysis results obtained by small angle neutron scattering. The volume fraction of Y-oxide increases after fabrication, and this result is considered to be due to the formation of non-stochiometric Y-Ti-oxides.

  8. 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.

  9. Initial stage oxidation on nano-trenched Si(1 0 0) surface

    NASA Astrophysics Data System (ADS)

    Sun, Yu; Liu, Yi-Lun; Izumi, Satoshi; Chen, Xue-Feng; Zhai, Zhi; Tian, Shao-Hua

    2018-01-01

    As the size of an electronic element shrinks to nanoscale, trench design of Si strongly influences the performance of related semiconductor devices. By reactive force field molecular dynamics (ReaxFF MD) simulation, the initial stage oxidation on nano-trenched Si(1 0 0) angled 60°, 90°, 120°, 150° under temperatures from 300 K to 1200 K has been studied. Inhomogeneous oxidation at the convex-concave corners of the Si surface was observed. In general, the initial oxidation process on the Si surface was that, firstly, the O atoms ballistically transported into surface, then a high O concentration induced compressive stress at the surface layers, which prevented further oxidation. Compared to the concave corner, the convex one contacted a larger volume of oxygen at the very beginning stage, leading an anisotropic absorption of O atoms. Afterwards, a critical compression was produced at both the convex and concave corners to limit the oxidation. As a result, an inhomogeneous oxide film grew on nano-trenched Si. Meanwhile, due to enhanced O transport and compression relaxation by increasing temperature, the inhomogeneous oxidation was more obvious under 1200 K. These present results explained the observed experimental phenomena on the oxidation of non-planar Si and provided an aspect on the design of nano-trenched electronic components in the semiconductor field.

  10. 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

  11. 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

  12. 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.

  13. 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.

  14. Nano lead oxide and epdm composite for development of polymer based radiation shielding material: Gamma irradiation and attenuation tests

    NASA Astrophysics Data System (ADS)

    Özdemir, T.; Güngör, A.; Akbay, I. K.; Uzun, H.; Babucçuoglu, Y.

    2018-03-01

    It is important to have a shielding material that is not easily breaking in order to have a robust product that guarantee the radiation protection of the patients and radiation workers especially during the medical exposure. In this study, nano sized lead oxide (PbO) particles were used, for the first time, to obtain an elastomeric composite material in which lead oxide nanoparticles, after the surface modification with silane binding agent, was used as functional material for radiation shielding. In addition, the composite material including 1%, 5%, 10%, 15% and 20% weight percent nano sized lead oxide was irradiated with doses of 81, 100 and 120 kGy up to an irradiation period of 248 days in a gamma ray source with an initial dose rate of 21.1 Gy/h. Mechanical, thermal properties of the irradiated materials were investigated using DSC, DMA, TGA and tensile testing and modifications in thermal and mechanical properties of the nano lead oxide containing composite material via gamma irradiation were reported. Moreover, effect of bismuth-III oxide addition on radiation attenuation of the composite material was investigated. Nano lead oxide and bismuth-III oxide particles were mixed with different weight ratios. Attenuation tests have been conducted to determine lead equivalent values for the developed composite material. Lead equivalent thickness values from 0.07 to 0.65 (2-6 mm sample thickness) were obtained.

  15. 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.

  16. 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.

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

    PubMed

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

    2015-09-30

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

  18. 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

  19. 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.

  20. 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.

  1. 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.

  2. Silica-F127 nanohybrid-encapsulated manganese oxide nanoparticles for optimized T1 magnetic resonance relaxivity

    NASA Astrophysics Data System (ADS)

    Wei Hsu, Benedict You; Wang, Miao; Zhang, Yu; Vijayaragavan, Vimalan; Wong, Siew Yee; Yuang-Chi Chang, Alex; Bhakoo, Kishore Kumar; Li, Xu; Wang, John

    2013-12-01

    To properly engineer MnO nanoparticles (MONPs) of high r1 relaxivity, a nanohybrid coating consisting of silica and F127 (PEO106PPO70PEO106) is designed to encapsulate MONPs. Achieved by an interfacial templating scheme, the nanohybrid encapsulating layer is highly permeable and hydrophilic to allow for an optimal access of water molecules to the encapsulated manganese oxide core. Hence, the efficacy of MONPs as MRI contrast agents is significantly improved, as demonstrated by an enhancement of the MR signal measured with a pre-clinical 7.0 T MRI scanner. The nanohybrid encapsulation strategy also confers high colloidal stability to the hydrophobic MONPs by the surface decoration of PEO chains and a small overall diameter (<100 nm) of the PEO-SiO2 nanohybrid-encapsulated MONPs (PEOMSNs). The PEOMSNs are not susceptible to Mn-ion leaching, and their biocompatibility is affirmed by a low toxicity profile. Moreover, these hybrid nanocapsules exhibit a nano-rattle structure, which would favor the facile loading of various therapeutic reagents for theranostic applications.To properly engineer MnO nanoparticles (MONPs) of high r1 relaxivity, a nanohybrid coating consisting of silica and F127 (PEO106PPO70PEO106) is designed to encapsulate MONPs. Achieved by an interfacial templating scheme, the nanohybrid encapsulating layer is highly permeable and hydrophilic to allow for an optimal access of water molecules to the encapsulated manganese oxide core. Hence, the efficacy of MONPs as MRI contrast agents is significantly improved, as demonstrated by an enhancement of the MR signal measured with a pre-clinical 7.0 T MRI scanner. The nanohybrid encapsulation strategy also confers high colloidal stability to the hydrophobic MONPs by the surface decoration of PEO chains and a small overall diameter (<100 nm) of the PEO-SiO2 nanohybrid-encapsulated MONPs (PEOMSNs). The PEOMSNs are not susceptible to Mn-ion leaching, and their biocompatibility is affirmed by a low toxicity profile

  3. 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 © 2010 Elsevier Ltd. All rights reserved.

  4. Defect Clustering and Nano-Phase Structure Characterization of Multi-Component Rare Earth Oxide Doped Zirconia-Yttria Thermal Barrier Coatings

    NASA Technical Reports Server (NTRS)

    Zhu, Dongming; Chen, Yuan L.; Miller, Robert A.

    2003-01-01

    Advanced oxide thermal barrier coatings have been developed by incorporating multi-component rare earth oxide dopants into zirconia-yttria to effectively promote the creation of the thermodynamically stable, immobile oxide defect clusters and/or nano-scale phases within the coating systems. The presence of these nano-sized defect clusters has found to significantly reduce the coating intrinsic thermal conductivity, improve sintering resistance, and maintain long-term high temperature stability. In this paper, the defect clusters and nano-structured phases, which were created by the addition of multi-component rare earth dopants to the plasma-sprayed and electron-beam physical vapor deposited thermal barrier coatings, were characterized by high-resolution transmission electron microscopy (TEM). The defect cluster size, distribution, crystallographic and compositional information were investigated using high-resolution TEM lattice imaging, selected area diffraction (SAD), electron energy-loss spectroscopy (EELS) and energy dispersive spectroscopy (EDS) analysis techniques. The results showed that substantial defect clusters were formed in the advanced multi-component rare earth oxide doped zirconia- yttria systems. The size of the oxide defect clusters and the cluster dopant segregation was typically ranging from 5 to 50 nm. These multi-component dopant induced defect clusters are an important factor for the coating long-term high temperature stability and excellent performance.

  5. Defect Clustering and Nano-Phase Structure Characterization of Multi-Component Rare Earth Oxide Doped Zirconia-Yttria Thermal Barrier Coatings

    NASA Technical Reports Server (NTRS)

    Zhu, Dongming; Chen, Yuan L.; Miller, Robert A.

    1990-01-01

    Advanced oxide thermal barrier coatings have been developed by incorporating multi- component rare earth oxide dopants into zirconia-yttria to effectively promote the creation of the thermodynamically stable, immobile oxide defect clusters and/or nano-scale phases within the coating systems. The presence of these nano-sized defect clusters has found to significantly reduce the coating intrinsic thermal conductivity, improve sintering resistance, and maintain long-term high temperature stability. In this paper, the defect clusters and nano-structured phases, which were created by the addition of multi-component rare earth dopants to the plasma- sprayed and electron-beam physical vapor deposited thermal barrier coatings, were characterized by high-resolution transmission electron microscopy (TEM). The defect cluster size, distribution, crystallographic and compositional information were investigated using high-resolution TEM lattice imaging, selected area diffraction (SAD), and energy dispersive spectroscopy (EDS) analysis techniques. The results showed that substantial defect clusters were formed in the advanced multi-component rare earth oxide doped zirconia-yttria systems. The size of the oxide defect clusters and the cluster dopant segregation was typically ranging fiom 5 to 50 nm. These multi-component dopant induced defect clusters are an important factor for the coating long-term high temperature stability and excellent performance.

  6. 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.

  7. 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.

  8. Size-separated particle fractions of stainless steel welding fume particles - A multi-analytical characterization focusing on surface oxide speciation and release of hexavalent chromium.

    PubMed

    Mei, N; Belleville, L; Cha, Y; Olofsson, U; Odnevall Wallinder, I; Persson, K-A; Hedberg, Y S

    2018-01-15

    Welding fume of stainless steels is potentially health hazardous. The aim of this study was to investigate the manganese (Mn) and chromium (Cr) speciation of welding fume particles and their extent of metal release relevant for an inhalation scenario, as a function of particle size, welding method (manual metal arc welding, metal arc welding using an active shielding gas), different electrodes (solid wires and flux-cored wires) and shielding gases, and base alloy (austenitic AISI 304L and duplex stainless steel LDX2101). Metal release investigations were performed in phosphate buffered saline (PBS), pH 7.3, 37°, 24h. The particles were characterized by means of microscopic, spectroscopic, and electroanalytical methods. Cr was predominantly released from particles of the welding fume when exposed in PBS [3-96% of the total amount of Cr, of which up to 70% as Cr(VI)], followed by Mn, nickel, and iron. Duplex stainless steel welded with a flux-cored wire generated a welding fume that released most Cr(VI). Nano-sized particles released a significantly higher amount of nickel compared with micron-sized particle fractions. The welding fume did not contain any solitary known chromate compounds, but multi-elemental highly oxidized oxide(s) (iron, Cr, and Mn, possibly bismuth and silicon). Copyright © 2017 The Authors. Published by Elsevier B.V. All rights reserved.

  9. Color stability of pigmented maxillofacial silicone elastomer: effects of nano-oxides as opacifiers.

    PubMed

    Han, Ying; Zhao, Yimin; Xie, Chao; Powers, John M; Kiat-amnuay, Sudarat

    2010-01-01

    This study evaluated the effects of nano-oxides on the color stability of pigmented silicone A-2186 maxillofacial prosthetic elastomers before and after artificial aging. Each of three widely used UV-shielding nano-sized particle oxides (TiO(2), ZnO, CeO(2)), based on recent survey of the industry at 1%, 2%, 2.5% concentrations were combined with each of five intrinsic silicone pigment types (no pigments, red, yellow, blue, and a mixture of the three pigments). Silicone A-2186 without nano-oxides or pigments served as control, for a total of 46 experimental groups of elastomers. In each group of the study, all specimens were aged in an artificial aging chamber for an energy exposure of 450kJ/m(2). CIE L*a*b* values were measured by a spectrophotometer. The 50:50% perceptibility (ΔE*=1.1) and acceptability threshold (ΔE*=3.0) were used in interpretation of recorded color differences. Color differences after aging were subjected to three-way analysis of variance. Means were compared by Fisher's PLSD intervals at the 0.05 level of significance. Yellow pigments mixed with all three nano-oxides at all intervals increased ΔE* values significantly from 3.7 up to 8.4. When mixed pigment groups were considered, TiO(2) at 2%, and 2.5% exhibited the smallest color changes, followed by ZnO and CeO(2), respectively (p<0.001). At 1%, CeO(2) exhibited the smallest color changes, followed by TiO(2) and ZnO, respectively (p<0.001). The smallest color differences, observed for nano-oxides groups, were recorded for CeO(2) at 1%, and TiO(2) at 2% and 2.5%. When the nano-oxides were tested at all concentrations, CeO(2) groups overall had the most color changes, and TiO(2) groups had the least. All ΔE* values of the mixed pigment groups were below the 50:50% acceptability threshold (ΔE*=1.2-2.3, below 3.0) except 2% CeO(2) (ΔE*=4.2). 1% nano-CeO(2) and 2% and 2.5% nano-TiO(2) used as opacifiers for silicone A-2186 maxillofacial prostheses with mixed pigments exhibited the least

  10. Solid oxide fuel cell cathode infiltrate particle size control and oxygen surface exchange resistance determination

    NASA Astrophysics Data System (ADS)

    Burye, Theodore E.

    Over the past decade, nano-sized Mixed Ionic Electronic Conducting (MIEC) -- micro-sized Ionic Conducting (IC) composite cathodes produced by the infiltration method have received much attention in the literature due to their low polarization resistance (RP) at intermediate (500-700°C) operating temperatures. Small infiltrated MIEC oxide nano-particle size and low intrinsic MIEC oxygen surface exchange resistance (Rs) have been two critical factors allowing these Nano-Micro-Composite Cathodes (NMCCs) to achieve high performance and/or low temperature operation. Unfortunately, previous studies have not found a reliable method to control or reduce infiltrated nano-particle size. In addition, controversy exists on the best MIEC infiltrate composition because: 1) Rs measurements on infiltrated MIEC particles are presently unavailable in the literature, and 2) bulk and thin film Rs measurements on nominally identical MIEC compositions often vary by up to 3 orders of magnitude. Here, two processing techniques, precursor nitrate solution desiccation and ceria oxide pre-infiltration, were developed to systematically produce a reduction in the average La0.6Sr0.4Co0.8Fe 0.2O3-delta (LSCF) infiltrated nano-particle size from 50 nm to 22 nm. This particle size reduction reduced the SOFC operating temperature, (defined as the temperature where RP=0.1 Ocm 2) from 650°C to 540°C. In addition, Rs values for infiltrated MIEC particles were determined for the first time through finite element modeling calculations on 3D Focused Ion Beam-Scanning Electron Microscope (FIB-SEM) reconstructions of electrochemically characterized infiltrated electrodes.

  11. 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.

  12. Implication of oxidative stress in size-dependent toxicity of silica nanoparticles in kidney cells.

    PubMed

    Passagne, Isabelle; Morille, Marie; Rousset, Marine; Pujalté, Igor; L'azou, Béatrice

    2012-09-28

    Silica nanoparticles (nano-SiO(2)) are one of the most popular nanomaterials used in industrial manufacturing, synthesis, engineering and medicine. While inhalation of nanoparticles causes pulmonary damage, nano-SiO(2) can be transported into the blood and deposit in target organs where they exert potential toxic effects. Kidney is considered as such a secondary target organ. However, toxicological information of their effect on renal cells and the mechanisms involved remain sparse. In the present study, the cytotoxicity of nano-SiO(2) of different sizes was investigated on two renal proximal tubular cell lines (human HK-2 and porcine LLC-PK(1)). The molecular pathways involved were studied with a focus on the involvement of oxidative stress. Nanoparticle characterization was performed (primary nanoparticle size, surface area, dispersion) in order to investigate a potential relationship between their physical properties and their toxic effects. Firstly, evidence of particle internalization was obtained by transmission electron microscopy and conventional flux cytometry techniques. The use of specific inhibitors of endocytosis pathways showed an internalization process by macropinocytosis and clathrin-mediated endocytosis for 100 nm nano-SiO(2) nanoparticles. These nanoparticles were localized in vesicles. Toxicity was size- and time-dependent (24h, 48 h, 72 h). Indeed, it increased as nanoparticles became smaller. Secondly, analysis of oxidative stress based on the assessment of ROS (reactive oxygen species) production (DHE, dihydroethidium) or lipid peroxidation (MDA, malondialdehyde) clearly demonstrated the involvement of oxidative stress in the toxicity of 20 nm nano-SiO(2). The induction of antioxidant enzymes (catalase, GSTpi, thioredoxin reductase) could explain their lesser toxicity with 100 nm nano-SiO(2). Copyright © 2012 Elsevier Ireland Ltd. All rights reserved.

  13. 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 +]…

  14. 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.

  15. Photocatalytic treatment of RDX wastewater with nano-sized titanium dioxide.

    PubMed

    Liu, Zongkuan; He, Yanling; Li, Feng; Liu, Yonghong

    2006-09-01

    The polynitramines, hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX), octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX), are important military explosives and regulated toxic hazardous compounds. Production, testing and use of the compounds has resulted in numerous acres of contaminated soils and groundwater near many munitions facilities. Economical and efficient methods for treatment of wastewater and cleanup of soils or groundwater containing RDX and HMX are needed. This study focuses on the photocatalytic treatment of RDX wastewater with nano-sized titanium dioxide (nano-TiO2) under simulated sunlight, whose intensity and wavelength are similar to that of the real sunlight in Xi'an at noon. The objective is to determine the potential for RDX destruction with nano-TiO2 in aqueous solution. An activated carbon fiber (ACF) cloth-loaded with nano-TiO2 was put into the RDX containing solution, and the concentration of RDX was measured (by HPLC-UV) at regular time intervals under simulated sunlight. The RDX degradation percentage of the photocatalytic process is higher than that of Fenton oxidation before 80 min, equivalent after 80 min, and it reaches 95% or above after 120 min. The nano-TiO2 catalyst can be used repeatedly. The photocatalytic degradation kinetics of RDX under simulated sunlight can be described by a first-order reaction kinetics equation. The possible degradation mechanism of RDX was presented and the degradation performance was compared with that of biological method. It was demonstrated that the degradation of RDX wastewater is very effective with nano-TiO2 as the photocatalytic catalyst under simulated sunlight. The efficiency of the nano-TiO2 catalyst for RDX degradation under simulated sunlight is nearly identical to that of Fenton oxidation. To date, a number of catalysts show poor absorption and utilization of sunlight, and still need ultraviolet light irradiation during wastewater degradation. The nano-TiO2 used in the described

  16. 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.

  17. Chemical Dynamics of nano-Aluminum and Iodine Based Oxidizers

    NASA Astrophysics Data System (ADS)

    Little, Brian; Ridge, Claron; Overdeep, Kyle; Slizewski, Dylan; Lindsay, Michael

    2017-06-01

    As observed in previous studies of nanoenergetic powder composites, micro/nano-structural features such as particle morphology and/or reactant spatial distance are expected to strongly influence properties that govern the combustion behavior of energetic materials (EM). In this study, highly reactive composites containing crystalline iodine (V) oxide or iodate salts with nano-sized aluminum (nAl) were blended by two different processing techniques and then collected as a powder for characterization. Physiochemical techniques such as thermal gravimetric analysis, calorimetry, X-ray diffraction, electron microscopy, high speed photography, pressure profile analysis, temperature programmed reactions, and spectroscopy were employed to characterize these EM with emphasis on correlating the chemical reactivity with inherent structural features and variations in stoichiometry. This work is a continuation of efforts to probe the chemical dynamics of nAl-iodine based composites.

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. Thermal Stress Behavior of Micro- and Nano-Size Aluminum Films

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

    Hanabusa, T.; Kusaka, K.; Nishida, M.

    2008-03-17

    In-situ observation of thermal stresses in thin films deposited on silicon substrate was made by X-ray and synchrotron radiation. Specimens prepared in this experiment were micro- and nano-size thin aluminum films with and without passivation film. The thickness of the film was 1 micrometer for micro-size films and 10, 20 and 50 nanometer for nano-size films. The stress measurement in micro-size films was made by X-ray radiation whereas the measurement of nano-size films was made by synchrotron radiation. Residual stress measurement revealed tensile stresses in all as-deposited films. Thermal stresses were measured in a series of heating- and cooling-stage. Thermalmore » stress behavior of micro-size films revealed hysteresis loop during a heating and cooling process. The width of a hysteresis loop was larger in passivated film that unpassivated film. No hysteresis loops were observed in nano-size films with SiO{sub 2} passivation. Strengthning mechanism in thin films was discussed on a passivation film and a film thickness.« less

  3. Sonochemical syntheses of a new nano-sized porous lead(II) coordination polymer as precursor for preparation of lead(II) oxide nanoparticles

    NASA Astrophysics Data System (ADS)

    Ranjbar, Zohreh Rashidi; Morsali, Ali

    2009-11-01

    Nano-scale of a new Pb(II) coordination polymer, {[Pb(bpacb)(OAc)]·DMF} n ( 1); bpacbH = 3,5-bis[(4-pyridylamino)carbonyl]benzoic acid], were synthesized by a sonochemical method. The nano-material was characterized by scanning electron microscopy, X-ray powder diffraction (XRD), 1H, 13C NMR, IR spectroscopy and elemental analyses. Crystal structure of compound 1 was determined by X-ray crystallography. Calcination of the nano-sized compound 1 at 700 °C under air atmospheres yields PbO nanoparticles. Thermal stability of nano-sized and single crystalline samples of compound 1 were studied and compared with each other.

  4. Efficient recovery of nano-sized iron oxide particles from synthetic acid-mine drainage (AMD) water using fuel cell technologies.

    PubMed

    Cheng, Shaoan; Jang, Je-Hun; Dempsey, Brian A; Logan, Bruce E

    2011-01-01

    Acid mine drainage (AMD) is an important contributor to surface water pollution due to the release of acid and metals. Fe(II) in AMD reacts with dissolved oxygen to produce iron oxide precipitates, resulting in further acidification, discoloration of stream beds, and sludge deposits in receiving waters. It has recently been shown that new fuel cell technologies, based on microbial fuel cells, can be used to treat AMD and generate electricity. Here we show that this approach can also be used as a technique to generate spherical nano-particles of iron oxide that, upon drying, are transformed to goethite (α-FeOOH). This approach therefore provides a relatively straightforward way to generate a product that has commercial value. Particle diameters ranged from 120 to 700 nm, with sizes that could be controlled by varying the conditions in the fuel cell, especially current density (0.04-0.12 mA/cm(2)), pH (4-7.5), and initial Fe(II) concentration (50-1000 mg/L). The most efficient production of goethite and power occurred with pH = 6.3 and Fe(II) concentrations above 200 mg/L. These results show that fuel cell technologies can not only be used for simultaneous AMD treatment and power generation, but that they can generate useful products such as iron oxide particles having sizes appropriate for used as pigments and other applications. Copyright © 2010 Elsevier Ltd. All rights reserved.

  5. 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.

  6. 3D Oxidized Graphene Frameworks for Efficient Nano Sieving

    PubMed Central

    Pawar, Pranav Bhagwan; Saxena, Sumit; Badhe, Dhanashree Kamlesh; Chaudhary, Raghvendra Pratap; Shukla, Shobha

    2016-01-01

    The small size of Na+ and Cl− ions provides a bottleneck in desalination and is a challenge in providing alternatives for continuously depleting fresh water resources. Graphene by virtue of its structural properties has the potential to address this issue. Studies have indicated that use of monolayer graphene can be used to filter micro volumes of saline solution. Unfortunately it is extremely difficult, resource intensive and almost impractical with current technology to fabricate operational devices using mono-layered graphene. Nevertheless, graphene based devices still hold the key to solve this problem due to its nano-sieving ability. Here we report synthesis of oxidized graphene frameworks and demonstrate a functional device to desalinate and purify seawater from contaminants including Na+ and Cl− ions, dyes and other microbial pollutants. Micro-channels in these frameworks help in immobilizing larger suspended solids including bacteria, while nano-sieving through graphene enables the removal of dissolved ions (e.g. Cl−). Nano-sieving incorporated with larger frameworks has been used in filtering Na+ and Cl− ions in functional devices. PMID:26892277

  7. 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.

  8. Nano-sized Adsorbate Structure Formation in Anisotropic Multilayer System

    NASA Astrophysics Data System (ADS)

    Kharchenko, Vasyl O.; Kharchenko, Dmitrii O.; Yanovsky, Vladimir V.

    2017-05-01

    In this article, we study dynamics of adsorbate island formation in a model plasma-condensate system numerically. We derive the generalized reaction-diffusion model for adsorptive multilayer system by taking into account anisotropy in transfer of adatoms between neighbor layers induced by electric field. It will be found that with an increase in the electric field strength, a structural transformation from nano-holes inside adsorbate matrix toward separated nano-sized adsorbate islands on a substrate is realized. Dynamics of adsorbate island sizes and corresponding distributions are analyzed in detail. This study provides an insight into details of self-organization of adatoms into nano-sized adsorbate islands in anisotropic multilayer plasma-condensate systems.

  9. Nano-graphene oxide carboxylation for efficient bioconjugation applications: a quantitative optimization approach

    NASA Astrophysics Data System (ADS)

    Imani, Rana; Emami, Shahriar Hojjati; Faghihi, Shahab

    2015-02-01

    A method for carboxylation of graphene oxide (GO) with chloroacetic acid that precisely optimizes and controls the efficacy of the process for bioconjugation applications is proposed. Quantification of COOH groups on nano-graphene oxide sheets (NGOS) is performed by novel colorimetric methylene blue (MB) assay. The GO is synthesized and carboxylated by chloroacetic acid treatment under strong basic condition. The size and morphology of the as-prepared NGOS are characterized by scanning electron microscopy, transmission electron microscopy (TEM), and atomic force microscopy (AFM). The effect of acid to base molar ratio on the physical, chemical, and morphological properties of NGOS is analyzed by Fourier-transformed infrared spectrometry (FTIR), UV-Vis spectroscopy, X-ray diffraction (XRD), AFM, and zeta potential. For evaluation of bioconjugation efficacy, the synthesized nano-carriers with different carboxylation ratios are functionalized by octaarginine peptide sequence (R8) as a biomolecule model containing amine groups. The quantification of attached R8 peptides to graphene nano-sheets' surface is performed with a colorimetric-based assay which includes the application of 2,4,6-Trinitrobenzene sulfonic acid (TNBS). The results show that the thickness and lateral size of nano-sheets are dramatically decreased to 0.8 nm and 50-100 nm after carboxylation process, respectively. X-ray analysis shows the nano-sheets interlaying space is affected by the alteration of chloroacetic acid to base ratio. The MB assay reveals that the COOH groups on the surface of NGOS are maximized at the acid to base ratio of 2 which is confirmed by FTIR, XRD, and zeta potential. The TNBS assay also shows that bioconjugation of the optimized carboxylated NGOS sample with octaarginine peptide is 2.5 times more efficient compared to bare NGOS. The present work provides evidence that treatment of GO by chloroacetic acid under an optimized condition would create a functionalized high surface

  10. Electrochemical water splitting using nano-zeolite Y supported tungsten oxide electrocatalysts

    NASA Astrophysics Data System (ADS)

    Anis, Shaheen Fatima; Hashaikeh, Raed

    2018-02-01

    Zeolites are often used as supports for metals and metal oxides because of their well-defined microporous structure and high surface area. In this study, nano-zeolite Y (50-150 nm range) and micro-zeolite Y (500-800 nm range) were loaded with WO3, by impregnating the zeolite support with ammonium metatungstate and thermally decomposing the salt thereafter. Two different loadings of WO3 were studied, 3 wt.% and 5 wt.% with respect to the overall catalyst. The prepared catalysts were characterized for their morphology, structure, and surface areas through scanning electron microscope (SEM), XRD, and BET. They were further compared for their electrocatalytic activity for hydrogen evolution reaction (HER) in 0.5 M H2SO4. On comparing the bare micro-zeolite particles with the nano-form, the nano-zeolite Y showed higher currents with comparable overpotentials and lower Tafel slope of 62.36 mV/dec. WO3 loading brought about a change in the electrocatalytic properties of the catalyst. The overpotentials and Tafel slopes were observed to decrease with zeolite-3 wt.% WO3. The smallest overpotential of 60 mV and Tafel slope of 31.9 mV/dec was registered for nano-zeolite with 3 wt.% WO3, while the micro-zeolite gave an overpotential of 370 mV and a Tafel slope of 98.1 mV/dec. It was concluded that even with the same metal oxide loading, nano-zeolite showed superior performance, which is attributed to its size and hence easier escape of hydrogen bubbles from the catalyst.

  11. Characteristics of nano-sized yttria powder synthesized by a polyvinyl alcohol solution route at low temperature.

    PubMed

    Lee, Sang-Jin; Jung, Choong-Hwan

    2012-01-01

    Nano-sized yttria (Y2O3) powders were successfully synthesized at a low temperature of 400 degrees C by a simple polymer solution route. PVA polymer, as an organic carrier, contributed to an atom-scale homogeneous precursor gel and it resulted in fully crystallized, nano-sized yttria powder with high specific surface area through the low temperature calcination. In this process, the content of PVA, calcination temperature and heating time affected the microstructure and crystallization behavior of the powders. The development of crystalline phase and the final particle size were strongly dependant on the oxidation reaction from the polymer burn-out step and the PVA content. In this paper, the PVA solution technique for the fabrication of nano-sized yttria powders is introduced. The effects of PVA content and holding time on the powder morphology and powder specific surface area are also studied. The characterization of the synthesized powders is examined by using XRD, DTA/TG, SEM, TEM and nitrogen gas adsorption. The yttria powder synthesized from the PVA content of 3:1 ratio and calcined at 400 degrees C had a crystallite size of about 20 nm or less with a high surface areas of 93.95-120.76 m2 g(-1).

  12. Biological Superoxide In Manganese Oxide Formation

    NASA Astrophysics Data System (ADS)

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

    2011-12-01

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

  13. Effect of graphene oxide nano filler on dynamic behaviour of GFRP composites

    NASA Astrophysics Data System (ADS)

    Pujar, Nagabhushan V.; Nanjundaradhya, N. V.; Sharma, Ramesh S.

    2018-04-01

    Nano fillers like Alumina oxide, Titanium oxide, Carbon nano tube, Nano clay have been used to improve the mechanical and damping properties of fiber reinforced polymer composites. In the recent years Graphene oxide nano filler is receiving considerable attention for its outstanding properties. Literature available shows that Graphene oxide nano filler can be used to improve the mechanical properties. The use of Graphene oxide in vibration attenuation by enhancing the passive damping in fiber reinforced polymer composite has not been fully explored. The objective of this work is to investigate the dynamic behaviour of Glass fiber-reinforced composite embedded with Graphene oxide nano filler. Graphene oxide is dispersed in epoxy resin with various concentration (0.1%, 0.5% and 1%wt) using ultra-sonification process. Composite laminates were made using the traditional hand-lay-up followed by vacuum bag process. Experimental modal analysis using traditional `strike method' is used to evaluate modal parameters using FFT analyzer and Data Acquisition System. Experiments were carried out for two different fiber orientations viz 0 ➙ & 45 ➙ and two boundary conditions (Free-Free and Cantilever). The modal parameters such as natural frequency, mode shape, damping ratio were studied. This research work demonstrates the vibration damping behaviour with incorporation of Graphene oxide and provides a basic understanding of the damping characteristics in design and manufacture of high performance composites.

  14. Elemental selenium at nano size possesses lower toxicity without compromising the fundamental effect on selenoenzymes: comparison with selenomethionine in mice.

    PubMed

    Wang, Huali; Zhang, Jinsong; Yu, Hanqing

    2007-05-15

    Glutathione peroxidase and thioredoxin reductase are major selenoenzymes through which selenium exerts powerful antioxidant effects. Selenium also elicits pro-oxidant effects at toxic levels. The antioxidant and pro-oxidant effects, or bioavailability and toxicity, of selenium depend on its chemical form. Selenomethionine is considered to be the most appropriate supplemental form due to its excellent bioavailability and lower toxicity compared to various selenium compounds. The present studies reveal that, compared with selenomethionine, elemental selenium at nano size (Nano-Se) possesses equal efficacy in increasing the activities of glutathione peroxidase and thioredoxin reductase but has much lower toxicity as indicated by median lethal dose, acute liver injury, and short-term toxicity. Our results suggest that Nano-Se can serve as an antioxidant with reduced risk of selenium toxicity.

  15. 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...

  16. 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.

  17. 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.

  18. Fabrication of nano-engineered transparent conducting oxides by pulsed laser deposition.

    PubMed

    Gondoni, Paolo; Ghidelli, Matteo; Di Fonzo, Fabio; Li Bassi, Andrea; Casari, Carlo S

    2013-02-27

    Nanosecond Pulsed Laser Deposition (PLD) in the presence of a background gas allows the deposition of metal oxides with tunable morphology, structure, density and stoichiometry by a proper control of the plasma plume expansion dynamics. Such versatility can be exploited to produce nanostructured films from compact and dense to nanoporous characterized by a hierarchical assembly of nano-sized clusters. In particular we describe the detailed methodology to fabricate two types of Al-doped ZnO (AZO) films as transparent electrodes in photovoltaic devices: 1) at low O₂ pressure, compact films with electrical conductivity and optical transparency close to the state of the art transparent conducting oxides (TCO) can be deposited at room temperature, to be compatible with thermally sensitive materials such as polymers used in organic photovoltaics (OPVs); 2) highly light scattering hierarchical structures resembling a forest of nano-trees are produced at higher pressures. Such structures show high Haze factor (>80%) and may be exploited to enhance the light trapping capability. The method here described for AZO films can be applied to other metal oxides relevant for technological applications such as TiO₂, Al₂O₃, WO₃ and Ag₄O₄.

  19. Fabrication of Nano-engineered Transparent Conducting Oxides by Pulsed Laser Deposition

    PubMed Central

    Gondoni, Paolo; Ghidelli, Matteo; Di Fonzo, Fabio; Li Bassi, Andrea; Casari, Carlo S.

    2013-01-01

    Nanosecond Pulsed Laser Deposition (PLD) in the presence of a background gas allows the deposition of metal oxides with tunable morphology, structure, density and stoichiometry by a proper control of the plasma plume expansion dynamics. Such versatility can be exploited to produce nanostructured films from compact and dense to nanoporous characterized by a hierarchical assembly of nano-sized clusters. In particular we describe the detailed methodology to fabricate two types of Al-doped ZnO (AZO) films as transparent electrodes in photovoltaic devices: 1) at low O2 pressure, compact films with electrical conductivity and optical transparency close to the state of the art transparent conducting oxides (TCO) can be deposited at room temperature, to be compatible with thermally sensitive materials such as polymers used in organic photovoltaics (OPVs); 2) highly light scattering hierarchical structures resembling a forest of nano-trees are produced at higher pressures. Such structures show high Haze factor (>80%) and may be exploited to enhance the light trapping capability. The method here described for AZO films can be applied to other metal oxides relevant for technological applications such as TiO2, Al2O3, WO3 and Ag4O4. PMID:23486076

  20. Weatherability and Leach Resistance of Wood Impregnated with Nano-Zinc Oxide

    NASA Astrophysics Data System (ADS)

    Clausen, Carol A.; Green, Frederick; Nami Kartal, S.

    2010-09-01

    Southern pine specimens vacuum-treated with nano-zinc oxide (nano-ZnO) dispersions were evaluated for leach resistance and UV protection. Virtually, no leaching occurred in any of the nano-ZnO-treated specimens in a laboratory leach test, even at the highest retention of 13 kg/m3. However, specimens treated with high concentrations of nano-ZnO showed 58-65% chemical depletion after 12 months of outdoor exposure. Protection from UV damage after 12 months exposure is visibly obvious on both exposed and unexposed surfaces compared to untreated controls. Graying was markedly diminished, although checking occurred in all specimens. Nano-zinc oxide treatment at a concentration of 2.5% or greater provided substantial resistance to water absorption following 12 months of outdoor exposure compared to untreated and unweathered southern pine. We conclude that nano-zinc oxide can be utilized in new wood preservative formulations to impart resistance to leaching, water absorption and UV damage of wood.

  1. 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.

  2. 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.

  3. 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).

  4. The influence of manganese-cobalt oxide/graphene on reducing fire hazards of poly(butylene terephthalate).

    PubMed

    Wang, Dong; Zhang, Qiangjun; Zhou, Keqing; Yang, Wei; Hu, Yuan; Gong, Xinglong

    2014-08-15

    By means of direct nucleation and growth on the surface of graphene and element doping of cobalt oxide (Co3O4) nano-particles, manganese-cobalt oxide/graphene hybrids (MnCo2O4-GNS) were synthesized to reduce fire hazards of poly(butylene terephthalate) (PBT). The structure, elemental composition and morphology of the obtained hybrids were surveyed by X-ray diffraction, X-ray photoelectron spectrometer and transmission electron microscopy, respectively. Thermogravimetric analysis was applied to simulate and study the influence of MnCo2O4-GNS hybrids on thermal degradation of PBT during combustion. The fire hazards of PBT and its composites were assessed by the cone calorimeter. The cone test results had showed that peak HRR and SPR values of MnCo2O4-GNS/PBT composites were lower than that of pure PBT and Co3O4-GNS/PBT composites. Furthermore, the incorporation of MnCo2O4-GNS hybrids gave rise to apparent decrease of pyrolysis products containing aromatic compounds, carbonyl compounds, carbon monoxide and carbon dioxide, attributed to combined impact of physical barrier for graphene and cat O4 for organic volatiles and carbon monoxide. Copyright © 2014 Elsevier B.V. All rights reserved.

  5. ChemCam Update – 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.

  6. 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).

  7. Nano-Sized Natural Colorants from Rocks and Soils

    NASA Astrophysics Data System (ADS)

    Ahmad, W. Y. W.; Ruznan, W. S.; Hamid, H. A.; Kadir, M. I. A.; Yusoh, M. K. M.; Ahmad, M. R.

    2010-03-01

    Colored rocks (lateritic) and soils (shales) are available in abundant all around Malaysia and they are from natural sources. The colorants will be useful if they can be transferred to substrates using dyeing, printing or brushing with acceptable fastness. First of all the rocks need to be crushed into powder form before coloration can take place. The sizes of the colorants particles obtained with coffee grinder were of 7-8 microns. They can be reduced to 3-5 micron using fluidized bed jetmill and to nano sizes with the help of planetary mono mill grinders. The experiment was conducted in both dyeing and printing of textiles using all three sizes (7-8 microns, 3-5 microns and nano sizes) of colorants on silk fabric. The colorants were applied on silk fabrics by dyeing and tie and dye techniques. In addition, the colorants can also be applied by brushing technique as in batik canting or batik block as well as silk screen printing. The evaluations of colored materials were based on the levelness of dyeing, fastness properties (washing, light and rubbing fastness) and color strength. The wash fastness testing shows that all colorants sizes have more or less the same fastness to washing but nano sized colorants produced better uniform dyes distribution (levelness of dyeing) and higher color strength.

  8. 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...

  9. 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.

  10. Nano-confinement inside molecular metal oxide clusters: Dynamics and modified encapsulation behavior

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

    Wang, Zhe; Daemen, Luke L.; Cheng, Yongqiang

    Encapsulation behavior, as well as the presence of internal catalytically-active sites, has been spurring the applications of a 3 nm hollow spherical metal oxide cluster {Mo 132} as an encapsulation host and a nano-reactor. Due to its well-defined and tunable cluster structures, and nano-scaled internal void space comparable to the volumes of small molecules, this cluster provides a good model to study the dynamics of materials under ultra-confinement. Neutron scattering studies suggest that bulky internal ligands inside the cluster show slower and limited dynamics compared to their counterparts in the bulk state, revealing the rigid nature of the skeleton ofmore » the internal ligands. Furthermore, NMR studies indicate that the rigid internal ligands that partially cover the interfacial pore on the molybdenum oxide shells are able to block some large guest molecules from going inside the capsule cluster, which provides a convincing protocol for size-selective encapsulation and separation.« less

  11. Nano-confinement inside molecular metal oxide clusters: Dynamics and modified encapsulation behavior

    DOE PAGES

    Wang, Zhe; Daemen, Luke L.; Cheng, Yongqiang; ...

    2016-08-19

    Encapsulation behavior, as well as the presence of internal catalytically-active sites, has been spurring the applications of a 3 nm hollow spherical metal oxide cluster {Mo 132} as an encapsulation host and a nano-reactor. Due to its well-defined and tunable cluster structures, and nano-scaled internal void space comparable to the volumes of small molecules, this cluster provides a good model to study the dynamics of materials under ultra-confinement. Neutron scattering studies suggest that bulky internal ligands inside the cluster show slower and limited dynamics compared to their counterparts in the bulk state, revealing the rigid nature of the skeleton ofmore » the internal ligands. Furthermore, NMR studies indicate that the rigid internal ligands that partially cover the interfacial pore on the molybdenum oxide shells are able to block some large guest molecules from going inside the capsule cluster, which provides a convincing protocol for size-selective encapsulation and separation.« less

  12. Uniform nano-sized valsartan for dissolution and bioavailability enhancement: influence of particle size and crystalline state.

    PubMed

    Ma, Qiuping; Sun, Hongrui; Che, Erxi; Zheng, Xin; Jiang, Tongying; Sun, Changshan; Wang, Siling

    2013-01-30

    The central purpose of this study was to evaluate the impact of drug particle size and crystalline state on valsartan (VAL) formulations in order to improve its dissolution and bioavailability. VAL microsuspension (mean size 22 μm) and nanosuspension (30-80nm) were prepared by high speed dispersing and anti-solvent precipitation method and converted into powders through spray drying. Differential scanning calorimetry studies indicated amorphization of VAL in the spray-dried valsartan nanosuspension (SD-VAL-Nano) but recrystallization occurred after 6 months storage at room temperature. The spray-dried valsartan microsuspension (SD-VAL-Micro) conserved the crystalline form. The VAL dissolution rate and extent were markedly enhanced with both SD-VAL-Micro and SD-VAL-Nano as compared to crude VAL crystals over the pH range of 1.2-6.8. Pharmacokinetic studies in rats demonstrated a 2.5-fold increase in oral bioavailability in the case of SD-VAL-Nano compared with the commercial product while the SD-VAL-Micro provided a much less desirable pharmacokinetic profile. In conclusion, reducing particle size to the nano-scale appears to be a worthwhile and promising approach to obtain VAL products with optimum bioavailability. In addition, the impact of crystalline state on the bioavailability of nano-sized VAL might be not as big as that of particle size. Copyright © 2012 Elsevier B.V. All rights reserved.

  13. Nano rare-earth oxides induced size-dependent vacuolization: an independent pathway from autophagy.

    PubMed

    Zhang, Ying; Yu, Chenguang; Huang, Guanyi; Wang, Changli; Wen, Longping

    2010-09-07

    Four rare earth oxides have been shown to induce autophagy. Interestingly, we often noticed plentiful vacuolization, which was not always involved in this autophagic process. In this study, we investigated three other rare-earth elements, including Yttrium (Y), Ytterbium (Yb), and Lanthanum (La). Autophagic effect could be induced by all of them but only Y(2)O(3) and Yb(2)O(3) could cause massive vacuolization. Y(2)O(3) and Yb(2)O(3) treated by sonication or centrifugation to reduce particle size were used to test vacuolization level in HeLa cell lines. The results showed that rare earth oxides-induced vacuolization is size-dependent and differs from autophagic pathway. To further clarify the characteristics of this autophagic process, we used MEF Atg-5 (autophagy associated gene 5) knockout cell line, and the result showed that the autophagic process induced by rare earth oxides is Atg-5-dependent and the observed vacuolization was independent from autophagy. Similar results could also be observed in our tests on 3-methyladenine(3-MA), a well-known autophagy inhibitor. In conclusion, for the first time, we clarified the relationship between massive vacuolization and autophagic process induced by rare earth oxides and pointed out the size effect of rare earth oxides on the formation of vacuoles, which give clues to further investigation on the mechanisms underlying their biological effects.

  14. Nano rare-earth oxides induced size-dependent vacuolization: an independent pathway from autophagy

    PubMed Central

    Zhang, Ying; Yu, Chenguang; Huang, Guanyi; Wang, Changli; Wen, Longping

    2010-01-01

    Four rare earth oxides have been shown to induce autophagy. Interestingly, we often noticed plentiful vacuolization, which was not always involved in this autophagic process. In this study, we investigated three other rare-earth elements, including Yttrium (Y), Ytterbium (Yb), and Lanthanum (La). Autophagic effect could be induced by all of them but only Y2O3 and Yb2O3 could cause massive vacuolization. Y2O3 and Yb2O3 treated by sonication or centrifugation to reduce particle size were used to test vacuolization level in HeLa cell lines. The results showed that rare earth oxides-induced vacuolization is size-dependent and differs from autophagic pathway. To further clarify the characteristics of this autophagic process, we used MEF Atg-5 (autophagy associated gene 5) knockout cell line, and the result showed that the autophagic process induced by rare earth oxides is Atg-5-dependent and the observed vacuolization was independent from autophagy. Similar results could also be observed in our tests on 3-methyladenine(3-MA), a well-known autophagy inhibitor. In conclusion, for the first time, we clarified the relationship between massive vacuolization and autophagic process induced by rare earth oxides and pointed out the size effect of rare earth oxides on the formation of vacuoles, which give clues to further investigation on the mechanisms underlying their biological effects. PMID:20856835

  15. Synthesis of graphene oxide and reduced graphene oxide using volumetric method by a novel approach without NaNO2 or NaNO3

    NASA Astrophysics Data System (ADS)

    Gunda, Rajitha; Madireddy, Buchi Suresh; Dash, Raj Kishora

    2018-02-01

    In the present work, graphite was processed to graphene oxide (GO) using modified Hummer's method by volumetric titration approach, without attaining zero temperature and the addition of toxic chemicals (NaNO2/NaNO3). The complete oxidation of graphite to graphene oxide was obtained by controlled addition (volumetric titration) of KMnO4. The addition of higher KMnO4 resulted in partial oxidation and 2-3 mono-layers with less defects/disordered structure of reduced graphene oxide (RGO) sheets were achieved. Samples were analyzed by XRD, FT-IR, Raman analysis, and TEM analysis. X-ray diffraction displayed the oxidized peak of graphene oxide at 11.9° and reduced graphene oxide at 23.8°. The prolonged stability of the synthesized GO with lower mole ratios of oxidizing agent was confirmed from UV-visible spectroscopy. Based on the results, processed graphene oxide is found to be a candidate material for thermally stable capacitor application.

  16. Nano-Graphene Oxide for Cellular Imaging and Drug Delivery

    PubMed Central

    Sun, Xiaoming; Liu, Zhuang; Welsher, Kevin; Robinson, Joshua Tucker; Goodwin, Andrew; Zaric, Sasa

    2010-01-01

    Two-dimensional graphene offers interesting electronic, thermal, and mechanical properties that are currently being explored for advanced electronics, membranes, and composites. Here we synthesize and explore the biological applications of nano-graphene oxide (NGO), i.e., single-layer graphene oxide sheets down to a few nanometers in lateral width. We develop functionalization chemistry in order to impart solubility and compatibility of NGO in biological environments. We obtain size separated pegylated NGO sheets that are soluble in buffers and serum without agglomeration. The NGO sheets are found to be photoluminescent in the visible and infrared regions. The intrinsic photoluminescence (PL) of NGO is used for live cell imaging in the near-infrared (NIR) with little background. We found that simple physisorption via π-stacking can be used for loading doxorubicin, a widely used cancer drug onto NGO functionalized with antibody for selective killing of cancer cells in vitro. Owing to its small size, intrinsic optical properties, large specific surface area, low cost, and useful non-covalent interactions with aromatic drug molecules, NGO is a promising new material for biological and medical applications. PMID:20216934

  17. Radiopacifier Particle Size Impacts the Physical Properties of Tricalcium Silicate–based Cements

    PubMed Central

    Saghiri, Mohammad Ali; Gutmann, James L.; Orangi, Jafar; Asatourian, Armen; Sheibani, Nader

    2016-01-01

    Introduction The aim of this study was to evaluate the impact of radiopaque additive, bismuth oxide, particle size on the physical properties, and radiopacity of tricalcium silicate–based cements. Methods Six types of tricalcium silicate cement (CSC) including CSC without bismuth oxide, CSC + 10% (wt%) regular bismuth oxide (particle size 10 μm), CSC + 20% regular bismuth oxide (simulating white mineral trioxide aggregate [WMTA]) as a control, CSC + 10% nano bismuth oxide (particle size 50–80 nm), CSC + 20% nano-size bismuth oxide, and nano WMTA (a nano modification of WMTA comprising nanoparticles in the range of 40–100 nm) were prepared. Twenty-four samples from each group were divided into 4 groups and subjected to push-out, surface microhardness, radiopacity, and compressive strength tests. Data were analyzed by 1-way analysis of variance with the post hoc Tukey test. Results The push-out and compressive strength of CSC without bismuth oxide and CSC with 10% and 20% nano bismuth oxide were significantly higher than CSC with 10% or 20% regular bismuth oxide (P < .05). The surface micro-hardness of CSC without bismuth oxide and CSC with 10% regular bismuth oxide had the lowest values (P < .05). The lowest radiopacity values were seen in CSC without bismuth oxide and CSC with 10% nano bismuth oxide (P < .05). Nano WMTA samples showed the highest values for all tested properties (P < .05) except for radiopacity. Conclusions The addition of 20% nano bismuth oxide enhanced the physical properties of CSC without any significant changes in radiopacity. Regular particle-size bismuth oxide reduced the physical properties of CSC material for tested parameters. PMID:25492489

  18. 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.

  19. 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.

  20. Control of manganese dioxide particles resulting from in situ chemical oxidation using permanganate.

    PubMed

    Crimi, Michelle; Ko, Saebom

    2009-02-01

    In situ chemical oxidation using permanganate is an approach to organic contaminant site remediation. Manganese dioxide particles are products of permanganate reactions. These particles have the potential to deposit in the subsurface and impact the flow-regime in/around permanganate injection, including the well screen, filter pack, and the surrounding subsurface formation. Control of these particles can allow for improved oxidant injection and transport and contact between the oxidant and contaminants of concern. The goals of this research were to determine if MnO(2) can be stabilized/controlled in an aqueous phase, and to determine the dependence of particle stabilization on groundwater characteristics. Bench-scale experiments were conducted to study the ability of four stabilization aids (sodium hexametaphosphate (HMP), Dowfax 8390, xanthan gum, and gum arabic) in maintaining particles suspended in solution under varied reaction conditions and time. Variations included particle and stabilization aid concentrations, ionic content, and pH. HMP demonstrated the most promising results, as compared to xanthan gum, gum arabic, and Dowfax 8390 based on results of spectrophotometric studies of particle behavior, particle filtration, and optical measurements of particle size and zeta potential. HMP inhibited particle settling, provided for greater particle stability, and resulted in particles of a smaller average size over the range of experimental conditions evaluated compared to results for systems that did not include HMP. Additionally, HMP did not react unfavorably with permanganate. These results indicate that the inclusion of HMP in a permanganate oxidation system improves conditions that may facilitate particle transport.

  1. 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

  2. Fabrication of polymeric nano-batteries array using anodic aluminum oxide templates.

    PubMed

    Zhao, Qiang; Cui, Xiaoli; Chen, Ling; Liu, Ling; Sun, Zhenkun; Jiang, Zhiyu

    2009-02-01

    Rechargeable nano-batteries were fabricated in the array pores of anodic aluminum oxide (AAO) template, combining template method and electrochemical method. The battery consisted of electropolymerized PPy electrode, porous TiO2 separator, and chemically polymerized PAn electrode was fabricated in the array pores of two-step anodizing aluminum oxide (AAO) membrane, based on three-step assembling method. It performs typical electrochemical battery behavior with good charge-discharge ability, and presents a capacity of 25 nAs. AFM results show the hexagonal array of nano-batteries' top side. The nano-battery may be a promising device for the development of Micro-Electro-Mechanical Systems (MEMS), and Nano-Electro-Mechanical Systems (NEMS).

  3. 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

  4. Modifications in Glass Ionomer Cements: Nano-Sized Fillers and Bioactive Nanoceramics

    PubMed Central

    Najeeb, Shariq; Khurshid, Zohaib; Zafar, Muhammad Sohail; Khan, Abdul Samad; Zohaib, Sana; Martí, Juan Manuel Nuñez; Sauro, Salvatore; Matinlinna, Jukka Pekka; Rehman, Ihtesham Ur

    2016-01-01

    Glass ionomer cements (GICs) are being used for a wide range of applications in dentistry. In order to overcome the poor mechanical properties of glass ionomers, several modifications have been introduced to the conventional GICs. Nanotechnology involves the use of systems, modifications or materials the size of which is in the range of 1–100 nm. Nano-modification of conventional GICs and resin modified GICs (RMGICs) can be achieved by incorporation of nano-sized fillers to RMGICs, reducing the size of the glass particles, and introducing nano-sized bioceramics to the glass powder. Studies suggest that the commercially available nano-filled RMGIC does not hold any significant advantage over conventional RMGICs as far as the mechanical and bonding properties are concerned. Conversely, incorporation of nano-sized apatite crystals not only increases the mechanical properties of conventional GICs, but also can enhance fluoride release and bioactivity. By increasing the crystallinity of the set matrix, apatites can make the set cement chemically more stable, insoluble, and improve the bond strength with tooth structure. Increased fluoride release can also reduce and arrest secondary caries. However, due to a lack of long-term clinical studies, the use of nano-modified glass ionomers is still limited in daily clinical dentistry. In addition to the in vitro and in vivo studies, more randomized clinical trials are required to justify the use of these promising materials. The aim of this paper is to review the modification performed in GIC-based materials to improve their physicochemical properties. PMID:27428956

  5. Engineering functionalized multi-phased silicon/silicon oxide nano-biomaterials to passivate the aggressive proliferation of cancer

    PubMed Central

    Premnath, P.; Tan, B.; Venkatakrishnan, K.

    2015-01-01

    Currently, the use of nano silicon in cancer therapy is limited as drug delivery vehicles and markers in imaging, not as manipulative/controlling agents. This is due to limited properties that native states of nano silicon and silicon oxides offers. We introduce nano-functionalized multi-phased silicon/silicon oxide biomaterials synthesized via ultrashort pulsed laser synthesis, with tunable properties that possess inherent cancer controlling properties that can passivate the progression of cancer. This nanostructured biomaterial is composed of individual functionalized nanoparticles made of a homogenous hybrid of multiple phases of silicon and silicon oxide in increasing concentration outwards from the core. The chemical properties of the proposed nanostructure such as number of phases, composition of phases and crystal orientation of each functionalized nanoparticle in the three dimensional nanostructure is defined based on precisely tuned ultrashort pulsed laser-material interaction mechanisms. The amorphous rich phased biomaterial shows a 30 fold (95%) reduction in number of cancer cells compared to bulk silicon in 48 hours. Further, the size of the cancer cells reduces by 76% from 24 to 48 hours. This method exposes untapped properties of combination of multiple phases of silicon oxides and its applications in cancer therapy. PMID:26190009

  6. Growth control of carbon nanotubes using by anodic aluminum oxide nano templates.

    PubMed

    Park, Yong Seob; Choi, Won Seek; Yi, Junsin; Lee, Jaehyeong

    2014-05-01

    Anodic Aluminum Oxide (AAO) template prepared in acid electrolyte possess regular and highly anisotropic porous structure with pore diameter range from five to several hundred nanometers, and with a density of pores ranging from 10(9) to 10(11) cm(-2). AAO can be used as microfilters and templates for the growth of CNTs and metal or semiconductor nanowires. Varying anodizing conditions such as temperature, electrolyte, applied voltage, anodizing and widening time, one can control the diameter, the length, and the density of pores. In this work, we deposited Al thin film by radio frequency magnetron sputtering method to fabricate AAO nano template and synthesized multi-well carbon nanotubes on a glass substrate by microwave plasma-enhanced chemical vapor deposition (MPECVD). AAO nano-porous templates with various pore sizes and depths were introduced to control the dimension and density of CNT arrays. The AAO nano template was synthesize on glass by two-step anodization technique. The average diameter and interpore distance of AAO nano template are about 65 nm and 82 nm. The pore density and AAO nano template thickness are about 2.1 x 10(10) pores/cm2 and 1 microm, respectively. Aligned CNTs on the AAO nano template were synthesized by MPECVD at 650 degrees C with the Ni catalyst layer. The length and diameter of CNTs were grown 2 microm and 50 nm, respectively.

  7. 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

  8. 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

  9. 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

  10. Nano-MnO2-mediated transformation of triclosan with humic molecules present: kinetics, products, and pathways.

    PubMed

    Sun, Kai; Li, Shunyao; Waigi, Michael Gatheru; Huang, Qingguo

    2018-05-01

    It has been shown that manganese dioxide (MnO 2 ) can mediate transformation of phenolic contaminants to form phenoxyl radical intermediates, and subsequently, these intermediates intercouple to form oligomers via covalent binding. However, the reaction kinetics and transformation mechanisms of phenolic contaminants with humic molecules present in nano-MnO 2 -mediated systems were still unclear. In this study, it was proven that nano-MnO 2 were effective in transforming triclosan under acidic conditions (pH 3.5-5.0) during manganese reduction, and the apparent pseudo first-order kinetics rate constants (k = 0.0599-1.5314 h -1 ) increased as the pH decreased. In particular, the transformation of triclosan by nano-MnO 2 was enhanced in the presence of low-concentration humic acid (1-10 mg L -1 ). The variation in the absorption of humic molecules at 275 nm supported possible covalent binding between humic molecules and triclosan in the nano-MnO 2 -mediated systems. A total of four main intermediate products were identified by high-resolution mass spectrometry (HRMS), regardless of humic molecules present in the systems or not. These products correspond to a suite of radical intercoupling reactions (dimers and trimers), ether cleavage (2,4-dichlorophenol), and oxidation to quinone-like products, triggered by electron transfer from triclosan molecules to nano-MnO 2 . A possible reaction pathway in humic acid solutions, including homo-coupling, decomposition, oxidation, and cross-coupling, was proposed. Our findings provide valuable information regarding the environmental fate and transformation mechanism of triclosan by nano-MnO 2 in complex water matrices.

  11. 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.

  12. 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.

  13. 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.

  14. Chromium(iii) oxidation by biogenic manganese oxides with varying structural ripening.

    PubMed

    Tang, Yuanzhi; Webb, Samuel M; Estes, Emily R; Hansel, Colleen M

    2014-09-20

    Manganese (Mn) oxides, which are generally considered biogenic in origin within natural systems, are the only oxidants of Cr(iii) under typical environmental conditions. Yet the influence of Mn biooxide mineral structural evolution on Cr(iii) oxidation under varying geochemical conditions is unknown. In this study we examined the role of light, organic carbon, pH, and the structure of biogenic Mn oxides on Cr(iii) oxidation. Aging of Mn oxides produced by a marine bacterium within the widespread Roseobacter clade resulted in structural ripening from a colloidal hexagonal to a particulate triclinic birnessite phase. The structurally diverse Mn oxides were then reacted with aqueous Cr(iii) within artificial seawater in the presence or absence of carbon and light. Here we found that Cr(iii) oxidation capacity was highest at near neutral pH and in the combined presence of carbon and light. Mn oxide ripening from a hexagonal to a triclinic birnessite phase led to decreased Cr(iii) oxidation in the presence of carbon and light, whereas no change in reactivity was observed in the absence of carbon and/or in the dark. As only minimal Cr(iii) oxidation was observed in the absence of Mn oxides, these results strongly point to coupled Mn oxide- and photo-induced generation of organic and/or oxygen radicals involved in Cr(iii) oxidation. Based on Mn oxide concentration and structural trends, we postulate that Mn(ii) produced from the oxidation of Cr(iii) by the primary Mn oxide is recycled in the presence of organics and light conditions, (re)generating secondary hexagonal birnessite and thereby allowing for continuous oxidation of Cr(iii). In the absence of this Mn oxide regeneration, Cr(iii) induced structural ripening of the hexagonal birnessite precludes further Cr(iii) oxidation. These results highlight the complexity of reactions involved in Mn oxide mediated Cr(iii) oxidation and suggest that photochemical carbon reactions are requisite for sustained Cr(iii) oxidation

  15. 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

  16. 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.

  17. 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.

  18. Weatherability and leach resistance of wood impregnated with nano-zinc oxide

    Treesearch

    Carol A. Clausen; Frederick Green; S. Nami Kartal

    2010-01-01

    Southern pine specimens vacuum-treated with nano-zinc oxide (nano-ZnO) dispersions were evaluated for leach resistance and UV protection. Virtually, no leaching occurred in any of the nano-ZnO–treated specimens in a laboratory leach test, even at the highest retention of 13 kg/m3. However, specimens treated with high concentrations of nano-ZnO...

  19. 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.

  20. 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.

  1. 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.

  2. The development of manganese oxide coated ceramic membranes for combined catalytic ozonation and ultrafiltration of drinking water

    NASA Astrophysics Data System (ADS)

    Corneal, Lindsay Marie

    A novel method for the preparation of hydrated MnO2 by the ozonation of MnCl2 in water is described. The hydrated MnO 2 was used to coat titania water filtration membranes using a layer-by-layer technique. The coated membranes were then sintered in air at 500°C for 45 minutes. Upon sintering, the MnO2 is converted to alpha-Mn 2O3 (as characterized by x-ray and electron diffraction). Atomic force microscopy (AFM) imaging showed no significant change in the roughness or height of the surface features of coated membranes, while scanning electron microscopy (SEM) imaging showed an increase in grain size with increasing number of coating layers. Energy dispersive x-ray spectroscopy (EDS) mapping and line scans revealed manganese present throughout the membrane, indicating that manganese dispersed into the porous membrane during the coating process and diffused into the titania grains during sintering. Selected area diffraction (SAD) of the coated and sintered membrane was used to index the surface layer as alpha-Mn2O3. The surface layer was uneven, although there was a trend of increasing thickness with increasing coating layers. The coating acts as a catalyst for the oxidation of organic matter when coated membranes are used in a hybrid ozonation-membrane filtration system. A trend of decreasing total organic carbon (TOC) in the permeate water was observed with increasing number of coating layers. The catalytic activity also manifests itself as improved recovery of the water flux due to oxidation of foulants on the membrane surface. Ceramic nanoparticle coatings on ceramic water filtration membranes must undergo high temperature sintering. However, this means that the underlying membrane, which has been engineered for a given molecular weight cut-off (MWCO), also undergoes a high temperature heat treatment that serves to increase pore size that have resulted in increases in permeability of titania membranes. Coating the titania membrane with manganese oxide followed

  3. Effect of Ozone Treatment on Nano-Sized Silver Sulfide in Wastewater Effluent.

    PubMed

    Thalmann, Basilius; Voegelin, Andreas; von Gunten, Urs; Behra, Renata; Morgenroth, Eberhard; Kaegi, Ralf

    2015-09-15

    Silver nanoparticles used in consumer products are likely to be released into municipal wastewater. Transformation reactions, most importantly sulfidation, lead to the formation of nanoscale silver sulfide (nano-Ag2S) particles. In wastewater treatment plants (WWTP), ozonation can enhance the effluent quality by eliminating organic micropollutants. The effect of ozonation on the fate of nano-Ag2S, however, is currently unknown. In this study, we investigate the interaction of ozone with nano-Ag2S and evaluate the effect of ozonation on the short-term toxicity of WWTP effluent spiked with nano-Ag2S. The oxidation of nano-Ag2S by ozone resulted in a stoichiometric factor (number of moles of ozone required to oxidize one mole of sulfide to sulfate) of 2.91, which is comparable to the results obtained for the reaction of bisulfide (HS(-)) with ozone. The second-order rate constant for the reaction of nano-Ag2S with ozone (k = 3.1 × 10(4) M(-1) s(-1)) is comparable to the rate constant of fast-reacting micropollutants. Analysis of the ozonation products of nano-Ag2S by transmission electron microscopy (TEM) and X-ray absorption spectroscopy (XAS) revealed that ozonation dominantly led to the formation of silver chloride in WWTP effluent. After ozonation of the Ag2S-spiked effluent, the short-term toxicity for the green algae Chlamydomonas reinhardtii increased and reached EC50 values comparable to Ag(+). This study thus reveals that ozone treatment of WWTP effluent results in the oxidation of Ag2S and, hence, an increase of the Ag toxicity in the effluent, which may become relevant at elevated Ag concentrations.

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

    USGS Publications Warehouse

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

    2009-01-01

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

  5. Constraints on superoxide mediated formation of manganese oxides

    PubMed Central

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

    2013-01-01

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

  6. Nano-sized crystalline drug production by milling technology.

    PubMed

    Moribe, Kunikazu; Ueda, Keisuke; Limwikrant, Waree; Higashi, Kenjirou; Yamamoto, Keiji

    2013-01-01

    Nano-formulation of poorly water-soluble drugs has been developed to enhance drug dissolution. In this review, we introduce nano-milling technology described in recently published papers. Factors affecting the size of drug crystals are compared based on the preparation methods and drug and excipient types. A top-down approach using the comminution process is a method conventionally used to prepare crystalline drug nanoparticles. Wet milling using media is well studied and several wet-milled drug formulations are now on the market. Several trials on drug nanosuspension preparation using different apparatuses, materials, and conditions have been reported. Wet milling using a high-pressure homogenizer is another alternative to preparing production-scale drug nanosuspensions. Dry milling is a simple method of preparing a solid-state drug nano-formulation. The effect of size on the dissolution of a drug from nanoparticles is an area of fundamental research, but it is sometimes incorrectly evaluated. Here, we discuss evaluation procedures and the associated problems. Lastly, the importance of quality control, process optimization, and physicochemical characterization are briefly discussed.

  7. 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

  8. Oxidative removal of aqueous steroid estrogens by manganese oxides.

    PubMed

    Xu, Lei; Xu, Chao; Zhao, Meirong; Qiu, Yuping; Sheng, G Daniel

    2008-12-01

    This study investigated the oxidative removal of steroid estrogens from water by synthetic manganese oxide (MnO2) and the factors influencing the reactions. Using 1 x 10(-5)M MnO2 at pH 4, estrone (E1), 17beta-estradiol (E2), estriol (E3) and 17alpha-ethinylestradiol (EE2), all at 4 x 10(-6)M, were rapidly removed within 220 min, indicating the effectiveness of MnO2 as an oxidizing agent towards estrogens. E2 removal increased with decreasing pH over the tested range of 4-8, due most likely to increased oxidizing power of MnO2 and a cleaner reactive surface in acidic solutions. Coexisting metal ions of 0.01 M (Cu(II), Zn(II), Fe(III) and Mn(II)) and Mn(II) released from MnO2 reduction competed with E2 for reactive sites leading to reduced E2 removal. Observed differential suppression on E2 removal may be related to different speciations of metals, as suggested by the MINTEQ calculations, and hence their different adsorptivities on MnO2. By suppressing the metal effect, humic acid substantially enhanced E2 removal. This was attributed to complexation of humic acid with metal ions. With 0.01 M ZnCl2 in solutions containing 1 mg l(-1) humic acid, the binding of humic acid for Zn(II) was determined at 251 mmol g(-1). An in vitro assay using human breast carcinoma MCF-7 cells indicated a near elimination of estrogenic activities without secondary risk of estrogen solutions treated with MnO2. Synthetic MnO2 is therefore a promising chemical agent under optimized conditions for estrogen removal from water. Metal chelators recalcitrant to MnO2 oxidation may be properly used to further enhance the MnO2 performance.

  9. 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.

  10. Grain Refinement and Mechanical Properties of Cu–Cr–Zr Alloys with Different Nano-Sized TiCp Addition

    PubMed Central

    Zhang, Dongdong; Bai, Fang; Wang, Yong; Wang, Jinguo; Wang, Wenquan

    2017-01-01

    The TiCp/Cu master alloy was prepared via thermal explosion reaction. Afterwards, the nano-sized TiCp/Cu master alloy was dispersed by electromagnetic stirring casting into the melting Cu–Cr–Zr alloys to fabricate the nano-sized TiCp-reinforced Cu–Cr–Zr composites. Results show that nano-sized TiCp can effectively refine the grain size of Cu–Cr–Zr alloys. The morphologies of grain in Cu–Cr–Zr composites changed from dendritic grain to equiaxed crystal because of the addition and dispersion of nano-sized TiCp. The grain size decreased from 82 to 28 μm with the nano-sized TiCp content. Compared with Cu–Cr–Zr alloys, the ultimate compressive strength (σUCS) and yield strength (σ0.2) of 4 wt% TiCp-reinforced Cu–Cr–Zr composites increased by 6.7% and 9.4%, respectively. The wear resistance of the nano-sized TiCp-reinforced Cu–Cr–Zr composites increased with the increasing nano-sized TiCp content. The wear loss of the nano-sized TiCp-reinforced Cu–Cr–Zr composites decreased with the increasing TiCp content under abrasive particles. The eletrical conductivity of Cu–Cr–Zr alloys, 2% and 4% nano-sized TiCp-reinforced Cu–Cr–Zr composites are 64.71% IACS, 56.77% IACS and 52.93% IACS, respectively. PMID:28786937

  11. Elemental selenium particles at nano-size (Nano-Se) are more toxic to Medaka (Oryzias latipes) as a consequence of hyper-accumulation of selenium: a comparison with sodium selenite.

    PubMed

    Li, Hongcheng; Zhang, Jinsong; Wang, Thanh; Luo, Wenru; Zhou, Qunfang; Jiang, Guibin

    2008-09-29

    Recent studies have shown that elemental selenium particles at nano-size (Nano-Se) exhibited comparable bioavailability and less toxicity in mice and rats when compared to sodium selenite, selenomethinine and methylselenocysteine. However, little is known about the toxicity profile of Nano-Se in aquatic animals. In the present study, toxicities of Nano-Se and selenite in selenium-sufficient Medaka fish were compared. Selenium bioaccumulation and subsequent clearance in fish livers, gills, muscles and whole bodies were examined after 10 days of exposure to Nano-Se and selenite (100 microg Se/L) and again after 7 days of depuration. Both forms of selenium exposure effectively increased selenium concentrations in the investigated tissues. Surprisingly, Nano-Se was found to be more hyper-accumulated in the liver compared to selenite with differences as high as sixfold. Selenium clearance of both Nano-Se and selenite occurred at similar ratios in whole bodies and muscles but was not rapidly cleared from livers and gills. Nano-Se exhibited strong toxicity for Medaka with an approximately fivefold difference in terms of LC(50) compared to selenite. Nano-Se also caused larger effects on oxidative stress, most likely due to more hyper-accumulation of selenium in liver. The present study suggests that toxicity of nanoparticles can largely vary between different species and concludes that the evaluation of nanotoxicology should be carried out on a case-by-case basis.

  12. 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

  13. Effects of nano-SiO(2) and different ash particle sizes on sludge ash-cement mortar.

    PubMed

    Lin, K L; Chang, W C; Lin, D F; Luo, H L; Tsai, M C

    2008-09-01

    The effects of nano-SiO(2) on three ash particle sizes in mortar were studied by replacing a portion of the cement with incinerated sewage sludge ash. Results indicate that the amount of water needed at standard consistency increased as more nano-SiO(2) was added. Moreover, a reduction in setting time became noticeable for smaller ash particle sizes. The compressive strength of the ash-cement mortar increased as more nano-SiO(2) was added. Additionally, with 2% nano-SiO(2) added and a cure length of 7 days, the compressive strength of the ash-cement mortar with 1 microm ash particle size was about 1.5 times better that of 75microm particle size. Further, nano-SiO(2) functioned to fill pores for ash-cement mortar with different ash particle sizes. However, the effects of this pore-filling varied with ash particle size. Higher amounts of nano-SiO(2) better influenced the ash-cement mortar with larger ash particle sizes.

  14. 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.

  15. [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.

  16. 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.

  17. Grain Refinement and Mechanical Properties of Cu-Cr-Zr Alloys with Different Nano-Sized TiCp Addition.

    PubMed

    Zhang, Dongdong; Bai, Fang; Wang, Yong; Wang, Jinguo; Wang, Wenquan

    2017-08-08

    The TiC p /Cu master alloy was prepared via thermal explosion reaction. Afterwards, the nano-sized TiC p /Cu master alloy was dispersed by electromagnetic stirring casting into the melting Cu-Cr-Zr alloys to fabricate the nano-sized TiC p -reinforced Cu-Cr-Zr composites. Results show that nano-sized TiC p can effectively refine the grain size of Cu-Cr-Zr alloys. The morphologies of grain in Cu-Cr-Zr composites changed from dendritic grain to equiaxed crystal because of the addition and dispersion of nano-sized TiC p . The grain size decreased from 82 to 28 μm with the nano-sized TiC p content. Compared with Cu-Cr-Zr alloys, the ultimate compressive strength (σ UCS ) and yield strength (σ 0.2 ) of 4 wt% TiC p -reinforced Cu-Cr-Zr composites increased by 6.7% and 9.4%, respectively. The wear resistance of the nano-sized TiCp-reinforced Cu-Cr-Zr composites increased with the increasing nano-sized TiCp content. The wear loss of the nano-sized TiC p -reinforced Cu-Cr-Zr composites decreased with the increasing TiC p content under abrasive particles. The eletrical conductivity of Cu-Cr-Zr alloys, 2% and 4% nano-sized TiCp-reinforced Cu-Cr-Zr composites are 64.71% IACS, 56.77% IACS and 52.93% IACS, respectively.

  18. Progress in Nano-Engineered Anodic Aluminum Oxide Membrane Development.

    PubMed

    Poinern, Gerrard Eddy Jai; Ali, Nurshahidah; Fawcett, Derek

    2011-02-25

    The anodization of aluminum is an electro-chemical process that changes the surface chemistry of the metal, via oxidation, to produce an anodic oxide layer. During this process a self organized, highly ordered array of cylindrical shaped pores can be produced with controllable pore diameters, periodicity and density distribution. This enables anodic aluminum oxide (AAO) membranes to be used as templates in a variety of nanotechnology applications without the need for expensive lithographical techniques. This review article is an overview of the current state of research on AAO membranes and the various applications of nanotechnology that use them in the manufacture of nano-materials and devices or incorporate them into specific applications such as biological/chemical sensors, nano-electronic devices, filter membranes and medical scaffolds for tissue engineering.

  19. Progress in Nano-Engineered Anodic Aluminum Oxide Membrane Development

    PubMed Central

    Poinern, Gerrard Eddy Jai; Ali, Nurshahidah; Fawcett, Derek

    2011-01-01

    The anodization of aluminum is an electro-chemical process that changes the surface chemistry of the metal, via oxidation, to produce an anodic oxide layer. During this process a self organized, highly ordered array of cylindrical shaped pores can be produced with controllable pore diameters, periodicity and density distribution. This enables anodic aluminum oxide (AAO) membranes to be used as templates in a variety of nanotechnology applications without the need for expensive lithographical techniques. This review article is an overview of the current state of research on AAO membranes and the various applications of nanotechnology that use them in the manufacture of nano-materials and devices or incorporate them into specific applications such as biological/chemical sensors, nano-electronic devices, filter membranes and medical scaffolds for tissue engineering. PMID:28880002

  20. Conductivity of laser printed copper structures limited by nano-crystal grain size and amorphous metal droplet shell

    NASA Astrophysics Data System (ADS)

    Winter, Shoshana; Zenou, Michael; Kotler, Zvi

    2016-04-01

    We present a study of the morphology and electrical properties of copper structures which are printed by laser induced forward transfer from bulk copper. The percentage of voids and the oxidation levels are too low to account for the high resistivities (~4 to 14 times the resistivity of bulk monocrystalline copper) of these structures. Transmission electron microscope (TEM) images of slices cut from the printed areas using a focused ion beam (FIB) show nano-sized crystal structures with grain sizes that are smaller than the electron free path length. Scattering from such grain boundaries causes a significant increase in the resistivity and can explain the measured resistivities of the structures. The TEM images also show a nano-amorphous layer (~5 nm) at the droplet boundaries which also contributes to the overall resistivity. Such morphological characteristics are best explained by the ultrafast cooling rate of the molten copper droplets during printing.

  1. Electrodeposition of nano-sized bismuth on copper foil as electrocatalyst for reduction of CO2 to formate

    NASA Astrophysics Data System (ADS)

    Lv, Weixin; Zhou, Jing; Bei, Jingjing; Zhang, Rui; Wang, Lei; Xu, Qi; Wang, Wei

    2017-01-01

    Electrochemical reduction of carbon dioxide (CO2) to formate is energetically inefficient because high overpotential is required for reduction of CO2 to formate on most traditional catalysts. In this paper, a novel nano-sized Bi-based electrocatalyst deposited on a Cu foil has been synthesized, which can be used as a cathode for electrochemical reduction of CO2 to formate with a low overpotential (0.69 V) and a high selectivity (91.3%). The electrocatalyst can show excellent catalytic performance toward reduction of CO2 which can probably be attributed to the nano-sized structure and the surface oxide layer. The energy efficiency for reduction of CO2 to formate can reach to 50% when an IrxSnyRuzO2/Ti electrode is used as anode, it is one of the highest values found in the literatures and very practicable for sustainable fuel synthesis.

  2. 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.

  3. 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.

  4. 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.

  5. Crossover from disordered to core-shell structures of nano-oxide Y{sub 2}O{sub 3} dispersed particles in Fe

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

    Higgins, M. P.; Wang, L. M.; Gao, F., E-mail: gaofeium@umich.edu

    Molecular dynamic simulations of Y{sub 2}O{sub 3} in bcc Fe and transmission electron microscopy (TEM) observations were used to understand the structure of Y{sub 2}O{sub 3} nano-clusters in an oxide dispersion strengthened steel matrix. The study showed that Y{sub 2}O{sub 3} nano-clusters below 2 nm were completely disordered. Y{sub 2}O{sub 3} nano-clusters above 2 nm, however, form a core-shell structure, with a shell thickness of 0.5–0.7 nm that is independent of nano-cluster size. Y{sub 2}O{sub 3} nano-clusters were surrounded by off-lattice Fe atoms, further increasing the stability of these nano-clusters. TEM was used to corroborate our simulation results and showed a crossover frommore » a disordered nano-cluster to a core-shell structure.« less

  6. Development of novel nonvolatile memory devices using the colossal magnetoresistive oxide praseodymium-calcium-manganese trioxide

    NASA Astrophysics Data System (ADS)

    Papagianni, Christina

    Pr0.7Ca0.3MnO3 (PCMO) manganese oxide belongs in the family of materials known as transition metal oxides. These compounds have received increased attention due to their perplexing properties such as Colossal Magnetoresistance effect, Charge-Ordered phase, existence of phase-separated states etc. In addition, it was recently discovered that short electrical pulses in amplitude and duration are sufficient to induce reversible and non-volatile resistance changes in manganese perovskite oxide thin films at room temperature, known as the EPIR effect. The existence of the EPIR effect in PCMO thin films at room temperature opens a viable way for the realization of fast, high-density, low power non-volatile memory devices in the near future. The purpose of this study is to investigate, optimize and understand the properties of Pr0.7Ca0.3MnO 3 (PCMO) thin film devices and to identify how these properties affect the EPIR effect. PCMO thin films were deposited on various substrates, such as metals, and conducting and insulating oxides, by pulsed laser and radio frequency sputtering methods. Our objective was to understand and compare the induced resistive states. We attempted to identify the induced resistance changes by considering two resistive models to be equivalent to our devices. Impedance spectroscopy was also utilized in a wide temperature range that was extended down to 70K. Fitted results of the temperature dependence of the resistance states were also included in this study. In the same temperature range, we probed the resistance changes in PCMO thin films and we examined whether the phase transitions affect the EPIR effect. In addition, we included a comparison of devices with electrodes consisting of different size and different materials. We demonstrated a direct relation between the EPIR effect and the phase diagram of bulk PCMO samples. A model that could account for the observed EPIR effect is presented.

  7. 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

  8. Fabrication, Characterization, and Biological Activity of Avermectin Nano-delivery Systems with Different Particle Sizes

    NASA Astrophysics Data System (ADS)

    Wang, Anqi; Wang, Yan; Sun, Changjiao; Wang, Chunxin; Cui, Bo; Zhao, Xiang; Zeng, Zhanghua; Yao, Junwei; Yang, Dongsheng; Liu, Guoqiang; Cui, Haixin

    2018-01-01

    Nano-delivery systems for the active ingredients of pesticides can improve the utilization rates of pesticides and prolong their control effects. This is due to the nanocarrier envelope and controlled release function. However, particles containing active ingredients in controlled release pesticide formulations are generally large and have wide size distributions. There have been limited studies about the effect of particle size on the controlled release properties and biological activities of pesticide delivery systems. In the current study, avermectin (Av) nano-delivery systems were constructed with different particle sizes and their performances were evaluated. The Av release rate in the nano-delivery system could be effectively controlled by changing the particle size. The biological activity increased with decreasing particle size. These results suggest that Av nano-delivery systems can significantly improve the controllable release, photostability, and biological activity, which will improve efficiency and reduce pesticide residues.

  9. Nanostructured Iron and Manganese Oxide Electrode Materials for Lithium Batteries: Influence of Chemical and Physical Properties on Electrochemistry

    NASA Astrophysics Data System (ADS)

    Durham, Jessica L.

    The widespread use of portable electronics and growing interest in electric and hybrid vehicles has generated a mass market for batteries with increased energy densities and enhanced electrochemical performance. In order to address a variety of applications, commercially fabricated secondary lithium-ion batteries employ transition metal oxide based electrodes, the most prominent of which include lithium nickel manganese cobalt oxide (LiNixMn yCo1-x-yO2), lithium iron phosphate (LiFePO4), and lithium manganese oxide (LiMn 2O4). Transition metal oxides are of particular interest as cathode materials due to their robust framework for lithium intercalation, potential for high energy density, and utilization of earth-abundant elements (i.e. iron and manganese) leading to decreased toxicity and cost-effective battery production on industrial scales. Specifically, this research focuses on MgFe2O4, AgxMn8O16, and AgFeO 2 transition metal oxides for use as electrode materials in lithium-based batteries. The electrode materials are prepared via co-precipitation, reflux, and hydrothermal methods and characterized by several techniques (XRD, SEM, BET, TGA, DSC, XPS, Raman, etc.). The low-temperature syntheses allowed for precise manipulation of structural, compositional, and/or functional properties of MgFe2O4, AgxMn8 O16, and AgFeO2 which have been shown to influence electrochemical behavior. In addition, advanced in situ and ex situ characterization techniques are employed to study the lithiation/de-lithiation process and establish valid redox mechanisms. With respect to both chemical and physical properties, the influence of MgFe2O4 particle size and morphology on electrochemical behavior was established using ex situ X-ray absorption spectroscopy (XAS) and transmission electron microscopy (TEM) imaging. Based on composition, tunneled AgxMn8O16 nanorods, prepared with distinct Ag+ contents and crystallite sizes, display dramatic differences in ion-transport kinetics due to

  10. Co-precipitation synthesis of nano-composites consists of zinc and tin oxides coatings on glass with enhanced photocatalytic activity on degradation of Reactive Blue 160 KE2B.

    PubMed

    Habibi, Mohammad Hossein; Mardani, Maryam

    2015-02-25

    Nano-composite containing zinc oxide-tin oxide was obtained by a facile co-precipitation route using tin chloride tetrahydrate and zinc chloride as precursors and coated on glass by Doctor Blade deposition. The crystalline structure and morphology of composites were evaluated by X-ray diffraction (XRD) and field emission scanning electron microscopy (FESEM). The XRD results showed peaks relative to zinc oxide with hexagonal wurtzite structure and tin oxide with tetragonal structure. FESEM observations showed that the nano-composite consisted of aggregates of particles with an average particle size of 18 nm. The photocatalytic activity of the pure SnO2, pure ZnO, ZnSnO3-Zn2SnO4 and ZnO-SnO2 nano-structure thin films was examined using the degradation of a textile dye Reactive Blue 160 (KE2B). ZnO-SnO2 nano-composite showed enhanced photo-catalytic activity than the pure zinc oxide and tin oxide. The enhanced photo-catalytic activity of the nano-composite was ascribed to an improved charge separation of the photo-generated electron-hole pairs. Copyright © 2014 Elsevier B.V. All rights reserved.

  11. Novel synergistic hydrous iron-nickel-manganese (HINM) trimetal oxide for hazardous arsenite removal.

    PubMed

    Nasir, A M; Goh, P S; Ismail, A F

    2018-06-01

    A novel hydrous iron-nickel-manganese (HINM) trimetal oxide was successfully fabricated using oxidation and coprecipitation method for metalloid arsenite removal. The atomic ratio of Fe:Ni:Mn for this adsorbent is 3:2:1. HINM adsorbent was identified as an amorphous nanosized adsorbent with particle size ranged from 30 nm to 60 nm meanwhile the total active surface area and pore diameter of HINM area of 195.78 m 2 /g and 2.43 nm, respectively. Experimental data of arsenite adsorption is best fitted into pseudo-second order and Freundlich isotherm model. The maximum adsorption capacity of arsenite onto HINM was 81.9 mg/g. Thermodynamic study showed that the adsorption of arsenite was a spontaneous and endothermic reaction with enthalpy change of 14.04 kJ/mol and Gibbs energy of -12 to -14 kJ/mol. Zeta potential, thermal gravimetric (TGA) and Fourier transform infrared (FTIR) analysis were applied to elucidate the mechanism of arsenite adsorption by HINM. Mechanism of arsenite adsorption by HINM involved both chemisorption and physisorption based on the electrostatic attraction between arsenite ions and surface charge of HINM. It also involved the hydroxyl substitution by arsenite ions through the formation of inner-sphere complex. Reusability of HINM trimetal oxide was up to 89% after three cycles of testing implied that HINM trimetal oxide is a promising and practical adsorbent for arsenite. Copyright © 2018 Elsevier Ltd. All rights reserved.

  12. 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.

  13. Oxygen Isotope Signatures of Biogenic Manganese(III/IV) Oxides

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

    Manganese (Mn) oxide minerals are pervasive throughout a number of surface earth environments as rock varnishes, ferromanganese nodules, crusts around deep-sea vents, and cave deposits among many other marine, freshwater, and terrestrial deposits. Mn(III,IV) oxides are also among the strongest sorbents and oxidants in surface earth environments and are crucial to understanding the fate of organic matter in sedimentary environments. The precipitation of Mn oxide minerals proceeds via both abiotic and biotic oxidation pathways, the latter due to the indirect or direct activity of Mn(II)- oxidizing microorganisms, including bacteria and fungi. Although the precipitation of Mn oxides is believed to be primarily controlled by Mn(II)-oxidizing organisms in most surface earth environments, confirmation of this generally held notion has remained illusive and limits our understanding of their formation on Earth and beyond (e.g., Mars). Previous work provided evidence that O atom incorporation by specific Mn oxidation pathways may exhibit unique and predictable isotopic fractionation. In this study, we expand upon this evidence by measuring the oxygen isotope signature of several biogenic and abiogenic Mn oxide minerals synthesized under a range of oxygen-18 labeled water. These results allow us to determine the relative amount oxygen atoms derived from water and molecular oxygen that are incorporated in the oxide and shed light on corresponding isotope fractionation factors. Additionally, we show that, once precipitated, Mn oxide isotope signatures are robust with respect to aqueous oxygen isotope exchange. The study provides a foundation on which to study and interpret Mn oxides in natural environments and determine which environmental controls may govern Mn(II) oxidation.

  14. Physical properties of spin-valve films grown on naturally oxidized metal nano-oxide surfaces

    NASA Astrophysics Data System (ADS)

    Mao, Ming; Cerjan, Charlie; Kools, Jacques

    2002-05-01

    The physical properties of spin-valve films NiFe 25 Å/CoFe 10 Å/Cu(tCu)/CoFe 30 Å/IrMn 70 Å/Ta 20 Å with graded Cu layer thickness (tCu=18-45 Å) grown on the surface of metal nano-oxide layers (NOLs) were studied. The NOLs were formed from ultrathin Al, Cr, Cu, Nb, Ta, CoFe, NiFe, and NiFeCr layers by natural oxidation. The growth of the spin-valve films on NOLs has led to an enhancement in giant magnetoresistance value by up to 48%. A corresponding reduction in minimum film resistance by over 10% confirms that this enhancement originates from an increase in the mean free path of spin-polarized electrons due to the resultant specular reflection at the nano-oxide surfaces. A wide spectrum of oscillatory interlayer exchange coupling dependence on tCu for these NOL-bearing films suggests that a specular nano-oxide surface does not necessarily result in a smoother multilayer structure. The observation of an enhanced exchange biasing among these spin-valve films appears in contradiction to the observed deterioration of their crystallographic quality. As an important application, TaOx, CrOx, and NbOx could be employed as an alternative to AlOx as the barrier layer for magnetic tunnel junctions.

  15. Synthesis of nano-sized ZnO particles by co-precipitation method with variation of heating time

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

    Purwaningsih, S. Y., E-mail: sriyanisaputri@gmail.com; Pratapa, S.; Triwikantoro

    Zinc oxide powders have been synthesized by a co-precipitation method at low temperature (85 °C), using zinc acetate dihydrate, ammonia, hydrochloric acid solutions as the reactants. A number of process parameters such as reaction temperature, solution basicity or pH and heating time are the main factors affecting the morphology and physical properties of the ZnO nanostructures. In this work the effect of heating time on the morphology and particles size were studied. The as-synthesized ZnO powders were characterized using transmission electron microscopy (TEM) and X-ray diffraction (XRD) techniques. The samples were also analyzed using Fourier transform infrared (FTIR). Rietveld refinementmore » of XRD data confirms that ZnO crystallizes in the hexagonal wurtzite structure with high degree of purity and the (101) plane predominant. The XRD results show that the average crystallite sizes were about 66, 27 and 12 nm for 3, 4 and 5 h of heating times, respectively. The XRD analysis indicated that a fraction of nano-sized ZnO powders were in the form of aggregates, which was also verified by TEM image. The TEM photograph demonstrated that the nano-sized ZnO particles were a pseudo-spherical shape.« less

  16. A novel copper (II) complex containing a tetradentate Schiff base: Synthesis, spectroscopy, crystal structure, DFT study, biological activity and preparation of its nano-sized metal oxide

    NASA Astrophysics Data System (ADS)

    Tohidiyan, Zeinab; Sheikhshoaie, Iran; Khaleghi, Mouj; Mague, Joel T.

    2017-04-01

    A new nano-sized copper (II) complex, [Cu(L)] with a tetra dentate Schiff base ligand, 2-((E)-(2-(E-5- bromo-2-hydroxybezenylideneamino) methyl)-4-bromophenol [H2L] was prepared by the reaction between of Cu (CH3COO)2·2H2O and (H2L) ligand with the ratio of 1:1, at the present of triethylamine by sonochemical method. The structure of [Cu (L)] complex was determined by FT-IR, UV-Vis, FESEM and molar conductivity. The structure of [Cu (L)] complex was characterized by single crystal X-ray diffraction. The geometry of [Cu (L)] complex was optimized using density functional theory (DFT) method with the B3LYP/6-31(d) level of theory. The calculated bond lengths and bond angles are in good agreement with the X-ray data. This complex was used as a novel precursor for preparing of CuO nano particles by the thermal decomposition method. The antibacterial activities of [H2L] ligand, nano-sized [Cu (L)] complex and nano-sized CuO have been screened against various strains of bacteria. According to the results, nano-sized CuO can be considered as an appropriate antibiotic agent.

  17. Metal Ions Removal Using Nano Oxide Pyrolox™ Material

    NASA Astrophysics Data System (ADS)

    Gładysz-Płaska, A.; Skwarek, E.; Budnyak, T. M.; Kołodyńska, D.

    2017-02-01

    The paper presents the use of Pyrolox™ containing manganese nano oxides used for the removal of Cu(II), Zn(II), Cd(II), and Pb(II) as well as U(VI) ions. Their concentrations were analyzed using the atomic absorption spectrometer SpectrAA 240 FS (Varian) as well as UV-vis method. For this purpose the static kinetic and equilibrium studies were carried out using the batch technique. The effect of solution pH, shaking time, initial metal ion concentrations, sorbent dosage, and temperature was investigated. The equilibrium data were analyzed using the sorption isotherm models proposed by Freundlich, Langmuir-Freundlich, Temkin, and Dubinin-Radushkevich. The kinetic results showed that the pseudo second order kinetic model was found to correlate the experimental data well. The results indicate that adsorption of Cu(II), Zn(II), Cd(II), and Pb(II) as well as U(VI) ions is strongly dependent on pH. The value of pH 4-7 was optimal adsorption. The time to reach the equilibrium was found to be 24 h, and after this time, the sorption percentage reached about 70%. Kinetics of Cu(II), Zn(II), Cd(II), Pb(II), and U(VI) adsorption on the adsorbent can be described by the pseudo second order rate equation. Nitrogen adsorption/desorption, infrared spectroscopy (FTIR), and scanning electron microscopy (SEM) measurements for adsorbent characterization were performed. Characteristic points of the double layer determined for the studied Pyrolox™ sample in 0.001 mol/dm3 NaCl solution are pHPZC = 4 and pHIEP < 2.

  18. Oxygen isotope analysis of bacterial and fungal manganese oxidation.

    PubMed

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

    2018-07-01

    The ability of micro-organisms to oxidize manganese (Mn) from Mn(II) to Mn(III/IV) oxides transcends boundaries of biological clade or domain. Many bacteria and fungi oxidize Mn(II) to Mn(III/IV) oxides directly through enzymatic activity or indirectly through the production of reactive oxygen species. Here, we determine the oxygen isotope fractionation factors associated with Mn(II) oxidation via various biotic (bacteria and fungi) and abiotic Mn(II) reaction pathways. As oxygen in Mn(III/IV) oxides may be derived from precursor water and molecular oxygen, we use a twofold approach to determine the isotope fractionation with respect to each oxygen source. Using both 18 O-labeled water and closed-system Rayleigh distillation approaches, we constrain the kinetic isotope fractionation factors associated with O atom incorporation during Mn(II) oxidation to -17.3‰ to -25.9‰ for O 2 and -1.9‰ to +1.8‰ for water. Results demonstrate that stable oxygen isotopes of Mn(III/IV) oxides have potential to distinguish between two main classes of biotic Mn(II) oxidation: direct enzymatic oxidation in which O 2 is the oxidant and indirect enzymatic oxidation in which superoxide is the oxidant. The fraction of Mn(III/IV) oxide-associated oxygen derived from water varies significantly (38%-62%) among these bio-oxides with only weak relationship to Mn oxidation state, suggesting Mn(III) disproportionation may account for differences in the fraction of mineral-bound oxygen from water and O 2 . Additionally, direct incorporation of molecular O 2 suggests that Mn(III/IV) oxides contain a yet untapped proxy of δ18OO2 of environmental O 2 , a parameter reflecting the integrated influence of global respiration, photorespiration, and several other biogeochemical reactions of global significance. © 2018 John Wiley & Sons Ltd.

  19. 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

  20. 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.

  1. 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.

  2. Oxidative degradation of nalidixic acid by nano-magnetite via Fe2+/O2-mediated reactions.

    PubMed

    Ardo, Sandy G; Nélieu, Sylvie; Ona-Nguema, Georges; Delarue, Ghislaine; Brest, Jessica; Pironin, Elsa; Morin, Guillaume

    2015-04-07

    Organic pollution has become a critical issue worldwide due to the increasing input and persistence of organic compounds in the environment. Iron minerals are potentially able to degrade efficiently organic pollutants sorbed to their surfaces via oxidative or reductive transformation processes. Here, we explored the oxidative capacity of nano-magnetite (Fe3O4) having ∼ 12 nm particle size, to promote heterogeneous Fenton-like reactions for the removal of nalidixic acid (NAL), a recalcitrant quinolone antibacterial agent. Results show that NAL was adsorbed at the surface of magnetite and was efficiently degraded under oxic conditions. Nearly 60% of this organic contaminant was eliminated after 30 min exposure to air bubbling in solution in the presence of an excess of nano-magnetite. X-ray diffraction (XRD) and Fe K-edge X-ray absorption spectroscopy (XANES and EXAFS) showed a partial oxidation of magnetite to maghemite during the reaction, and four byproducts of NAL were identified by liquid chromatography-mass spectroscopy (UHPLC-MS/MS). We also provide evidence that hydroxyl radicals (HO(•)) were involved in the oxidative degradation of NAL, as indicated by the quenching of the degradation reaction in the presence of ethanol. This study points out the promising potentialities of mixed valence iron oxides for the treatment of soils and wastewater contaminated by organic pollutants.

  3. Green synthesis of manganese oxide nanoparticles for the electrochemical sensing of p-nitrophenol

    NASA Astrophysics Data System (ADS)

    Kumar, Vineet; Singh, Kulvinder; Panwar, Shaily; Mehta, Surinder Kumar

    2017-03-01

    Manganese oxide (MnO) NPs are widely used in contaminant sensing, drug delivery, data storage, catalysis and biomedical imaging. Green synthesis of NPs is important due to increased concern of environmental pollution. Green chemistry based synthesis of NPs is preferred due to its ecofriendly nature. In this study, MnO NPs of different sizes were synthesized in aqueous medium using clove, i.e., Syzygium aromaticum extract (CE) as reducing and stabilizing agents. These NPs were used for the electrochemical sensing of p-nitrophenol (PNP). The synthesis of MnO NPs was over in 30 min. MnO NPs of different sizes were obtained by varying metal ion concentration, metal ion volume ratio, CE concentration, CE volume ratio, and incubation temperature. Selectively, 4 nm MnO NPs were used for electrochemical sensing of paranitrophenol. The MnO NPs modified gold electrodes detected PNP with good sensitivity, 0.16 µA µM-1 cm2. The limit of PNP detection was 15.65 µM. The MnO NPs prepared using CE based green chemistry approach is useful for PNP sensing. These NPs can also be useful for various in vivo applications in which the NPs come in human contact.

  4. Synthesis and characterization of nano-sized CaCO3 in purified diet

    NASA Astrophysics Data System (ADS)

    Mulyaningsih, N. N.; Tresnasari, D. R.; Ramahwati, M. R.; Juwono, A. L.; Soejoko, D. S.; Astuti, D. A.

    2017-07-01

    The growth and development of animals depend strongly on the balanced nutrition in the diet. This research aims is to characterize the weight variations of nano-sized calcium carbonate (CaCO3) in purified diet that to be fed to animal model of rat. The nano-sized CaCO3 was prepared by milling the calcium carbonate particles for 20 hours at a rotation speed of 1000 rpm and resulting particle size in a range of 2-50 nm. Nano-sized CaCO3 added to purified diet to the four formulas that were identified as normal diet (N), deficiency calcium (DC), rich in calcium (RC), and poor calcium (PC) with containing in nano-sized CaCO3 much as 0.50 %, 0.00 %, 0.75 % and 0.25 % respectively. The nutritional content of the purified diet was proximate analyzed, it resulted as followed moisture, ash, fat, protein, crude fiber. The quantities of chemical element were analyzed by atomic absorption spectrometry (AAS), it resulted iron, magnesium, potassium and calcium. The results showed that N diet (Ca: 16,914.29 ppm) were suggested for healthy rats and RC diet (Ca: 33,696.13 ppm) for conditioned osteoporosis rats. The crystalline phases of the samples that were examined by X-ray diffraction showed that crystalline phase increased with the increasing concentration of CaCO3.

  5. High-voltage nano-oxidation in deionized water and atmospheric environments by atomic force microscopy.

    PubMed

    Huang, Jen-Ching; Chen, Chung-Ming

    2012-01-01

    This study used atomic force microscopy (AFM), metallic probes with a nanoscale tip, and high-voltage generators to investigate the feasibility of high-voltage nano-oxidation processing in deionized water (DI water) and atmospheric environments. Researchers used a combination of wire-cutting and electrochemical etching to transform a 20-μm-thick stainless steel sheet into a conductive metallic AFM probe with a tip radius of 60 nm, capable of withstanding high voltages. The combination of AFM, high-voltage generators, and nanoscale metallic probes enabled nano-oxidation processing at 200 V in DI water environments, producing oxides up to 66.6 nm in height and 467.03 nm in width. Oxides produced through high-voltage nano-oxidation in atmospheric environments were 117.29 nm in height and 551.28 nm in width, considerably exceeding the dimensions of those produced in DI water. An increase in the applied bias voltage led to an apparent logarithmic increase in the height of the oxide dots in the range of 200-400 V. The performance of the proposed high-voltage nano-oxidation technique was relatively high with seamless integration between the AFM machine and the metallic probe fabricated in this study. © Wiley Periodicals, Inc.

  6. 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.

  7. 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.

  8. A polymer solution technique for the synthesis of nano-sized Li 2TiO 3 ceramic breeder powders

    NASA Astrophysics Data System (ADS)

    Jung, Choong-Hwan; Lee, Sang Jin; Kriven, Waltraud M.; Park, Ji-Yeon; Ryu, Woo-Seog

    2008-02-01

    Nano-sized Li 2TiO 3 powder was fabricated by an organic-inorganic solution route. A steric entrapment route employing ethylene glycol was used for the preparation of the nano-sized Li 2TiO 3 particles. Titanium isopropoxide and lithium nitrate were dissolved in liquid-type ethylene glycol without any precipitation. With the optimum amount of the polymer, the metal cations (Li and Ti) were dispersed in the solution and a homogeneous polymeric network was formed. The organic-inorganic precursor gels were turned to crystalline powders through an oxidation reaction during a calcination process. The dried precursor gel showed the carbon-free Li 2TiO 3 crystalline form which was observed above 400 °C. The primary particle size of the carbon-free Li 2TiO 3 was about 70 nm, and the structure of the crystallized powder was porous and agglomerated. The powder compact was densified to 92% of TD at a relatively low sintering temperature of 1100 °C for 2 h.

  9. 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.

  10. Synthesis and improved explosion behaviors of aluminum powders coated with nano-sized nickel film

    NASA Astrophysics Data System (ADS)

    Kim, Kyung Tae; Kim, Dong Won; Kim, Soo Hyung; Kim, Chang Kee; Choi, Yoon Jeong

    2017-09-01

    Nickel (Ni) materials with a thickness of a few hundred nm were homogeneously coated on the surfaces of aluminum (Al) powders by an electroless plating process. The Ni-coated Al powders show characteristic interfacial structures mixed of Ni, Al and O instead of densely packed Al oxide at the surface. The explosion test of the Ni-coated Al powders utilizing flame ignition showed that the powders had a 3.6 times enhanced pressurization rate of 405 kPa/ms compared to 111 kPa/ms of uncoated Al powders. It was found that this is due to a feasible diffusion of oxygen atoms into the Al powders through the thin and rough interfacial layers present at the Ni/Al interface. These results clearly indicate that nano-sized Ni film introduced instead of surface oxide acts as a very profitable layer to achieve efficient combustion behaviors by a rapid oxidation of Al powders.

  11. 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

  12. 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

  13. 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

  14. 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.

  15. Size-Dependent Neurotoxicity of Aluminum Oxide Particles: a Comparison Between Nano- and Micrometer Size on the Basis of Mitochondrial Oxidative Damage.

    PubMed

    Mirshafa, Atefeh; Nazari, Mehdi; Jahani, Daniel; Shaki, Fatemeh

    2018-06-01

    Aluminum nanoparticles (AlNPs) are among the most abundantly produced nanosized particles in the market. There is limited information about the potential harmful effects of aluminum oxide due to its particle size on human health. Considering the toxic effects of Al on brain as its target tissue, in this study, the toxicity of nanoparticles, microparticles, and ionic forms of Al on rat brain and isolated mitochondria was evaluated. Sixty male Wistar rats were divided into ten groups (six rats each), in which group I was the control, and the other groups were administered different doses of Al nanoparticles, Al microparticles (AlMP), and Al ionic forms (2, 4, and 8 mg/kg, i.p.) for 28 days. After 24 h, the animals were killed, brain tissue was separated, the mitochondrial fraction was isolated, and oxidative stress markers were measured. Also, mitochondrial function was assayed by MTT test. The results showed that all forms of Al particles induced ROS formation, lipid peroxidation, protein oxidation, glutathione depletion, mitochondrial dysfunction, and gait abnormalities in a dose-dependent manner. In addition, Al particles decreased mitochondrial membrane potential. These data indicated that oxidative stress might contribute to the toxicity effects of Al. Comparison of oxidative stress markers between all forms of Al revealed that the toxic effect of AlNP on brain tissue was substantially more than that caused by AlMP and bulk form. This study showed more neurotoxicity of AlNPs compared to other forms on brain oxidative damage that probably is due to more penetration into the brain.

  16. 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

  17. Controlled deposition of size-selected MnO nanoparticle thin films for water splitting applications: reduction of onset potential with particle size

    NASA Astrophysics Data System (ADS)

    Khojasteh, Malak; Haghighat, Shima; Dawlaty, Jahan M.; Kresin, Vitaly V.

    2018-05-01

    Emulating water oxidation catalyzed by the oxomanganese clusters in the photosynthetic apparatus of plants has been a long-standing scientific challenge. The use of manganese oxide films has been explored, but while they may be catalytically active on the surface, their poor conductivity hinders their overall performance. We have approached this problem by using manganese oxide nanoparticles with sizes of 4, 6 and 8 nm, produced in a sputter-gas-aggregation source and soft-landed onto conducting electrodes. The mass loading of these catalytic particles was kept constant and corresponded to 45%–80% of a monolayer coverage. Measurements of the water oxidation threshold revealed that the onset potential decreases significantly with decreasing particle size. The final stoichiometry of the catalytically active nanoparticles, after exposure to air, was identified as predominantly MnO. The ability of such a sub-monolayer film to lower the reaction threshold implies that the key role is played by intrinsic size effects, i.e., by changes in the electronic properties and surface fields of the nanoparticles with decreasing size. We anticipate that this work will serve to bridge the knowledge gap between bulk thick film electrocatalysts and natural photosynthetic molecular-cluster complexes.

  18. 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.

  19. 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.

  20. Secretome-based Manganese(II) Oxidation by Filamentous Ascomycete Fungi

    NASA Astrophysics Data System (ADS)

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

    2017-12-01

    Manganese (Mn) oxides are among the strongest oxidants in the environment, and Mn(II) oxidation to Mn(III/IV) (hydr)oxides includes both abiotic and microbially-mediated processes. While white-rot Basidiomycete fungi oxidize Mn(II) using laccases and Mn peroxidases in association with lignocellulose degradation, the mechanisms by which filamentous Ascomycete fungi oxidize Mn(II) and a physiological role for Mn(II) oxidation in these organisms remain poorly understood. Through a combination of chemical and in-gel assays, bulk mass spectrometry, and iTRAQ proteomics, we demonstrate enzymatic Mn(II) oxidation in the secretomes of three phylogenetically diverse Ascomycetes that were isolated from Mn-laden sediments. Candidate Mn(II)-oxidizing enzymes were species-specific and included bilirubin oxidase and tyrosinase in Stagonospora sp. SRC1lsM3a, GMC oxidoreductase in Paraconiothyrium sporulosum AP3s5-JAC2a, and FAD-binding oxidoreductases in Pyrenochaeta sp. DS3sAY3a. These findings were supported by full proteomic characterization of the secretomes, which revealed a lack of Mn, lignin, and versatile peroxidases in these Ascomycetes but a substantially higher proportion of LMCOs and GMC oxidoreductases compared to wood-rot Basidiomycetes. We also identified the potential for indirect enzymatic Mn(II) oxidation by hydroxyl radical, as the secretomes were rich in diverse lignocellulose-degrading enzymes that could participate in Fenton chemistry. A link between Mn(II) oxidation and carbon oxidation analogous to white-rot Basidiomycetes remains unknown in these Ascomycetes. Interestingly, growth rates on rich medium were unaffected by the presence of Mn(II), and the production of Mn(II)-oxidizing proteins in the secretome was constitutive and not inducible by Mn(II). Thus, no physiological benefit of Mn(II) oxidation in these Ascomycetes has yet been identified, and Mn(II) oxidation appears to be a side reaction. Future work will explore the lignin-degrading capacity of

  1. Structural, morphological, magnetic and dielectric characterization of nano-phased antimony doped manganese zinc ferrites

    NASA Astrophysics Data System (ADS)

    Sridhar, Ch. S. L. N.; Lakshmi, Ch. S.; Govindraj, G.; Bangarraju, S.; Satyanarayana, L.; Potukuchi, D. M.

    2016-05-01

    Nano-phased doped Mn-Zn ferrites, viz., Mn0.5-x/2Zn0.5-x/2SbXFe2O4 for x=0 to 0.3 (in steps of 0.05) prepared by hydrothermal method are characterized by X-ray diffraction, Infrared and scanning electron microscopy. XRD and SEM infer the growth of nano-crystalline cubic and hematite (α-Fe2O3) phase structures. IR reveals the ferrite phase abundance and metal ion replacement with dopant. Decreasing trend of lattice constant with dopant reflects the preferential replacement of Fe3+ions by Sb5+ion. Doping is found to cause for the decrease (i.e., 46-14 nm) of grain size. An overall trend of decreasing saturation magnetization is observed with doping. Low magnetization is attributed to the diamagnetic nature of dopant, abundance of hematite (α-Fe2O3) phase, non-stoichiometry and low temperature (800 °C) sintering conditions. Increasing Yafet-Kittel angle reflects surface spin canting to pronounce lower Ms. Lower coercivity is observed for x≤0.1, while a large Hc results for higher concentrations. High ac resistivity (~106 ohm-cm) and low dielectric loss factor (tan δ~10-2-10-3) are witnessed. Resistivity is explained on the base of a transformation in the Metal Cation-to-Oxide anion bond configuration and blockade of conductivity path. Retarded hopping (between adjacent B-sites) of carriers across the grain boundaries is addressed. Relatively higher resistivity and low dielectric loss in Sbdoped Mn-Zn ferrite systems pronounce their utility in high frequency applications.

  2. Environmental risk assessment of engineered nano-SiO2 , nano iron oxides, nano-CeO2 , nano-Al2 O3 , and quantum dots.

    PubMed

    Wang, Yan; Nowack, Bernd

    2018-05-01

    Many research studies have endeavored to investigate the ecotoxicological hazards of engineered nanomaterials (ENMs). However, little is known regarding the actual environmental risks of ENMs, combining both hazard and exposure data. The aim of the present study was to quantify the environmental risks for nano-Al 2 O 3 , nano-SiO 2 , nano iron oxides, nano-CeO 2 , and quantum dots by comparing the predicted environmental concentrations (PECs) with the predicted-no-effect concentrations (PNECs). The PEC values of these 5 ENMs in freshwaters in 2020 for northern Europe and southeastern Europe were taken from a published dynamic probabilistic material flow analysis model. The PNEC values were calculated using probabilistic species sensitivity distribution (SSD). The order of the PNEC values was quantum dots < nano-CeO 2  < nano iron oxides < nano-Al 2 O 3  < nano-SiO 2 . The risks posed by these 5 ENMs were demonstrated to be in the reverse order: nano-Al 2 O 3  > nano-SiO 2  > nano iron oxides > nano-CeO 2  > quantum dots. However, all risk characterization values are 4 to 8 orders of magnitude lower than 1, and no risk was therefore predicted for any of the investigated ENMs at the estimated release level in 2020. Compared to static models, the dynamic material flow model allowed us to use PEC values based on a more complex parameterization, considering a dynamic input over time and time-dependent release of ENMs. The probabilistic SSD approach makes it possible to include all available data to estimate hazards of ENMs by considering the whole range of variability between studies and material types. The risk-assessment approach is therefore able to handle the uncertainty and variability associated with the collected data. The results of the present study provide a scientific foundation for risk-based regulatory decisions of the investigated ENMs. Environ Toxicol Chem 2018;37:1387-1395. © 2018 SETAC. © 2018 SETAC.

  3. 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

  4. 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

  5. Nano-sized and micro-sized polystyrene particles affect phagocyte function

    PubMed Central

    Prietl, B.; Meindl, C.; Roblegg, E.; Pieber, T. R.; Lanzer, G.; Fröhlich, E.

    2015-01-01

    Adverse effect of nanoparticles may include impairment of phagocyte function. To identify the effect of nanoparticle size on uptake, cytotoxicity, chemotaxis, cytokine secretion, phagocytosis, oxidative burst, nitric oxide production and myeloperoxidase release, leukocytes isolated from human peripheral blood, monocytes and macrophages were studied. Carboxyl polystyrene (CPS) particles in sizes between 20 and 1,000 nm served as model particles. Twenty nanometers CPS particles were taken up passively, while larger CPS particles entered cells actively and passively. Twenty nanometers CPS were cytotoxic to all phagocytes, ≥500 nm CPS particles only to macrophages. Twenty nanometers CPS particles stimulated IL-8 secretion in human monocytes and induced oxidative burst in monocytes. Five hundred nanometers and 1,000 nm CPS particles stimulated IL-6 and IL-8 secretion in monocytes and macrophages, chemotaxis towards a chemotactic stimulus of monocytes and phagocytosis of bacteria by macrophages and provoked an oxidative burst of granulocytes. At very high concentrations, CPS particles of 20 and 500 nm stimulated myeloperoxidase release of granulocytes and nitric oxide generation in macrophages. Cytotoxic effect could contribute to some of the observed effects. In the absence of cytotoxicity, 500 and 1,000 nm CPS particles appear to influence phagocyte function to a greater extent than particles in other sizes. PMID:24292270

  6. Nano-sized and micro-sized polystyrene particles affect phagocyte function.

    PubMed

    Prietl, B; Meindl, C; Roblegg, E; Pieber, T R; Lanzer, G; Fröhlich, E

    2014-02-01

    Adverse effect of nanoparticles may include impairment of phagocyte function. To identify the effect of nanoparticle size on uptake, cytotoxicity, chemotaxis, cytokine secretion, phagocytosis, oxidative burst, nitric oxide production and myeloperoxidase release, leukocytes isolated from human peripheral blood, monocytes and macrophages were studied. Carboxyl polystyrene (CPS) particles in sizes between 20 and 1,000 nm served as model particles. Twenty nanometers CPS particles were taken up passively, while larger CPS particles entered cells actively and passively. Twenty nanometers CPS were cytotoxic to all phagocytes, ≥500 nm CPS particles only to macrophages. Twenty nanometers CPS particles stimulated IL-8 secretion in human monocytes and induced oxidative burst in monocytes. Five hundred nanometers and 1,000 nm CPS particles stimulated IL-6 and IL-8 secretion in monocytes and macrophages, chemotaxis towards a chemotactic stimulus of monocytes and phagocytosis of bacteria by macrophages and provoked an oxidative burst of granulocytes. At very high concentrations, CPS particles of 20 and 500 nm stimulated myeloperoxidase release of granulocytes and nitric oxide generation in macrophages. Cytotoxic effect could contribute to some of the observed effects. In the absence of cytotoxicity, 500 and 1,000 nm CPS particles appear to influence phagocyte function to a greater extent than particles in other sizes.

  7. Formation and anisotropic magnetoresistance of Co/Pt nano-contacts through aluminum oxide barrier

    NASA Astrophysics Data System (ADS)

    Al-Mahdawi, Muftah; Sahashi, Masashi

    2014-01-01

    We report on the observation of anisotropic magnetoresistance (AMR) in vertical asymmetric nano-contacts (NCs) made through AlOx nano-oxide layer (NOL) formed by ion-assisted oxidation method in the film stack of Co/AlOx-NOL/Pt. Analysis of NC formation was based on in situ conductive atomic force microscopy and transmission electron microscopy. Depending on the purity of NCs from Al contamination, we observed up to 29% AMR ratio at room temperature.

  8. 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.

  9. 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

  10. 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.

  11. 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.

  12. Iron oxide-mediated semiconductor photocatalysis vs. heterogeneous photo-Fenton treatment of viruses in wastewater. Impact of the oxide particle size.

    PubMed

    Giannakis, Stefanos; Liu, Siting; Carratalà, Anna; Rtimi, Sami; Talebi Amiri, Masoud; Bensimon, Michaël; Pulgarin, César

    2017-10-05

    The photo-Fenton process is recognized as a promising technique towards microorganism disinfection in wastewater, but its efficiency is hampered at near-neutral pH operating values. In this work, we overcome these obstacles by using the heterogeneous photo-Fenton process as the default disinfecting technique, targeting MS2 coliphage in wastewater. The use of low concentrations of iron oxides in wastewater without H 2 O 2 (wüstite, maghemite, magnetite) has demonstrated limited semiconductor-mediated MS2 inactivation. Changing the operational pH and the size of the oxide particles indicated that the isoelectric point of the iron oxides and the active surface area are crucial in the success of the process, and the possible underlying mechanisms are investigated. Furthermore, the addition of low amounts of Fe-oxides (1mgL -1 ) and H 2 O 2 in the system (1, 5 and 10mgL -1 ) greatly enhanced the inactivation process, leading to heterogeneous photo-Fenton processes on the surface of the magnetically separable oxides used. Additionally, photo-dissolution of iron in the bulk, lead to homogeneous photo-Fenton, further aided by the complexation by the dissolved organic matter in the solution. Finally, we assess the impact of the presence of the bacterial host and the difference caused by the different iron sources (salts, oxides) and the Fe-oxide size (normal, nano-sized). Copyright © 2017 Elsevier B.V. All rights reserved.

  13. 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.

  14. Flame Retardant Effect of Nano Fillers on Polydimethylsiloxane Composites.

    PubMed

    Jagdale, Pravin; Salimpour, Samera; Islam, Md Hujjatul; Cuttica, Fabio; Hernandez, Francisco C Robles; Tagliaferro, Alberto; Frache, Alberto

    2018-02-01

    Polydimethylsiloxane has exceptional fire retardancy characteristics, which make it a popular polymer in flame retardancy applications. Flame retardancy of polydimethylsiloxane with different nano fillers was studied. Polydimethylsiloxane composite fire property varies because of the shape, size, density, and chemical nature of nano fillers. In house made carbon and bismuth oxide nano fillers were used in polydimethylsiloxane composite. Carbon from biochar (carbonised bamboo) and a carbon by-product (carbon soot) were selected. For comparative study of nano fillers, standard commercial multiwall carbon nano tubes (functionalised, graphitised and pristine) as nano fillers were selected. Nano fillers in polydimethylsiloxane positively affects their fire retardant properties such as total smoke release, peak heat release rate, and time to ignition. Charring and surface ceramization are the main reasons for such improvement. Nano fillers in polydimethylsiloxane may affect the thermal mobility of polymer chains, which can directly affect the time to ignition. The study concludes that the addition of pristine multiwall carbon nano tubes and bismuth oxide nano particles as filler in polydimethylsiloxane composite improves the fire retardant property.

  15. Detection of bisphenol A using palm-size NanoAptamer analyzer.

    PubMed

    Lim, Hyun Jeong; Chua, Beelee; Son, Ahjeong

    2017-08-15

    We have demonstrated a palm-size NanoAptamer analyzer capable of detecting bisphenol A (BPA) at environmentally relevant concentrations (<1ng/mL or ppb). It is designed for performing reaction and fluorescence measurement on single cuvette sample. Modified NanoGene assay was used as the sensing mechanism where signaling DNA and QD 655 was tethered to QD 565 and magnetic bead via the aptamer. Aptamer affinity with BPA resulted in the release of the signaling DNA and QD 655 from the complex and hence corresponding decrease in QD 655 fluorescence measurement signal. Baseline characterization was first performed with empty cuvettes, quantum dots and magnetic beads under near-ideal conditions to establish essential functionality of the NanoAptamer analyzer. Duration of incubation time, number of rinse cycles, and necessity of cuvette vibration were also investigated. In order to demonstrate the capability of the NanoAptamer analyzer to detect BPA, samples with BPA concentrations ranging from 0.0005 to 1.0ng/mL (ppb) were used. The performance of the NanoAptamer analyzer was further examined by using laboratory protocol and commercial spectrofluorometer as reference. Correlation between NanoAptamer analyzer and laboratory protocol as well as commercial spectrofluorometer was evaluated via correlation plots and correlation coefficients. Copyright © 2017 Elsevier B.V. All rights reserved.

  16. 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

  17. 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.

  18. Nano-graphene in biomedicine: theranostic applications.

    PubMed

    Yang, Kai; Feng, Liangzhu; Shi, Xiaoze; Liu, Zhuang

    2013-01-21

    Owing to their unique physical and chemical properties, graphene and its derivatives such as graphene oxide (GO), reduced graphene oxide (RGO) and GO-nanocomposites have attracted tremendous interest in many different fields including biomedicine in recent years. With every atom exposed on its surface, single-layered graphene shows ultra-high surface area available for efficient molecular loading and bioconjugation, and has been widely explored as novel nano-carriers for drug and gene delivery. Utilizing the intrinsic near-infrared (NIR) optical absorbance, in vivo graphene-based photothermal therapy has been realized, achieving excellent anti-tumor therapeutic efficacy in animal experiments. A variety of inorganic nanoparticles can be grown on the surface of nano-graphene, obtaining functional graphene-based nanocomposites with interesting optical and magnetic properties useful for multi-modal imaging and imaging-guided cancer therapy. Moreover, significant efforts have also been devoted to study the behaviors and toxicology of functionalized nano-graphene in animals. It has been uncovered that both surface chemistry and sizes play key roles in controlling the biodistribution, excretion, and toxicity of nano-graphene. Biocompatibly coated nano-graphene with ultra-small sizes can be cleared out from body after systemic administration, without rendering noticeable toxicity to the treated mice. In this review article, we will summarize the latest progress in this rapidly growing field, and discuss future prospects and challenges of using graphene-based materials for theranostic applications.

  19. Nano sand filter with functionalized nanoparticles embedded in anodic aluminum oxide templates

    PubMed Central

    Phuong, NguyenThi; Andisetiawan, Anugrah; Van Lam, Do; Kim, Jeong Hwan; Choi, Doo-Sun; Whang, Kyung-Hyun; Nham, Jeasun; Lee, Yun Jung; Yoo, Yeong-Eun; Yoon, Jae Sung

    2016-01-01

    Since the ancient Egyptians had used sand as filter media for water purification, its principle has been inherited through generations and it is still being used now in industries. The sand filter consists of sand literally, and the voids within the sand bed are the pores for filtration. Here we present a filtration principle using nanoparticles, so that the voids between the nanoparticles can be considered as effective pores in nanoscale dimension. Anodic aluminum oxide (AAO) membrane has been used as the working template, and the nanoparticles have been injected and embedded within the pores of the AAO template. Nanoparticles with multiple sizes have been used in order to obtain smaller voids. Moreover, the nanoparticles have been functionalized, or electrically charged, with arginine/phenylalanine (RF) peptide group. In this way, filtration performance for charged particles or molecules, such as methylene blue, has been enhanced. Consequently, this study is expected to provide a new principle for fabrication of nano voids, or nano pores, and for filtration in nanoscale dimension. PMID:27876886

  20. Nano sand filter with functionalized nanoparticles embedded in anodic aluminum oxide templates.

    PubMed

    Phuong, NguyenThi; Andisetiawan, Anugrah; Van Lam, Do; Kim, Jeong Hwan; Choi, Doo-Sun; Whang, Kyung-Hyun; Nham, Jeasun; Lee, Yun Jung; Yoo, Yeong-Eun; Yoon, Jae Sung

    2016-11-23

    Since the ancient Egyptians had used sand as filter media for water purification, its principle has been inherited through generations and it is still being used now in industries. The sand filter consists of sand literally, and the voids within the sand bed are the pores for filtration. Here we present a filtration principle using nanoparticles, so that the voids between the nanoparticles can be considered as effective pores in nanoscale dimension. Anodic aluminum oxide (AAO) membrane has been used as the working template, and the nanoparticles have been injected and embedded within the pores of the AAO template. Nanoparticles with multiple sizes have been used in order to obtain smaller voids. Moreover, the nanoparticles have been functionalized, or electrically charged, with arginine/phenylalanine (RF) peptide group. In this way, filtration performance for charged particles or molecules, such as methylene blue, has been enhanced. Consequently, this study is expected to provide a new principle for fabrication of nano voids, or nano pores, and for filtration in nanoscale dimension.

  1. Nano sand filter with functionalized nanoparticles embedded in anodic aluminum oxide templates

    NASA Astrophysics Data System (ADS)

    Phuong, Nguyenthi; Andisetiawan, Anugrah; van Lam, Do; Kim, Jeong Hwan; Choi, Doo-Sun; Whang, Kyung-Hyun; Nham, Jeasun; Lee, Yun Jung; Yoo, Yeong-Eun; Yoon, Jae Sung

    2016-11-01

    Since the ancient Egyptians had used sand as filter media for water purification, its principle has been inherited through generations and it is still being used now in industries. The sand filter consists of sand literally, and the voids within the sand bed are the pores for filtration. Here we present a filtration principle using nanoparticles, so that the voids between the nanoparticles can be considered as effective pores in nanoscale dimension. Anodic aluminum oxide (AAO) membrane has been used as the working template, and the nanoparticles have been injected and embedded within the pores of the AAO template. Nanoparticles with multiple sizes have been used in order to obtain smaller voids. Moreover, the nanoparticles have been functionalized, or electrically charged, with arginine/phenylalanine (RF) peptide group. In this way, filtration performance for charged particles or molecules, such as methylene blue, has been enhanced. Consequently, this study is expected to provide a new principle for fabrication of nano voids, or nano pores, and for filtration in nanoscale dimension.

  2. Protective effects of Nano-elemental selenium against chromium-vi-induced oxidative stress in broiler liver.

    PubMed

    Xueting, L; Rehman, M U; Zhang, H; Tian, X; Wu, X; Shixue; Mehmood, K; Zhou, D

    2018-01-01

    The valuable role of selenium in mitigation of oxidative stress and heavy metal toxicity is well-known. Thus, the aim of the current study on broiler chickens was to examine whether nano elemental selenium (Nano-Se) supplementation can reduce the effects of chromium VI (K2Cr2O7) toxicity. For this purpose, a total of 150, one-day-old broiler chickens were allotted to five groups with three replicates: control group (standard diet), poisoned group (K2Cr2O7 via drinking water), protection group (K2Cr2O7 + Nano- Se), cure group (K2Cr2O7 for initial 2 weeks and then Nano-Se), and prevention group (opposite to the cure group). The broilers were detected by the activities of marker enzymes and oxidative stress markers including, aspartate aminotransferase (AST), alanine transaminase (ALT), gamma-glutamyl transferase (GGT) and superoxide dismutase (SOD), glutathione peroxidase (GSH-px), malondialdehyde (MDA), respectively. The (K2Cr2O7 administration caused histopathological damage in the liver of the chickens. Moreover, changes in serum biochemical indicators and oxidative stress parameters were also observed. Nano-Se supplementation increased the levels of GSH-px but reduced the activities of SOD, MDA, GGT, ALT and AST in the experimental groups (P less than 0.05). Our results showed that Nano-Se plays a protective role by preventing the oxidative stress induced by the chromium VI in broiler chickens.

  3. Synthesis and characterization of barium hexaferrite with manganese (Mn) doping material as anti-radar

    NASA Astrophysics Data System (ADS)

    Susilawati, Doyan, Aris; Khalilurrahman

    2017-01-01

    Have been successfully synthesized barium powder doping Manganese hexaferrite with the expected potential as anti-radar material. Synthesis was done by using the co-precipitation method, the variation of the variable x concentrations used were 0; 0.2; 0.4; and 0.6 and calcined at temperatures of 400, 600 and 800°C. Characterization powders of hexaferrite have used XRD (X-Ray Diffraction), SEM (Scanning Electron Microscopy), TEM (Transmission Electron Microscopy), LCR (inductance, capacitance, and resistance) meter, and VSM (Vibrating Sample Magnetometer). The higher the concentration and temperature of calcinations given affect the color of the powder. The test results using XRD indicates that it has formed barium hexaferrite phase with a hexagonal crystal structure. Tests using SEM showed that all the constituent elements barium powder hexaferrite by doping Manganese powders have been spread evenly. XRD test results were confirmed by a test using a TEM showing the crystal structure and the powder was sized nano particles. The results from the LCR meter showed that the barium powder hexaferrite by doping Manganese that has been synthesized classified in semiconductor materials. The result from VSM showed that the value of coercivity magnetic powder doped barium hexaferrite Manganese is smaller when compared with barium hexaferrite without doping and belong to the soft magnetic. Based on the results of the synthesis and characterization, we can conclude that the barium powder heksaferrite by doping Manganese potential as a material anti-radar.

  4. 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.

  5. Size dependent compressibility of nano-ceria: Minimum near 33 nm

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

    Rodenbough, Philip P.; Chemistry Department, Columbia University, New York, New York 10027; Song, Junhua

    2015-04-20

    We report the crystallite-size-dependency of the compressibility of nanoceria under hydrostatic pressure for a wide variety of crystallite diameters and comment on the size-based trends indicating an extremum near 33 nm. Uniform nano-crystals of ceria were synthesized by basic precipitation from cerium (III) nitrate. Size-control was achieved by adjusting mixing time and, for larger particles, a subsequent annealing temperature. The nano-crystals were characterized by transmission electron microscopy and standard ambient x-ray diffraction (XRD). Compressibility, or its reciprocal, bulk modulus, was measured with high-pressure XRD at LBL-ALS, using helium, neon, or argon as the pressure-transmitting medium for all samples. As crystallite sizemore » decreased below 100 nm, the bulk modulus first increased, and then decreased, achieving a maximum near a crystallite diameter of 33 nm. We review earlier work and examine several possible explanations for the peaking of bulk modulus at an intermediate crystallite size.« less

  6. 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

  7. 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).

  8. Thiolated polyethylene oxide as a non-fouling element for nano-patterned bio-devices

    NASA Astrophysics Data System (ADS)

    Lisboa, Patrícia; Valsesia, Andrea; Colpo, Pascal; Gilliland, Douglas; Ceccone, Giacomo; Papadopoulou-Bouraoui, Andri; Rauscher, Hubert; Reniero, Fabiano; Guillou, Claude; Rossi, François

    2007-03-01

    This work describes the synthesis of a thiolated polyethylene oxide that self-assembles on gold to create a non-fouling surface. Thiolated polyethylene oxide was synthesised by reacting 16-mercaptohexadecanoic acid with polyethylene glycol mono methyl ether. The coverage of the thiolated polyethylene oxide on gold was studied by cyclic voltammetry, and the modified surfaces were characterised by X-ray photoelectron spectroscopy and ellipsometry. Protein resistance was assessed using quartz crystal microbalance. Results showed a non-fouling character produced by the thiolated polyethylene oxide. The synthesised product was used as the passivation layer on nano-patterned surfaces consisting of arrayed nano-spots, fabricated by plasma based colloidal lithography. The specific adsorption of anti-bovine serum albumin in the mercaptohexadecanoic acid spots was verified by atomic force microscopy.

  9. 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

  10. 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.

  11. Synthesis and Oxidation of Silver Nano-particles

    DTIC Science & Technology

    2011-01-01

    solution (20%wt propyl alcohol, 5%wt hydrochloric acid and 5%wt stannous chloride in water). Scheme 1b and c illustrate the sensitization and silver... Synthesis and Oxidation of Silver Nano-particles Hua Qi*, D. A. Alexson, O.J. Glembocki and S. M. Prokes* Electronics Science and Technology...energy dispersive x-ray (EDX) techniques. The results Quantum Dots and Nanostructures: Synthesis , Characterization, and Modeling VIII, edited by Kurt

  12. Size effect of elemental selenium nanoparticles (Nano-Se) at supranutritional levels on selenium accumulation and glutathione S-transferase activity.

    PubMed

    Peng, Dungeng; Zhang, Jinsong; Liu, Qingliang; Taylor, Ethan Will

    2007-10-01

    It has been shown that 36 nm Nano-Se has lower toxicity than selenite or selenomethionine, but these forms of selenium (Se) all possess similar ability to increase selenoenzyme levels. The size of nanoparticles plays an important role in their biological activity: as expected, 5-200 nm Nano-Se can directly scavenge free radicals in vitro in a size-dependent fashion. However, in Se-deficient cells and Se-deficient mice, the size effect of Nano-Se on increasing selenoenzymes and liver Se disappears unexpectedly. We hypothesize that under conditions of Se deficiency, the avidity of Se uptake mechanisms may be increased to maintain the biosynthesis of selenoenzymes, which are fundamental for redox homeostasis. This increased avidity may override the potential advantage of small size Nano-Se seen under Se-replete conditions, thereby eliminating the size effect. Once selenoenzymes have been saturated, Se uptake mechanisms may downregulate; accordingly, the size effect of Nano-Se can then reappear. To test this hypothesis, Se-deficient mice were administered either 36 or 90 nm Nano-Se at supranutritional doses, in both a short-term model and a single-dose model. Under these conditions, Nano-Se showed a size effect on Se accumulation and glutathione S-transferase (GST) activity. A size effect of Nano-Se was found in 15 out of 18 total comparisons between sizes at the same dose and time in the two models. Furthermore, the magnitude of the size effect was more prominent on Se accumulation than on GST activity. GST is strictly regulated by transcriptional and translational mechanisms, so its increase in activity normally does not exceed 3-fold. In contrast, the homeostasis of Se accumulation is not as tightly controlled. In the present experiments, GST activity had reached or was approaching saturation, but liver Se was far below saturation. Therefore, our results strongly suggest that the saturation profile of the tested biomarker has an impact on the size effect of Nano

  13. Characterizations of Ca- and Mg-incorporating micro/nano-structured surfaces on titanium fabricated by microarc oxidation and hydrothermal treatments

    NASA Astrophysics Data System (ADS)

    Ko, Sang-Hoon; Hwang, Moon-Jin; Moon, Won-Jin; Park, Yeong-Joon; Song, Ho-Jun

    2015-12-01

    The micro/nano-surface characteristics of magnesium- and calcium-incorporating titanium oxide layers fabricated on titanium metal using microarc oxidation (MAO) and hydrothermal (HT) treatments were investigated. Calcium acetate monohydrate (CA), magnesium acetate monohydrate (MA), and β-glycerophosphoric acid disodium salt pentahydrate were used as electrolytes for MAO treatment of titanium disks. CA/MA electrolyte concentrations (all in M) were 0.2/0.0 (CA20-MAO), 0.15/0.05 (CA15MA5-MAO), 0.1/0.1 (CA10MA10-MAO), 0.05/0.15 (CA5MA15-MAO), and 0.0/0.2 (MA20-MAO). MAO-HT groups were prepared by hydrothermal treatment of MAO groups. The porous surface morphology was consistent even after HT treatment. The incorporation of Mg ions in the oxide layer during MAO treatment was more favorable than incorporation of Ca ions. However, Mg ions were released more rapidly than Ca ions after HT treatment. The anatase TiO2 structure was dominant for all the groups and an increase in the rutile TiO2 structure was observed with an increase in MA concentration. Nano-sized crystallites were observed on the porous surface for all MAO-HT groups. Nano-needle-like crystallites were observed on the surface of CA20-MAO-HT. The crystallites exhibited shorter and thicker characteristics with an increase in Mg concentration.

  14. 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 ...

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

    PubMed

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

    2016-06-07

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

  16. 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.

  17. Electrical and magnetic properties of nano-sized magnesium ferrite

    NASA Astrophysics Data System (ADS)

    T, Smitha; X, Sheena; J, Binu P.; Mohammed, E. M.

    2015-02-01

    Nano-sized magnesium ferrite was synthesized using sol-gel techniques. Structural characterization was done using X-ray diffractometer and Fourier Transform Infrared Spectrometer. Vibration Sample Magnetometer was used to record the magnetic measurements. XRD analysis reveals the prepared sample is single phasic without any impurity. Particle size calculation shows the average crystallite size of the sample is 19nm. FTIR analysis confirmed spinel structure of the prepared samples. Magnetic measurement study shows that the sample is ferromagnetic with high degree of isotropy. Hysterisis loop was traced at temperatures 100K and 300K. DC electrical resistivity measurements show semiconducting nature of the sample.

  18. A Novel Approach of Using Ground CNTs as the Carbon Source to Fabricate Uniformly Distributed Nano-Sized TiCx/2009Al Composites

    PubMed Central

    Wang, Lei; Qiu, Feng; Ouyang, Licheng; Wang, Huiyuan; Zha, Min; Shu, Shili; Zhao, Qinglong; Jiang, Qichuan

    2015-01-01

    Nano-sized TiCx/2009Al composites (with 5, 7, and 9 vol% TiCx) were fabricated via the combustion synthesis of the 2009Al-Ti-CNTs system combined with vacuum hot pressing followed by hot extrusion. In the present study, CNTs were used as the carbon source to synthesize nano-sized TiCx particles. An attempt was made to correlate the effect of ground CNTs by milling and the distribution of synthesized nano-sized TiCx particles in 2009Al as well as the tensile properties of nano-sized TiCx/2009Al composites. Microstructure analysis showed that when ground CNTs were used, the synthesized nano-sized TiCx particles dispersed more uniformly in the 2009Al matrix. Moreover, when 2 h-milled CNTs were used, the 5, 7, and 9 vol% nano-sized TiCx/2009Al composites had the highest tensile properties, especially, the 9 vol% nano-sized TiCx/2009Al composites. The results offered a new approach to improve the distribution of in situ nano-sized TiCx particles and tensile properties of composites. PMID:28793749

  19. Nano-Sized Grain Refinement Using Friction Stir Processing

    DTIC Science & Technology

    2013-03-01

    friction stir weld is a very fine grain microstructure produced as a result of dynamic recrystallization. The friction stir ... Friction Stir Processing, Magnesium, Nano-size grains Abstract A key characteristic of a friction stir weld is a very fine grain microstructure...state process developed on the basis of the friction stir welding (FSW) technique invented by The Welding Institute (TWI) in 1991 [2]. During

  20. Preparation of Nano-sized Bismuth-Doped Fe3O4 as an Excellent Magnetic Material for Supercapacitor Electrodes

    NASA Astrophysics Data System (ADS)

    Aghazadeh, Mustafa; Karimzadeh, Isa; Ganjali, Mohammad Reza

    2018-03-01

    Nano-sized Bi3+-doped iron oxide (n-Bi-IO) particles were prepared through a one-pot electrochemical procedure, and the product was evaluated using x-ray diffraction, field-emission scanning electron microscopy and energy-dispersive x-ray spectroscopy. Based on the analyses, the average size of the n-Bi-IO was determined to be 10 nm. Galvanostatic charge-discharge (GCD) evaluations revealed that the specific capacitance of the material reached 235 F g-1 at a discharge condition of 0.2 A g-1. n-Bi-IO had a 94.2% capacity retention after 2000 GCD cycles. Further vibrating sample magnetometery analyses showed that the product has enhanced superparamagnetic qualities (i.e. M r = 0.15 emu g-1 and H Ci = 2.71 G) in comparison to iron oxide nanoparticles (i.e. M r = 0.95 emu g-1 and H Ci = 14.62 G). Given the results, the product is considered to be a promising material for developing high performance supercapacitor electrodes.

  1. 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.

  2. 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

  3. 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.

  4. 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.

  5. 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.

  6. 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

  7. 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.

  8. 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

  9. 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

  10. A Novel Approach of Using Ground CNTs as the Carbon Source to Fabricate Uniformly Distributed Nano-Sized TiCx/2009Al Composites.

    PubMed

    Wang, Lei; Qiu, Feng; Ouyang, Licheng; Wang, Huiyuan; Zha, Min; Shu, Shili; Zhao, Qinglong; Jiang, Qichuan

    2015-12-17

    Nano-sized TiC x /2009Al composites (with 5, 7, and 9 vol% TiC x ) were fabricated via the combustion synthesis of the 2009Al-Ti-CNTs system combined with vacuum hot pressing followed by hot extrusion. In the present study, CNTs were used as the carbon source to synthesize nano-sized TiC x particles. An attempt was made to correlate the effect of ground CNTs by milling and the distribution of synthesized nano-sized TiC x particles in 2009Al as well as the tensile properties of nano-sized TiC x /2009Al composites. Microstructure analysis showed that when ground CNTs were used, the synthesized nano-sized TiC x particles dispersed more uniformly in the 2009Al matrix. Moreover, when 2 h-milled CNTs were used, the 5, 7, and 9 vol% nano-sized TiC x /2009Al composites had the highest tensile properties, especially, the 9 vol% nano-sized TiC x /2009Al composites. The results offered a new approach to improve the distribution of in situ nano-sized TiC x particles and tensile properties of composites.

  11. 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.

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

    PubMed

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

    2007-07-19

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

  13. Presence of nano-sized silica during in vitro digestion of foods containing silica as a food additive.

    PubMed

    Peters, Ruud; Kramer, Evelien; Oomen, Agnes G; Rivera, Zahira E Herrera; Oegema, Gerlof; Tromp, Peter C; Fokkink, Remco; Rietveld, Anton; Marvin, Hans J P; Weigel, Stefan; Peijnenburg, Ad A C M; Bouwmeester, Hans

    2012-03-27

    The presence, dissolution, agglomeration state, and release of materials in the nano-size range from food containing engineered nanoparticles during human digestion is a key question for the safety assessment of these materials. We used an in vitro model to mimic the human digestion. Food products subjected to in vitro digestion included (i) hot water, (ii) coffee with powdered creamer, (iii) instant soup, and (iv) pancake which either contained silica as the food additive E551, or to which a form of synthetic amorphous silica or 32 nm SiO(2) particles were added. The results showed that, in the mouth stage of the digestion, nano-sized silica particles with a size range of 5-50 and 50-500 nm were present in food products containing E551 or added synthetic amorphous silica. However, during the successive gastric digestion stage, this nano-sized silica was no longer present for the food matrices coffee and instant soup, while low amounts were found for pancakes. Additional experiments showed that the absence of nano-sized silica in the gastric stage can be contributed to an effect of low pH combined with high electrolyte concentrations in the gastric digestion stage. Large silica agglomerates are formed under these conditions as determined by DLS and SEM experiments and explained theoretically by the extended DLVO theory. Importantly, in the subsequent intestinal digestion stage, the nano-sized silica particles reappeared again, even in amounts higher than in the saliva (mouth) digestion stage. These findings suggest that, upon consumption of foods containing E551, the gut epithelium is most likely exposed to nano-sized silica. © 2012 American Chemical Society

  14. 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

  15. Oxidative damage and neurodegeneration in manganese-induced neurotoxicity

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

    Milatovic, Dejan; Zaja-Milatovic, Snjezana; Gupta, Ramesh C.

    2009-10-15

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

  16. Nano red elemental selenium has no size effect in the induction of seleno-enzymes in both cultured cells and mice.

    PubMed

    Zhang, Jinsong; Wang, Huali; Bao, Yongping; Zhang, Lide

    2004-05-28

    We previous reported that a nano red elemental selenium (Nano-Se) in the range from 20 approximately 60 nm had similar bioavailability to sodium selenite (BioFactors 15 (2001) 27). We recently found that Nano-Se with different size had marked difference in scavenging an array of free radicals in vitro, the smaller the particle, the better scavenging activity (Free Radic. Biol. Med. 35 (2003) 805). In order to examine whether there is a size effect of Nano-Se in the induction of Se-dependent enzymes, a range of Nano-Se (5 approximately 200 nm) have been prepared based on the control of elemental Se atom aggregation. The sizes of Nano-Se particles were inversely correlated with protein levels in the redox system of selenite and glutathione. Different sizes of red elemental Se were prepared by adding varying amount of bovine serum albumin (BSA). Three different sizes of Nano-Se (5 approximately 15 nm, 20 approximately 60 nm, and 80 approximately 200 nm) have been chosen for the comparison of biological activity in terms of the induction of seleno-enzyme activities. Results showed that there was no significant size effect of Nano-Se from 5 to 200 nm in the induction of glutathione peroxidase (GPx), phospholipid hydroperoxide glutathione peroxidase (PHGPx) and thioredoxin reductase-1 (TrxR-1) in human hepatoma HepG2 cells and the livers of mice.

  17. 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.

  18. Effect of Nano-Al₂O₃ on the Toxicity and Oxidative Stress of Copper towards Scenedesmus obliquus.

    PubMed

    Li, Xiaomin; Zhou, Suyang; Fan, Wenhong

    2016-06-09

    Nano-Al₂O₃ has been widely used in various industries; unfortunately, it can be released into the aquatic environment. Although nano-Al₂O₃ is believed to be of low toxicity, it can interact with other pollutants in water, such as heavy metals. However, the interactions between nano-Al₂O₃ and heavy metals as well as the effect of nano-Al₂O₃ on the toxicity of the metals have been rarely investigated. The current study investigated copper toxicity in the presence of nano-Al₂O₃ towards Scenedesmus obliquus. Superoxide dismutase activity and concentration of glutathione and malondialdehyde in cells were determined in order to quantify oxidative stress in this study. Results showed that the presence of nano-Al₂O₃ reduced the toxicity of Cu towards S. obliquus. The existence of nano-Al₂O₃ decreased the growth inhibition of S. obliquus. The accumulation of copper and the level of oxidative stress in algae were reduced in the presence of nano-Al₂O₃. Furthermore, lower copper accumulation was the main factor that mitigated copper toxicity with the addition of nano-Al₂O₃. The decreased copper uptake could be attributed to the adsorption of copper onto nanoparticles and the subsequent decrease of available copper in water.

  19. Synthesis of nano-sized lithium cobalt oxide via a sol-gel method

    NASA Astrophysics Data System (ADS)

    Li, Guangfen; Zhang, Jing

    2012-07-01

    In this study, nano-structured LiCoO2 thin film were synthesized by coupling a sol-gel process with a spin-coating method using polyacrylic acid (PAA) as chelating agent. The optimized conditions for obtaining a better gel formulation and subsequent homogenous dense film were investigated by varying the calcination temperature, the molar mass of PAA, and the precursor's molar ratios of PAA, lithium, and cobalt ions. The gel films on the silicon substrate surfaces were deposited by multi-step spin-coating process for either increasing the density of the gel film or adjusting the quantity of PAA in the film. The gel film was calcined by an optimized two-step heating procedure in order to obtain regular nano-structured LiCoO2 materials. Both atomic force microscopy (AFM) and scanning electron microscopy (SEM) were utilized to analyze the crystalline and the morphology of the films, respectively.

  20. 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.

  1. Nano-structured Platinum-based Catalysts for the Complete Oxidation of Ethylene Glycol and Glycerol

    NASA Astrophysics Data System (ADS)

    Falase, Akinbayowa

    Direct alcohol fuel cells are a viable alternative to the traditional hydrogen PEM fuel cell. Fuel versatility, integration with existing distribution networks, and increased safety when handling these fuels increases their appeal for portable power applications. In order to maximize their utility, the liquid fuel must be fully oxidized to CO2 so as to harvest the full amount of energy. Methanol and ethanol are widely researched as potential fuels to power these devices, but methanol is a toxic substance, and ethanol has a much lower energy density than other liquids such as gasoline or glucose. Oxidation of complex fuels is difficult to realize, due to difficulty in breaking carbon-carbon bonding and poisoning of the catalysts by oxidative byproducts. In order to achieve the highest efficiency, an anode needs to be engineered in such a way as to maximize activity while minimizing poisoning effects of reaction byproducts. We have engineered an anode that uses platinum-based catalysts that is capable of completely oxidizing ethylene glycol and glycerol in neutral and alkaline media with little evidence of CO poisoning. We have constructed a hybrid anode consisting of a nano-structured PtRu electrocatayst with an NAD-dependent alcohol dehydrogenase for improved oxidation of complex molecules. A nano-structured PtRu catalyst was used to oxidize ethylene glycol and glycerol in neutral media. In situ infrared spectroscopy was used to verify complete oxidation via CO2 generation. There was no evidence of poisoning by CO species. A pH study was performed to determine the effect of pH on oxidative current. The peak currents did not trend at 60 mV/pH unit as would be expected from the Nernst equation, suggesting that adsorption of fuel to the surface of the electrode is not an electron-transfer step. We synthesized nano-structured PtRu, PtSn, and PtRuSn catalysts for oxidation of ethylene glycol and glycerol in alkaline media. The PtRu electrocatalyst the highest oxidative

  2. Ultrasonic-assisted synthesis of nano lead(II) coordination polymer as precursors for preparation of lead(II) oxide nano-structures: Thermal, optical properties and XRD studies.

    PubMed

    Ghavidelaghdam, Elham; Shahverdizadeh, Gholam Hossein; Motameni Tabatabai, Javad; Mirtamizdoust, Babak

    2018-04-01

    Nano structure of a lead (II) coordination polymer [Pb 2 (C 2 Cl 3 O 2 ) 2 (NO 3 ) 2 (C l2 H 8 N 2 ) 2 ] n (1), has been synthesized by a sonochemical method in different concentrations. The nano particles were characterized by scanning electron microscopy (SEM) X-ray powder diffraction (XRD), FT-IR spectroscopy and elemental analyses. The thermal stability of nano structure is closely investigated via thermal gravimetric (TGA), and compared with crystalline structure. The compounds are then heated to 600 °C to produce PbO nano particles. The resulting PbO is characterized through XRD and SEM analyses. Concentration of initial reagents effects on size and morphology of nano-structured compound 1 have been studied and show that low concentrations of initial reagents decreased particles size and leaded to uniform nano particles morphology. The photoluminescence properties of the prepared compound, as crystalline and as nanoparticles, have been investigated. The result showed a good correlation between the size and emission wavelength. Copyright © 2017. Published by Elsevier B.V.

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

    PubMed

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

    2016-05-17

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

  4. 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

  5. Manganese Driven Carbon Oxidation along Oxic-Anoxic Interfaces in Forest Soils

    NASA Astrophysics Data System (ADS)

    Jones, M. E.; Keiluweit, M.

    2017-12-01

    Soils are the largest and most dynamic terrestrial carbon pool, storing a total of 3000 Pg of C - more than the atmosphere and biosphere combined. Because microbial oxidation determines the proportion of carbon that is either stored in the soil or emitted as climate active CO2, its rate directly impacts the global carbon cycle. Recently, a strong correlation between oxidation rates and manganese (Mn) content has been observed in forest soils globally, leading researchers conclude that Mn "is the single main factor governing" the oxidation of plant-derived particulate organic carbon (POC). Many soils are characterized by steep oxygen gradients, forming oxic-anoxic transitions that enable rapid redox cycling of Mn. Oxic-anoxic interfaces have been shown to promote fungal Mn oxidation and the formation of ligand-stabilized Mn(III), which ranks second only to superoxide as the most powerful oxidizing agent in the environment. Here we examined fungal Mn(III) formation along redox gradients in forest soils and their impact on POC oxidation rates. In both field and laboratory settings, oxic-anoxic transition zones showed the greatest Mn(III) concentrations, along with enhanced fungal growth, oxidative potential, production of soluble oxidation products, and CO2 production. Additional electrochemical and X-ray (micro)spectroscopic analyses indicated that oxic-anoxic interfaces represent ideal niches for fungal Mn(III) formation, owing to the ready supply of Mn(II), ligands and O2. Combined, our results suggest that POC oxidation relies on fungal Mn cycling across oxic-anoxic interfaces to produce Mn(III) based oxidants. Because predicted changes in the frequency and timing of precipitation dramatically alter soil moisture regimes in forest soils, understanding the mechanistic link between Mn cycling and carbon oxidation along oxic-anoxic interfaces is becoming increasingly important.

  6. Investigation of Thin Layered Cobalt Oxide Nano-Islands on Gold

    NASA Astrophysics Data System (ADS)

    Bajdich, Michal; Walton, Alex S.; Fester, Jakob; Arman, Mohammad A.; Osiecki, Jacek; Knudsen, Jan; Vojvodic, Aleksandra; Lauritsen, Jeppe V.

    2015-03-01

    Layered cobalt oxides have been shown to be highly active catalysts for the oxygen evolution reaction (OER), but the synergistic effect of contact with gold is yet to be fully understood. The synthesis of three distinct types of thin-layered cobalt oxide nano-islands supported on a single crystal gold (111) substrate is confirmed by combination of STM and XAS methods. In this work, we present DFT+U theoretical investigation of above nano-islands using several previously known structural models. Our calculations confirm stability of two low-oxygen pressure phases: (a) rock-salt Co-O bilayer and (b) wurtzite Co-O quadlayer and single high-oxygen pressure phase: (c) O-Co-O trilayer. The optimized geometries agree with STM structures and calculated oxidation states confirm the conversion from Co2+ to Co3+ found experimentally in XAS. The O-Co-O trilayer islands have the structure of a single layer of CoOOH proposed to be the true active phase for OER catalyst. For that reason, the effect of water on the Pourbaix stabilities of basal planes and edge sites is fully investigated. Lastly, we also present the corresponding OER theoretical overpotentials.

  7. Nano-sized TiO2 (nTiO2) induces metabolic perturbations in Physarum polycephalum macroplasmodium to counter oxidative stress under dark conditions.

    PubMed

    Zhang, Zhi; Liang, Zhi Cheng; Zhang, Jian Hua; Tian, Sheng Li; Le Qu, Jun; Tang, Jiao Ning; De Liu, Shi

    2018-06-15

    Nano-sized TiO 2 (nTiO 2 ) exerts an oxidative effect on cells upon exposure to solar or UV irradiation and ecotoxicity of the nTiO 2 is an urgent concern. Little information is available regarding the effect of TiO 2 on cells under dark conditions. Metabolomics is a unique approach to the discovery of biomarkers of nTiO 2 cytotoxicity, and leads to the identification of perturbed metabolic pathways and the mechanism underlying nTiO 2 toxicity. In the present study, gas chromatography mass spectrometry (GC/MS)-based metabolomics was performed to investigate the effect of nTiO 2 on sensitive cells (P. polycephalum macroplasmodium) under dark conditions. According to the multivariate pattern recognition analysis, at least 60 potential metabolic biomarkers related to sugar metabolism, amino acid metabolism, nucleotide metabolism, polyamine biosynthesis, and secondary metabolites pathways were significantly perturbed by nTiO 2 . Notably, many metabolic biomarkers and pathways were related to anti-oxidant mechanisms in the living organism, suggesting that nTiO 2 may induce oxidative stress, even under dark conditions. This speculation was further validated by the biochemical levels of reactive oxygen species (ROS), 8-hydroxy-2-deoxyguanosine (8-OHdG), and total soluble phenols (TSP). We inferred that the oxidative stress might be related to nTiO 2 -induced imbalance of cellular ROS. To the best of our knowledge, the present study is the first to investigate the nTiO 2 -induced metabolic perturbations in slime mold, provide a new perspective of the mechanism underlying nTiO 2 toxicity under dark conditions, and show that metabolomics can be employed as a rapid, reliable and powerful tool to investigate the interaction among organisms, the environment, and nanomaterials. Copyright © 2018 Elsevier Inc. All rights reserved.

  8. High-volumetric performance aligned nano-porous microwave exfoliated graphite oxide-based electrochemical capacitors.

    PubMed

    Ghaffari, Mehdi; Zhou, Yue; Xu, Haiping; Lin, Minren; Kim, Tae Young; Ruoff, Rodney S; Zhang, Q M

    2013-09-20

    Ultra-high volumetric performance electrochemical double layer capacitors based on high density aligned nano-porous microwave exfoliated graphite oxide have been studied. Elimination of macro-, meso-, and larger micro-pores from electrodes and controlling the nano-morphology results in very high volumetric capacitance, energy, and power density values. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Manganese

    MedlinePlus

    ... de Manganèse, Dioxyde de Manganèse, Gluconate de Manganèse, Glycérophosphate de Manganèse, Manganèse, Manganese Amino Acid Chelate, Manganese ... Chloridetetrahydrate, Manganese Citrate, Manganese Dioxide, Manganese ... Sulfate, Manganese Sulfate Monohydrate, Manganese Sulfate Tetrahydrate, ...

  10. Nano-sized metabolic precursors for heterogeneous tumor-targeting strategy using bioorthogonal click chemistry in vivo.

    PubMed

    Lee, Sangmin; Jung, Seulhee; Koo, Heebeom; Na, Jin Hee; Yoon, Hong Yeol; Shim, Man Kyu; Park, Jooho; Kim, Jong-Ho; Lee, Seulki; Pomper, Martin G; Kwon, Ick Chan; Ahn, Cheol-Hee; Kim, Kwangmeyung

    2017-12-01

    Herein, we developed nano-sized metabolic precursors (Nano-MPs) for new tumor-targeting strategy to overcome the intrinsic limitations of biological ligands such as the limited number of biological receptors and the heterogeneity in tumor tissues. We conjugated the azide group-containing metabolic precursors, triacetylated N-azidoacetyl-d-mannosamine to generation 4 poly(amidoamine) dendrimer backbone. The nano-sized dendrimer of Nano-MPs could generate azide groups on the surface of tumor cells homogeneously regardless of cell types via metabolic glycoengineering. Importantly, these exogenously generated 'artificial chemical receptors' containing azide groups could be used for bioorthogonal click chemistry, regardless of phenotypes of different tumor cells. Furthermore, in tumor-bearing mice models, Nano-MPs could be mainly localized at the target tumor tissues by the enhanced permeation and retention (EPR) effect, and they successfully generated azide groups on tumor cells in vivo after an intravenous injection. Finally, we showed that these azide groups on tumor tissues could be used as 'artificial chemical receptors' that were conjugated to bioorthogonal chemical group-containing liposomes via in vivo click chemistry in heterogeneous tumor-bearing mice. Therefore, overall results demonstrated that our nano-sized metabolic precursors could be extensively applied to new alternative tumor-targeting technique for molecular imaging and drug delivery system, regardless of the phenotype of heterogeneous tumor cells. Copyright © 2017 Elsevier Ltd. All rights reserved.

  11. 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.

  12. Fire performance, microstructure and thermal degradation of an epoxy based nano intumescent fire retardant coating for structural applications

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

    Aziz, Hammad, E-mail: engr.hammad.aziz03@gmail.com; Ahmad, Faiz, E-mail: faizahmad@petronas.com.my; Yusoff, P. S. M. Megat

    Intumescent fire retardant coating (IFRC) is a passive fire protection system which swells upon heating to form expanded multi-cellular char layer that protects the substrate from fire. In this research work, IFRC’s were developed using different flame retardants such as ammonium polyphosphate, expandable graphite, melamine and boric acid. These flame retardants were bound together with the help of epoxy binder and cured together using curing agent. IFRC was then reinforced with nano magnesium oxide and nano alumina as inorganic fillers to study their effect towards fire performance, microstructure and thermal degradation. Small scale fire test was conducted to investigate themore » thermal insulation of coating whereas fire performance was calculated using thermal margin value. Field emission scanning electron microscopy was used to examine the microstructure of char obtained after fire test. Thermogravimetric analysis was conducted to investigate the residual weight of coating. Results showed that the performance of the coating was enhanced by reinforcement with nano size fillers as compared to non-filler based coating. Comparing both nano size magnesium oxide and nano size alumina; nano size alumina gave better fire performance with improved microstructure of char and high residual weight.« less

  13. Fire performance, microstructure and thermal degradation of an epoxy based nano intumescent fire retardant coating for structural applications

    NASA Astrophysics Data System (ADS)

    Aziz, Hammad; Ahmad, Faiz; Yusoff, P. S. M. Megat; Zia-ul-Mustafa, M.

    2015-07-01

    Intumescent fire retardant coating (IFRC) is a passive fire protection system which swells upon heating to form expanded multi-cellular char layer that protects the substrate from fire. In this research work, IFRC's were developed using different flame retardants such as ammonium polyphosphate, expandable graphite, melamine and boric acid. These flame retardants were bound together with the help of epoxy binder and cured together using curing agent. IFRC was then reinforced with nano magnesium oxide and nano alumina as inorganic fillers to study their effect towards fire performance, microstructure and thermal degradation. Small scale fire test was conducted to investigate the thermal insulation of coating whereas fire performance was calculated using thermal margin value. Field emission scanning electron microscopy was used to examine the microstructure of char obtained after fire test. Thermogravimetric analysis was conducted to investigate the residual weight of coating. Results showed that the performance of the coating was enhanced by reinforcement with nano size fillers as compared to non-filler based coating. Comparing both nano size magnesium oxide and nano size alumina; nano size alumina gave better fire performance with improved microstructure of char and high residual weight.

  14. 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.

  15. 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.

  16. On the Size Dependence of Molar and Specific Properties of Independent Nano-phases and Those in Contact with Other Phases

    NASA Astrophysics Data System (ADS)

    Kaptay, George

    2018-05-01

    Nano-materials are materials with at least one nano-phase. A nano-phase is a phase with at least one of its dimensions below 100 nm. It is shown here that nano-phases have at least 1% of their atoms along their surface layer. The ratio of surface atoms is proportional to the specific surface area of the phase, defined as the ratio of its surface area to its volume. Each specific/molar property has its bulk value and its surface value for the given phase, being always different, as the energetic states of the atoms in the bulk and in the surface layer of a phase are different. The average specific/molar property of a nano-phase is modeled here as a linear combination of the bulk and surface values of the same property, scaled with the ratio of the surface atoms. That makes the performance of all nano-phases proportional to their specific surface area. As the characteristic size of the nano-phase is inversely proportional to its specific surface area, all specific/molar properties of nano-phases are inversely proportional to the characteristic size of the phase. This is applied to the size dependence of the molar Gibbs energy of the nano-phase, which appears to be in agreement with the thermodynamics of Gibbs. This agreement proves the general validity of the present model on the size dependence of the specific/molar properties of independent nano-phases. It is shown that the properties of nano-phases are different for independent nano-phases (surrounded only by their equilibrium vapor phase) and for nano-phases in multi-phase situations, such as a liquid nano-droplet in the sessile drop configuration.

  17. Effect of drying environment on grain size of titanium dioxide nano-powder synthesized via sol-gel method

    NASA Astrophysics Data System (ADS)

    Zandi, Pegah; Hosseini, Elham; Rashchi, Fereshteh

    2018-01-01

    Titanium dioxide Nano powder has been synthesized from titanium isopropoxide (TTIP) in chloride media by sol-gel method. In this research, the effect of the drying environment, from air to oven drying at 100 °C, calcination time and temperature on nano TiO2 grain size was investigated. The synthesized powder was analyzed by x-ray diffraction and scanning electron microscope. Based on the results, the powder has been crystallized in anatase and rutile phases, due to different calcination temperatures. At temperatures above 600 °C, the Titanium dioxide nano powder has been crystallized as rutile. The crystalline structure of titanium dioxide nano powder changed because of the different calcination temperatures and time applied. The average particle size of the powder dried in air was larger than the powder dried in oven. The minimum particle size of the powder dried in air was 50 nm and in the oven was 9 nm, observed and calculated Williamson-Hall equation. All in all, with overall increasing of calcination time and temperature the grain size increased. Moreover, in the case of temperature, after a certain temperature, the grain size became constant and didn't change significantly.

  18. Characterization of High-Velocity Solution Precursor Flame-Sprayed Manganese Cobalt Oxide Spinel Coatings for Metallic SOFC Interconnectors

    NASA Astrophysics Data System (ADS)

    Puranen, Jouni; Laakso, Jarmo; Kylmälahti, Mikko; Vuoristo, Petri

    2013-06-01

    A modified high-velocity oxy-fuel spray (HVOF) thermal spray torch equipped with liquid feeding hardware was used to spray manganese-cobalt solutions on ferritic stainless steel grade Crofer 22 APU substrates. The HVOF torch was modified in such a way that the solution could be fed axially into the combustion chamber through 250- and 300-μm-diameter liquid injector nozzles. The solution used in this study was prepared by diluting nitrates of manganese and cobalt, i.e., Mn(NO3)2·4H2O and Co(NO3)2·6H2O, respectively, in deionized water. The as-sprayed coatings were characterized by X-ray diffraction and field-emission scanning electron microscopy operating in secondary electron mode. Chemical analyses were performed on an energy dispersive spectrometer. Coatings with remarkable density could be prepared by the novel high-velocity solution precursor flame spray (HVSPFS) process. Due to finely sized droplet formation in the HVSPFS process and the use of as delivered Crofer 22 APU substrate material having very low substrate roughness ( R a < 0.5 μm), thin and homogeneous coatings, with thicknesses lower than 10 μm could be prepared. The coatings were found to have a crystalline structure equivalent to MnCo2O4 spinel with addition of Co-oxide phases. Crystallographic structure was restored back to single-phase spinel structure by heat treatment.

  19. Nano-silymarin provides protection against γ-radiation-induced oxidative stress in cultured human embryonic kidney cells.

    PubMed

    Adhikari, Manish; Arora, Rajesh

    2015-10-01

    Radiation can produce biological damage, mainly oxidative stress, via production of free radicals, including reactive oxygen species (ROS). Nanoparticles are of interest as radioprotective agents, particularly due to their high solubility and bioavailability. Silymarin is a hepatoprotective agent but has poor oral bioavailability. Silymarin was formulated as a nanoemulsion with the aim of improving its bioavailability and therapeutic efficacy. In the present study, we evaluated self-nanoemulsifying drug delivery systems (SNEDDS) formulated with surfactants and co-surfactants. Nano-silymarin was characterized by estimating % transmittance, globule size, and polydispersity index, and by transmission electron microscopy (TEM). The nano-silymarin obtained was in the range of 3-8nm diameter. With regard to DNA damage, measured by a plasmid relaxation assay, maximum protection was obtained at 10μg/mL. Cytotoxicity of nano-silymarin to human embryonic kidney (HEK) cells was evaluated using the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl-tetrazolium bromide (MTT) assay. Protective efficacy against γ-radiation was assessed by reduction in micronucleus frequency and ROS generation, using the 2',7'-dichlorodihydrofluorescein diacetate (H2DCFDA) assay. Radiation-induced apoptosis was estimated by microscopic analysis and cell-cycle estimation. Nano-silymarin was radioprotective, supporting the possibility of developing new approaches to radiation protection via nanotechnology. Copyright © 2015 Elsevier B.V. All rights reserved.

  20. 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.

  1. Hawaiian submarine manganese-iron oxide crusts - A dating tool?

    USGS Publications Warehouse

    Moore, J.G.; Clague, D.A.

    2004-01-01

    Black manganese-iron oxide crusts form on most exposed rock on the ocean floor. Such crusts are well developed on the steep lava slopes of the Hawaiian Ridge and have been sampled during dredging and submersible dives. The crusts also occur on fragments detached from bedrock by mass wasting, on submerged coral reefs, and on poorly lithified sedimentary rocks. The thickness of the crusts was measured on samples collected since 1965 on the Hawaiian Ridge from 140 dive or dredge localities. Fifty-nine (42%) of the sites were collected in 2001 by remotely operated vehicles (ROVs). The thinner crusts on many samples apparently result from post-depositional breakage, landsliding, and intermittent burial of outcrops by sediment. The maximum crust thickness was selected from each dredge or dive site to best represent crusts on the original rock surface at that site. The measurements show an irregular progressive thickening of the crusts toward the northwest-i.e., progressive thickening toward the older volcanic features with increasing distance from the Hawaiian hotspot. Comparison of the maximum crust thickness with radiometric ages of related subaerial features supports previous studies that indicate a crust-growth rate of about 2.5 mm/m.y. The thickness information not only allows a comparison of the relative exposure ages of two or more features offshore from different volcanoes, but also provides specific age estimates of volcanic and landslide deposits. The data indicate that some of the landslide blocks within the south Kona landslide are the oldest exposed rock on Mauna Loa, Kilauea, or Loihi volcanoes. Crusts on the floors of submarine canyons off Kohala and East Molokai volcanoes indicate that these canyons are no longer serving as channelways for downslope, sediment-laden currents. Mahukona volcano was approximately synchronous with Hilo Ridge, both being younger than Hana Ridge. The Nuuanu landslide is considerably older than the Wailau landslide. The Waianae

  2. 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

  3. 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 - .

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

    PubMed

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

    2016-02-01

    Preoxidation is manipulated to improve performance of algae and soluble manganese (Mn) removal by coagulation-sedimentation for water treatment plants (WTPs) when large amount of soluble Mn presents in algae-laden waters. This study aimed to investigate the effects of preoxidation on the performance of coagulation-sedimentation for the simultaneous removal of algae and soluble Mn, including ionic and complexed Mn. NaOCl, ClO2, and KMnO4 were used to pretreat such algae-laden and Mn containing waters. The variation of algal cell viability, residual cell counts, and concentrations of Mn species prior to and after coagulation-sedimentation step were investigated. Results show that NaOCl dosing was effective in reducing the viability of algae, but precipitated little Mn. ClO2 dosing had a strongest ability to lower algae viability and oxidize ionic and complexed soluble Mn, where KMnO4 dosing oxidized ionic and complexed Mn instead of reducing the viability of cells. Preoxidation by NaOCl only improved the algae removal by sedimentation, whereas most of soluble Mn still remained. On the other hand, ClO2 preoxidation substantially improved the performance of coagulation-sedimentation for simultaneous removal of algae and soluble Mn. Furthermore, KMnO4 preoxidation did improve the removal of algae by sedimentation, but left significant residual Mn in the supernatant. Images from FlowCAM showed changes in aspect ratio (AR) and transparency of algae-Mn flocs during oxidation-assisted coagulation, and indicates that an effective oxidation can improve the removal of most compact algae-Mn flocs by sedimentation. It suggests that an effective preoxidation for reducing algal cell viability and the concentration of soluble Mn is a crucial step for upgrading the performance of coagulation-sedimentation. Copyright © 2015 Elsevier Ltd. All rights reserved.

  5. Nano-sized Fe2O3/Fe3O4 facilitate anaerobic transformation of hexavalent chromium in soil-water systems.

    PubMed

    Zhang, Yaxian; Li, Hua; Gong, Libo; Dong, Guowen; Shen, Liang; Wang, Yuanpeng; Li, Qingbiao

    2017-07-01

    The purpose of this study is to investigate the effects of nano-sized or submicro Fe 2 O 3 /Fe 3 O 4 on the bioreduction of hexavalent chromium (Cr(VI)) and to evaluate the effects of nano-sized Fe 2 O 3 /Fe 3 O 4 on the microbial communities from the anaerobic flooding soil. The results indicated that the net decreases upon Cr(VI) concentration from biotic soil samples amended with nano-sized Fe 2 O 3 (317.1±2.1mg/L) and Fe 3 O 4 (324.0±22.2mg/L) within 21days, which were approximately 2-fold of Cr(VI) concentration released from blank control assays (117.1±5.6mg/L). Furthermore, the results of denaturing gradient gel electrophoresis (DGGE) and high-throughput sequencing indicated a greater variety of microbes within the microbial community in amendments with nano-sized Fe 2 O 3 /Fe 3 O 4 than the control assays. Especially, Proteobacteria occupied a predominant status on the phylum level within the indigenous microbial communities from chromium-contaminated soils. Besides, some partial decrease of soluble Cr(VI) in abiotic nano-sized Fe 2 O 3 /Fe 3 O 4 amendments was responsible for the adsorption of nano-sized Fe 2 O 3 /Fe 3 O 4 to soluble Cr(VI). Hence, the presence of nano-sized Fe 2 O 3 /Fe 3 O 4 could largely facilitate the mobilization and biotransformation of Cr(VI) from flooding soils by adsorption and bio-mediated processes. Copyright © 2017. Published by Elsevier B.V.

  6. 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.

  7. 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

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

    DOE PAGES

    Salter-Blanc, Alexandra J.; Bylaska, Eric J.; Lyon, Molly A.; ...

    2016-04-13

    New energetic compounds are designed to minimize their potential environmental impacts, which includes their transformation and the fate and effects of their transformation products. The nitro groups of energetic compounds are readily reduced to amines, and the resulting aromatic amines are subject to oxidation and coupling reactions. Manganese dioxide (MnO 2) is a common environmental oxidant and model system for kinetic studies of aromatic amine oxidation. Here in this study, a training set of new and previously reported kinetic data for the oxidation of model and energetic-derived aromatic amines was assembled and subjected to correlation analysis against descriptor variables that ranged from general purpose [Hammettmore » $$\\sigma$$ constants ($$\\sigma^-$$), pK as of the amines, and energies of the highest occupied molecular orbital (E HOMO)] to specific for the likely rate-limiting step [one-electron oxidation potentials (E ox)]. The selection of calculated descriptors (pK a), E HOMO, and E ox) was based on validation with experimental data. All of the correlations gave satisfactory quantitative structure-activity relationships (QSARs), but they improved with the specificity of the descriptor. The scope of correlation analysis was extended beyond MnO 2 to include literature data on aromatic amine oxidation by other environmentally relevant oxidants (ozone, chlorine dioxide, and phosphate and carbonate radicals) by correlating relative rate constants (normalized to 4-chloroaniline) to E HOMO (calculated with a modest level of theory).« less

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

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

    Salter-Blanc, Alexandra J.; Bylaska, Eric J.; Lyon, Molly A.

    New energetic compounds are designed to minimize their potential environmental impacts, which includes their transformation and the fate and effects of their transformation products. The nitro groups of energetic compounds are readily reduced to amines, and the resulting aromatic amines are subject to oxidation and coupling reactions. Manganese dioxide (MnO 2) is a common environmental oxidant and model system for kinetic studies of aromatic amine oxidation. Here in this study, a training set of new and previously reported kinetic data for the oxidation of model and energetic-derived aromatic amines was assembled and subjected to correlation analysis against descriptor variables that ranged from general purpose [Hammettmore » $$\\sigma$$ constants ($$\\sigma^-$$), pK as of the amines, and energies of the highest occupied molecular orbital (E HOMO)] to specific for the likely rate-limiting step [one-electron oxidation potentials (E ox)]. The selection of calculated descriptors (pK a), E HOMO, and E ox) was based on validation with experimental data. All of the correlations gave satisfactory quantitative structure-activity relationships (QSARs), but they improved with the specificity of the descriptor. The scope of correlation analysis was extended beyond MnO 2 to include literature data on aromatic amine oxidation by other environmentally relevant oxidants (ozone, chlorine dioxide, and phosphate and carbonate radicals) by correlating relative rate constants (normalized to 4-chloroaniline) to E HOMO (calculated with a modest level of theory).« less

  10. Development of an electrochemical process for production of nano-copper oxides: Agglomeration kinetics modeling.

    PubMed

    Shahcheraghi, Seyed Hadi; Schaffie, Mahin; Ranjbar, Mohammad

    2018-06-01

    The main objective of this study was the development of a simple, clean, and industrial applicable electrochemical process for production of high pure nano-copper oxides from mining and industrial resources (e.g., ore, spent, slag and wastewater). To conduct the proposed process, a special set up containing an electrochemical cell in an ultrasonic system (28 kHz and 160 W) was proposed. Accordingly, using this set up and applying appropriate voltage (≈ 5 V) at 25 °C, in the presence of N 2 gas, the simultaneous anode dissolution and nano-copper oxides formation (≈ 24 nm) can be occurred, rapidly (less than 45 min). Then, the effect of N 2 gas and free radicals generated by ultrasonic irradiation was studied. The results showed, in the absence of ultrasonic irradiation and N 2 , an increase of electrolyte pH from 6.42 to 10.92, a decrease of electrolyte Eh from 285 mV to -1.14 V, and formation of copper nanoparticles. While, in the presence of ultrasonic and N 2 , the CuO nanoparticles were formed due to presence of H 2 O 2 generated by interaction of free radicals. Moreover, a novel method for kinetics modeling of nanoparticles agglomeration was proposed according to distributed activation energy model and Arrhenius parameters variation. The results showed that, in the absence of ultrasonic irradiation, the nanoparticle agglomerates were firstly formed (interface controlled mechanism) and then, the diffusion of nanoparticle agglomerates was occurred (diffusion controlled mechanism). Therefore, the control of nanoparticles size and shape may be impossible without surfactant. Also, in the presence of ultrasonic irradiation, the whole of agglomeration process followed interface controlled mechanism. Therefore, using ultrasonic irradiation, the nanoparticles shape and size don't change due to prevention of agglomerates diffusion. Copyright © 2018 Elsevier B.V. All rights reserved.

  11. Structure of Nano-sized CeO 2 Materials: Combined Scattering and Spectroscopic Investigations

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

    Marchbank, Huw R.; Clark, Adam H.; Hyde, Timothy I.

    Here, the nature of nano-sized ceria, CeO 2, systems were investigated using neutron and X-ray diffraction and X-ray absorption spectroscopy. Whilst both diffraction andtotal pair distribution functions (PDFs) revealed that in all the samples the occupancy of both Ce 4+ and O 2- are very close to the ideal stoichiometry, the analysis using reverse Monte Carlo technique revealedsignificant disorder around oxygen atoms in the nano sized ceria samples in comparison to the highly crystalline NIST standard.In addition, the analysis reveal that the main differences observed in the pair correlations from various X-ray and neutron diffraction techniques were attributed to themore » particle size of the CeO 2 prepared by the reported three methods. Furthermore, detailed analysis of the Ce L 3– and K-edge EXAFS data support this finding; in particular the decrease in higher shell coordination numbers with respect to the NIST standard, are attributed to differences in particle size.« less

  12. Structure of Nano-sized CeO 2 Materials: Combined Scattering and Spectroscopic Investigations

    DOE PAGES

    Marchbank, Huw R.; Clark, Adam H.; Hyde, Timothy I.; ...

    2016-08-29

    Here, the nature of nano-sized ceria, CeO 2, systems were investigated using neutron and X-ray diffraction and X-ray absorption spectroscopy. Whilst both diffraction andtotal pair distribution functions (PDFs) revealed that in all the samples the occupancy of both Ce 4+ and O 2- are very close to the ideal stoichiometry, the analysis using reverse Monte Carlo technique revealedsignificant disorder around oxygen atoms in the nano sized ceria samples in comparison to the highly crystalline NIST standard.In addition, the analysis reveal that the main differences observed in the pair correlations from various X-ray and neutron diffraction techniques were attributed to themore » particle size of the CeO 2 prepared by the reported three methods. Furthermore, detailed analysis of the Ce L 3– and K-edge EXAFS data support this finding; in particular the decrease in higher shell coordination numbers with respect to the NIST standard, are attributed to differences in particle size.« less

  13. Effect of Particle Size and Impact Velocity on Collision Behaviors Between Nano-Scale TiN Particles: MD Simulation.

    PubMed

    Yao, Hai-Long; Hu, Xiao-Zhen; Yang, Guan-Jun

    2018-06-01

    Inter-particle bonding formation which determines qualities of nano-scale ceramic coatings is influenced by particle collision behaviors during high velocity collision processes. In this study, collision behaviors between nano-scale TiN particles with different diameters were illuminated by using Molecular Dynamics simulation through controlling impact velocities. Results show that nano-scale TiN particles exhibit three states depending on particle sizes and impact velocities, i.e., bonding, bonding with localized fracturing, and rebounding. These TiN particles states are summarized into a parameter selection map providing an overview of the conditions in terms of particle sizes and velocities. Microstructure results show that localized atoms displacement and partial fracture around the impact region are main reasons for bonding formation of nano-scale ceramic particles, which shows differences from conventional particles refining and amorphization. A relationship between the adhesion energy and the rebound energy is established to understand bonding formation mechanism for nano-scale TiN particle collision. Results show that the energy relationship is depended on the particle sizes and impact velocities, and nano-scale ceramic particles can be bonded together as the adhesion energy being higher than the rebound energy.

  14. Dispersion and interaction of graphene oxide in amorphous and semi-crystalline nano-composites: a PALS study

    NASA Astrophysics Data System (ADS)

    Maurer, Frans H. J.; Arza, Carlos R.

    2015-06-01

    The influence of dispersion and interaction of Graphene Oxide (GO) in semicrystalline Polyhydroxy butyrate (PHB) and glassy amorphous Poly(tBP-oda) is explored by Positron Annihilation Lifetime Spectroscopy (PALS). The ortho-Positronium lifetimes which represent the main free volume hole size of both polymers are mainly affected by the large differences in internal stresses built up by the shrinkage of the polymers during their preparation, restricted by the platelet structure of GO. The ortho-Positronium intensities, which represent the ortho-Positronium formation probabilities, suggest a strong dependency of on the dispersion of the nano-particles and their aspect ratio.

  15. Membrane fouling by extracellular polymeric substances after ozone pre-treatment: Variation of nano-particles size.

    PubMed

    Yu, Wenzheng; Zhang, Dizhong; Graham, Nigel J D

    2017-09-01

    The application of ozone pre-treatment for ultrafiltration (UF) in drinking water treatment has been studied for more than 10 years, but its performance in mitigating or exacerbating membrane fouling has been inconclusive, and sometimes contradictory. To help explain this, our study considers the significance of the influent organic matter and its interaction with ozone on membrane fouling, using solutions of two representative types of extracellular polymeric substances (EPS), alginate and bovine serum albumin (BSA), and samples of surface water. The results show that at typical ozone doses there is no measurable mineralization of alginate and BSA, but substantial changes in their structure and an increase in the size of nano-particle aggregates (micro-flocculation). The impact of ozonation on membrane fouling, as indicated by the membrane flux, was markedly different for the two types of EPS and found to be related to the size of the nano-particle aggregates formed in comparison with the UF pore size. Thus, for BSA, ozonation created aggregate sizes similar to the UF pore size (100 k Dalton) which led to an increase in fouling. In contrast, ozonation of alginate created the nano-particle aggregates greater than the UF pore size, giving reduced membrane fouling/greater flux. For solutions containing a mixture of the two species of EPS the overall impact of ozonation on UF performance depends on the relative proportion of each, and the ozone dose, and the variable behaviour has been demonstrated by the surface water. These results provide new information about the role of nano-particle aggregate size in explaining the reported ambiguity over the benefits of applying ozone as pre-treatment for ultrafiltration. Copyright © 2017. Published by Elsevier Ltd.

  16. Electrochemical Nanoparticle Sizing Via Nano-Impacts: How Large a Nanoparticle Can be Measured?

    PubMed Central

    Bartlett, Thomas R; Sokolov, Stanislav V; Compton, Richard G

    2015-01-01

    The field of nanoparticle (NP) sizing encompasses a wide array of techniques, with electron microscopy and dynamic light scattering (DLS) having become the established methods for NP quantification; however, these techniques are not always applicable. A new and rapidly developing method that addresses the limitations of these techniques is the electrochemical detection of NPs in solution. The ‘nano-impacts’ technique is an excellent and qualitative in situ method for nanoparticle characterization. Two complementary studies on silver and silver bromide nanoparticles (NPs) were used to assess the large radius limit of the nano-impact method for NP sizing. Noting that by definition a NP cannot be larger than 100 nm in diameter, we have shown that the method quantitatively sizes at the largest limit, the lower limit having been previously reported as ∼6 nm.1 PMID:26491639

  17. Multi scale modeling of ignition and combustion of micro and nano aluminum particles

    NASA Astrophysics Data System (ADS)

    Puri, Puneesh

    With renewed interest in nano scale energetic materials like aluminum, many fundamental issues concerning the ignition and combustion characteristics at nano scales, remain to be clarified. The overall aim of the current study is the establishment of a unified theory accommodating the various processes and mechanisms involved in the combustion and ignition of aluminum particles at micro and nano scales. A comprehensive review on the ignition and combustion of aluminum particles at multi scales was first performed identifying various processes and mechanisms involved. Research focus was also placed on the establishment of a Molecular Dynamics (MD) simulation tool to investigate the characteristics of nano-particulate aluminum through three major studies. The general computational framework involved parallelized preprocessing, post-processing and main code with capability to simulate different ensembles using appropriate algorithms. Size dependence of melting temperature of pure aluminum particles was investigated in the first study. Phenomena like dynamic coexistence of solid and liquid phase and effect of surface charges on melting were explored. The second study involved the study of effect of defects in the form of voids on melting of bulk and particulate phase aluminum. The third MD study was used to analyze the thermo-mechanical behavior of nano-sized aluminum particles with total diameter of 5-10 nm and oxide thickness of 1-2.5 nm. The ensuing solid-solid and solid-liquid phase changes in the core and shell, stresses developed within the shell, and the diffusion of aluminum cations in the oxide layer, were explored in depth for amorphous and crystalline oxide layers. In the limiting case, the condition for pyrophoricity/explosivity of nano-particulate aluminum was analyzed and modified. The size dependence of thermodynamic properties at nano scales were considered and incorporated into the existing theories developed for micro and larger scales. Finally, a

  18. Millimeter wave complementary metal-oxide-semiconductor on-chip hexagonal nano-ferrite circulator

    NASA Astrophysics Data System (ADS)

    Chao, Liu; Oukacha, Hassan; Fu, Enjin; Koomson, Valencia Joyner; Afsar, Mohammed N.

    2015-05-01

    Hexagonal ferrites such as M-type BaFe12O19 and SrFe12O19 have strong uniaxial anisotropic magnetic field and remanent magnetism. The nano-sized ferrite powder exhibits high compatibility and processability in composite material. New magnetic devices using the M-type ferrite materials can work in the tens of GHz frequency range from microwave to millimeter wave without the application of strong external magnetic field. The micro- and nano-sized hexagonal ferrite can be conveniently utilized to fabricate magnetic components integrated in CMOS integrated circuits as thin as several micrometers. The micro-fabrication method of such nano ferrite device is presented in this paper. A circulator working at 60 GHz is designed and integrated into the commercial CMOS process. The circulator exhibits distinct circulation properties in the frequency range from 56 GHz to 58 GHz.

  19. Description of the first fungal dye-decolorizing peroxidase oxidizing manganese(II)

    DOE PAGES

    Fernandez-Fueyo, Elena; Linde, Dolores; Almendral, David; ...

    2015-05-13

    Two phylogenetically divergent genes of the new family of dye-decolorizing peroxidases (DyPs) were found during comparison of the four DyP genes identified in the Pleurotus ostreatus genome with over 200 DyP genes from other basidiomycete genomes. The heterologously expressed enzymes ( Pleos-DyP1 and Pleos-DyP4, following the genome nomenclature) efficiently oxidize anthraquinoid dyes (such as Reactive Blue 19), which are characteristic DyP substrates, as well as low redox-potential dyes (such as 2,2-azinobis-(3-ethylbenzothiazoline-6-sulfonic acid)) and substituted phenols. However, only Pleos-DyP4 oxidizes the high redox-potential dye Reactive Black 5, at the same time that it displays high thermal and pH stability. Unexpectedly, bothmore » enzymes also oxidize Mn 2+ to Mn 3+, albeit with very different catalytic efficiencies. Pleos-DyP4 presents a Mn 2+ turnover (56 s –1) nearly in the same order of the two other Mn 2+-oxidizing peroxidase families identified in the P. ostreatus genome: manganese peroxidases (100 s–1 average turnover) and versatile peroxidases (145 s –1 average turnover), whose genes were also heterologously expressed. Oxidation of Mn 2+ has been reported for an Amycolatopsis DyP (24 s –1) and claimed for other bacterial DyPs, albeit with lower activities, but this is the first time that Mn 2+ oxidation is reported for a fungal DyP. Interestingly, Pleos-DyP4 (together with ligninolytic peroxidases) is detected in the secretome of P. ostreatus grown on different lignocellulosic substrates. In conclusion, it is suggested that generation of Mn 3+ oxidizers plays a role in the P. ostreatus white-rot lifestyle since three different families of Mn 2+-oxidizing peroxidase genes are present in its genome being expressed during lignocellulose degradation.« less

  20. Description of the first fungal dye-decolorizing peroxidase oxidizing manganese(II)

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

    Fernandez-Fueyo, Elena; Linde, Dolores; Almendral, David

    Two phylogenetically divergent genes of the new family of dye-decolorizing peroxidases (DyPs) were found during comparison of the four DyP genes identified in the Pleurotus ostreatus genome with over 200 DyP genes from other basidiomycete genomes. The heterologously expressed enzymes ( Pleos-DyP1 and Pleos-DyP4, following the genome nomenclature) efficiently oxidize anthraquinoid dyes (such as Reactive Blue 19), which are characteristic DyP substrates, as well as low redox-potential dyes (such as 2,2-azinobis-(3-ethylbenzothiazoline-6-sulfonic acid)) and substituted phenols. However, only Pleos-DyP4 oxidizes the high redox-potential dye Reactive Black 5, at the same time that it displays high thermal and pH stability. Unexpectedly, bothmore » enzymes also oxidize Mn 2+ to Mn 3+, albeit with very different catalytic efficiencies. Pleos-DyP4 presents a Mn 2+ turnover (56 s –1) nearly in the same order of the two other Mn 2+-oxidizing peroxidase families identified in the P. ostreatus genome: manganese peroxidases (100 s–1 average turnover) and versatile peroxidases (145 s –1 average turnover), whose genes were also heterologously expressed. Oxidation of Mn 2+ has been reported for an Amycolatopsis DyP (24 s –1) and claimed for other bacterial DyPs, albeit with lower activities, but this is the first time that Mn 2+ oxidation is reported for a fungal DyP. Interestingly, Pleos-DyP4 (together with ligninolytic peroxidases) is detected in the secretome of P. ostreatus grown on different lignocellulosic substrates. In conclusion, it is suggested that generation of Mn 3+ oxidizers plays a role in the P. ostreatus white-rot lifestyle since three different families of Mn 2+-oxidizing peroxidase genes are present in its genome being expressed during lignocellulose degradation.« less

  1. Fabrication and mechanical evaluation of hydroxyapatite/oxide nano-composite materials.

    PubMed

    Mohamed, Khaled R; Beherei, Hanan H; El Bassyouni, Gehan T; El Mahallawy, Nahed

    2013-10-01

    In the current study, the semiconducting metal oxides such as nano-ZnO and SiO2 powders were prepared via sol-gel technique and conducted on nano-hydroxyapatite (nHA) which was synthesized by chemical precipitation. The properties of fabricated nano-structured composites containing different ratios of HA, ZnO and SiO2 were examined using X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy, scanning electron microscope (SEM) and transmission electron microscope (TEM) techniques. The effect of the variation of ratios between the three components on mechanical, microstructure and in-vitro properties was assessed to explore the possibility of enhancing these properties. The results proved that the mechanical properties exhibited an increment with increasing the ZnO content at the extent of HA. In-vitro study proved the formation and nucleation of apatite onto the surface of the fabricated composites after one week of immersion. It is concluded that HA composites containing SiO2 or SiO2/ZnO content had a suitable mechanical properties and ability to form apatite particles onto the composite surface. Based on bioactivity behavior, Si-HA is more bioactive than pure hydroxyapatite and nano-arrangements will provide an interface for better bone formation. Therefore, these nano-composites will be promising as bone substitutes especially in load bearing sites. Copyright © 2013 Elsevier B.V. All rights reserved.

  2. Effect of size on bulk and surface cohesion energy of metallic nano-particles

    NASA Astrophysics Data System (ADS)

    Yaghmaee, M. S.; Shokri, B.

    2007-04-01

    The knowledge of nano-material properties not only helps us to understand the extreme behaviour of small-scale materials better (expected to be different from what we observe from their bulk value) but also helps us to analyse and design new advanced functionalized materials through different nano technologies. Among these fundamental properties, the cohesion (binding) energy mainly describes most behaviours of materials in different environments. In this work, we discuss this fundamental property through a nano-thermodynamical approach using two algorithms, where in the first approach the size dependence of the inner (bulk) cohesion energy is studied, and in the second approach the surface cohesion energy is considered too. The results, which are presented through a computational demonstration (for four different metals: Al, Ga, W and Ag), can be compared with some experimental values for W metallic nano-particles.

  3. Fabrication of a Ni nano-imprint stamp for an anti-reflective layer using an anodic aluminum oxide template.

    PubMed

    Park, Eun-Mi; Lim, Seung-Kyu; Ra, Senug-Hyun; Suh, Su-Jung

    2013-11-01

    Aluminum anodizing can alter pore diameter, density distribution, periodicity and layer thickness in a controlled way. Because of this property, porous type anodic aluminum oxide (AAO) was used as a template for nano-structure fabrication. The alumina layer generated at a constant voltage increased the pore size from 120 nm to 205 nm according to an increasing process time from 60 min to 150 min. The resulting fabricated AAO templates had pore diameters at or less than 200 nm. Ni was sputtered as a conductive layer onto this AAO template and electroplated using DC and pulse power. Comparing these Ni stamps, those generated from electroplating using on/reverse/off pulsing had an ordered pillar array and maintained the AAO template morphology. This stamp was used for nano-imprinting on UV curable resin coated glass wafer. Surface observations via electron microscopy showed that the nano-imprinted patterned had the same shape as the AAO template. A soft mold was subsequently fabricated and nano-imprinted to form a moth-eye structure on the glass wafer. An analysis of the substrate transmittance using UV-VIS/NIR spectroscopy showed that the transmittance of the substrate with the moth-eye structure was 5% greater that the non-patterned substrate.

  4. Using size-selected gold clusters on graphene oxide films to aid cryo-transmission electron tomography alignment

    PubMed Central

    Arkill, Kenton P.; Mantell, Judith M.; Plant, Simon R.; Verkade, Paul; Palmer, Richard E.

    2015-01-01

    A three-dimensional reconstruction of a nano-scale aqueous object can be achieved by taking a series of transmission electron micrographs tilted at different angles in vitreous ice: cryo-Transmission Electron Tomography. Presented here is a novel method of fine alignment for the tilt series. Size-selected gold clusters of ~2.7 nm (Au561 ± 14), ~3.2 nm (Au923 ± 22), and ~4.3 nm (Au2057 ± 45) in diameter were deposited onto separate graphene oxide films overlaying holes on amorphous carbon grids. After plunge freezing and subsequent transfer to cryo-Transmission Electron Tomography, the resulting tomograms have excellent (de-)focus and alignment properties during automatic acquisition. Fine alignment is accurate when the evenly distributed 3.2 nm gold particles are used as fiducial markers, demonstrated with a reconstruction of a tobacco mosaic virus. Using a graphene oxide film means the fiducial markers are not interfering with the ice bound sample and that automated collection is consistent. The use of pre-deposited size-selected clusters means there is no aggregation and a user defined concentration. The size-selected clusters are mono-dispersed and can be produced in a wide size range including 2–5 nm in diameter. The use of size-selected clusters on a graphene oxide films represents a significant technical advance for 3D cryo-electron microscopy. PMID:25783049

  5. 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.

  6. Bone marrow mesenchymal stem cell response to nano-structured oxidized and turned titanium surfaces.

    PubMed

    Annunziata, Marco; Oliva, Adriana; Buosciolo, Antonietta; Giordano, Michele; Guida, Agostino; Guida, Luigi

    2012-06-01

    The aim of this study was to analyse the topographic features of a novel nano-structured oxidized titanium implant surface and to evaluate its effect on the response of human bone marrow mesenchymal stem cells (BM-MSC) compared with a traditional turned surface. The 10 × 10 × 1 mm turned (control) and oxidized (test) titanium samples (P.H.I. s.r.l.) were examined by scanning electron microscopy (SEM) and atomic force microscopy (AFM) and characterized by height, spatial and hybrid roughness parameters at different dimensional ranges of analysis. Primary cultures of BM-MSC were seeded on titanium samples and cell morphology, adhesion, proliferation and osteogenic differentiation, in terms of alkaline phosphatase activity, osteocalcin synthesis and extracellular matrix mineralization, were evaluated. At SEM and AFM analyses turned samples were grooved, whereas oxidized surfaces showed a more complex micro- and nano-scaled texture, with higher values of roughness parameters. Cell adhesion and osteogenic parameters were greater on oxidized (P<0.05 at least) vs. turned surfaces, whereas the cell proliferation rate was similar on both samples. Although both control and test samples were in the range of average roughness proper of smooth surfaces, they exhibited significantly different topographic properties in terms of height, spatial and, mostly, of hybrid parameters. This different micro- and nano-structure resulted in an enhanced adhesion and differentiation of cells plated onto the oxidized surfaces. © 2011 John Wiley & Sons A/S.

  7. Nano-sized, quaternary titanium(IV) metal-organic frameworks with multidentate ligands.

    PubMed

    Baranwal, Balram Prasad; Singh, Alok Kumar

    2010-12-01

    Some mononuclear nano-sized, quaternary titanium(IV) complexes having the general formula [Ti(acac)(OOCR)2(SB)] (where Hacac=acetylacetone, R=C15H31 or C17H35, HSB=Schiff bases) have been synthesized using different multidentate ligands. These were characterized by elemental analyses, molecular weight determinations and spectral (FTIR, 1H NMR and powder XRD) studies. Conductance measurement indicated their non-conducting nature which may behave like insulators. Structural parameters like the values of limiting indices h, k, l, cell constants a, b, c, angles α, β, γ and particle size are calculated from powder XRD data for complex 1 which indicated nano-sized triclinic system in them. Bidentate chelating nature of acetylacetone, carboxylate and Schiff base anions in the complexes was established by their infrared spectra. Molecular weight determinations confirmed mononuclear nature of the complexes. On the basis of physico-chemical studies, coordination number 8 was assigned for titanium(IV) in the complexes. Transmission electron microscopy (TEM) and the selected area electron diffraction (SAED) studies indicated spherical particles with poor crystallinity. Copyright © 2010 Elsevier B.V. All rights reserved.

  8. Preparation of nano fluids by mechanical method

    NASA Astrophysics Data System (ADS)

    Boopathy, J.; Pari, R.; Kavitha, M.; Angelo, P. C.

    2012-07-01

    Nanofluids are conventional heat transfer fluids that contain nano particles of metals, oxides, carbides, nitrides, or nanotubes. Nanofluids exhibit enhanced thermal conductivity and heat transfer coefficients compared to the base fluids. This paper presents the procedure for preparing nanofluids consisting of Copper and Aluminium nano powders in base fluids. Copper and Aluminium nano powders were produced by planetary ball wet milling at 300rpm for 50hrs. Toluene was added to ensure wet milling. These powders were characterized in XRD and SEM for their purity, particle size and shape. The XRD results confirmed the final particle sizes of Copper and Aluminium in the nano range. Then the 0.01 gm of nano metal powders was added in 150 ml of double distilled water and magnetic stirring was done at 1500 rpm for 15 minutes. Sodium lauryl sulphate (0.05%) was added in water as surfactant to ensure the stability of the dispersion. Ultrasonication in the 3000 watts bath was done for 10 minutes to enhance the uniform dispersion of metal powders in water. The pH, dynamic viscosity, ionic conductivity and the stability of the fluids were determined for further usage of synthesized nanofluids as coolant during grinding operation.

  9. 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.

  10. Biogenic manganese oxide nanoparticle formation by a multimeric multicopper oxidase Mnx.

    PubMed

    Romano, Christine A; Zhou, Mowei; Song, Yang; Wysocki, Vicki H; Dohnalkova, Alice C; Kovarik, Libor; Paša-Tolić, Ljiljana; Tebo, Bradley M

    2017-09-29

    Bacteria that produce Mn oxides are extraordinarily skilled engineers of nanomaterials that contribute significantly to global biogeochemical cycles. Their enzyme-based reaction mechanisms may be genetically tailored for environmental remediation applications or bioenergy production. However, significant challenges exist for structural characterization of the enzymes responsible for biomineralization. The active Mn oxidase in Bacillus sp. PL-12, Mnx, is a complex composed of a multicopper oxidase (MCO), MnxG, and two accessory proteins, MnxE and MnxF. MnxG shares sequence similarity with other, structurally characterized MCOs. MnxE and MnxF have no similarity to any characterized proteins. The ~200 kDa complex has been recalcitrant to crystallization, so its structure is unknown. Here, we show that native mass spectrometry defines the subunit topology and copper binding of Mnx, while high-resolution electron microscopy visualizes the protein and nascent Mn oxide minerals. These data provide critical structural information for understanding Mn biomineralization by such unexplored enzymes.Significant challenges exist for structural characterization of enzymes responsible for biomineralization. Here the authors show that native mass spectrometry and high resolution electron microscopy can define the subunit topology and copper binding of a manganese oxidizing complex, and describe early stage formation of its mineral products.

  11. Mechanical behavior of shock-wave consolidated nano and micron-sized aluminum/silicon carbide and aluminum/aluminum oxide two-phase systems characterized by light and electron metallography

    NASA Astrophysics Data System (ADS)

    Alba-Baena, Noe Gaudencio

    This dissertation reports the results of the exploratory study of two-phase systems consisting of 150 microm diameter aluminum powder mechanically mixed with 30 nm and 30 microm diameter SiC and Al2O3 powders (in volume fractions of 2, 4, and 21 percent). Powders were mechanically mixed and green compacted to ˜80% theorical density in a series of cylindrical fixtures (steel tubes). The compacted arrangements were explosively consolidated using ammonium nitrate-fuel oil (ANFO) to form stacks of two-phase systems. As result, successfully consolidated cylindrical monoliths of 50 mm (height) x 32 mm (in diameter) were obtained. By taking advantage of the use of SWC (shock wave consolidation) and WEDM (wire-electric discharge machining), the heterogeneous systems were machined in a highly efficiency rate. The sample cuts used for characterization and mechanical properties testing, require the use of less that 10cc of each monolith, in consequence there was preserved an average of 60% of the obtained system monoliths. Consolidated test cylinders of the pure Al and two-phase composites were characterized by optical metallography and TEM. The light micrographs for the five explosively consolidated regimes: aluminum powder, nano and micron-sized Al/Al2O3 systems, and the nano and micron-sized Al/SiC systems exhibit similar ductility in the aluminum grains. Low volume fraction systems exhibit small agglomerations at the grain boundaries for the Al/Al2O3 system and the Al/SiC system reveal a well distributed phase at the grain boundaries. Large and partially bonded agglomerations were observable in the nano-sized high volume fraction (21%) systems, while the micron-sized Al/ceramic systems exhibit homogeneous distribution along the aluminum phase grains. TEM images showed the shock-induced dislocation cell structure, which has partially recrystallized to form a nano grain structure in the consolidated aluminum powder. Furthermore, the SiC nano-agglomerates appeared to have

  12. 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.

  13. Synthesis and mechanical/magnetic properties of nano-grained iron-oxides prepared with an inert gas condensation and pulse electric current sintering process

    NASA Astrophysics Data System (ADS)

    Choa, Yong-Ho; Nakayama, Tatachika; Sekino, Tohru; Niihara, Koichi

    1999-04-01

    Nanocrystalline iron-oxide powder was fabricated with an inert gas condensation (IGC) method combined with evaporation, and in-situ oxidation techniques. The particle size of iron-oxide powder was controlled by varying the helium gas pressure between 0.1 and 10 Torr, with the smallest one =10 nm at 0.1 Torr. The nanostructure was characterized by TEM. Nanocrystalline iron-oxide powder was sintered with the pulse electric current sintering (PECS) method to obtain densified γ-Fe2O3 materials, and suitably densified nano-grained γ-Fe2O3 materials (≈ 40 nm) of great hardness were obtained. The correlation between the nanostructure and magnetic properties of nanocrystalline powder and densified γ-Fe2O3 materials was also investigated.

  14. 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.

  15. X-ray absorption spectroscopy characterization of embedded and extracted nano-oxides

    DOE PAGES

    Stan, Tiberiu; Sprouster, David J.; Ofan, Avishai; ...

    2016-12-29

    Here, the chemistries and structures of both embedded and extracted Ysingle bondTisingle bondO nanometer-scale oxides in a nanostructured ferritic alloy (NFA) were probed by x-ray absorption spectroscopy (XAS). Y 2Ti 2O 7 is the primary embedded phase, while the slightly larger extracted oxides are primarily Y 2TiO 5. Analysis of the embedded nano-oxides is difficult partly due to the multiple Ti environments associated with different oxides and those still residing in matrix lattice sites. Thus, bulk extraction followed by selective filtration was used to isolate the larger Y 2TiO 5 oxides for XAS, while the smaller predominant embedded phase Ymore » 2Ti 2O 7 oxides passed through the filters and were analyzed using the log-ratio method.« less

  16. Effects of properties of manganese oxide-impregnated catalysts and flue gas condition on multipollutant control of Hg0 and NO.

    PubMed

    Chiu, Chun-Hsiang; Hsi, Hsing-Cheng; Lin, Hong-Ping; Chang, Tien-Chin

    2015-06-30

    This research investigated the effects of manganese oxide (MnOx) impregnation on the physical/chemical properties and multi pollutant control effectiveness of Hg(0) and NO using a V2O5-WO3/TiO2-SiO2 selective catalytic reduction (SCR) catalyst. Raw and MnOx-treated SCR samples were bean-shaped nanoparticles with sizes within 10-30 nm. Impregnating MnOx of ≤ 5 wt% caused limited changes in physical properties of the catalyst. The decrease in surface area when the impregnated MnOx amount was 10 wt% may stem from the pore blockage and particle growth or aggregation of the catalyst. Mn(4+) was the main valence state of impregnated MnOx. Apparent crystallinity of MnOx was not observed based on X-ray diffraction. MnOx impregnation enhanced the Hg(0) oxidation and NO/SO2 removal of SCR catalyst. The 5 and 10% MnOx-impregnated samples had the greatest multi pollutant control potentials for Hg(0) oxidation and NO removal; however, the increasing SO2 removal that may be mainly due to SO2-SO3 conversion should be cautioned. HCl and O2 greatly promoted Hg(0) oxidation. SO2 enhanced Hg(0) oxidation at ≤ 200 ppm while NO and NH3 consistently inhibited Hg(0) oxidation. Elevating flue gas temperature enhanced Hg(0) oxidation. Overall, MnOx-impregnated catalysts show stable and consistent multi pollutant removal effectiveness under the test conditions. Copyright © 2015 Elsevier B.V. All rights reserved.

  17. The role of allophane nano-structure and Fe oxide speciation for hosting soil organic matter in an allophanic Andosol

    NASA Astrophysics Data System (ADS)

    Filimonova, Svetlana; Kaufhold, Stephan; Wagner, Friedrich E.; Häusler, Werner; Kögel-Knabner, Ingrid

    2016-05-01

    We evaluated the impact of nano-structural characteristics of allophanic compounds and Fe oxide speciation on the efficiency of organo-mineral interactions in an allophanic Andosol derived from volcanic ash (Eifel mountains, Germany). The samples selected for our work represented a gradient from: (i) a pure synthetic allophane and (ii) model organo-mineral mixtures to (iii) particle size fractions of the natural Andosol. We thus aimed to link the processes operating at the individual molecular scale to the phenomena active at the aggregate scale. For a non-destructive characterization of the samples, we applied 129Xe NMR spectroscopy of adsorbed Xe atoms (to identify the mineral nano-structure and surface acid centres), ESEM (verifying the nano-spherical structure of allophane), 13C CPMAS NMR (for the nature of the soil organic matter (SOM)), 57Fe Mössbauer spectroscopy (Fe oxide speciation), and N2 adsorption (contribution of micro- and mesoporosity). By using the atomic probe Xe, we obtained evidence for a coupled mechanism of adsorption onto allophane requiring both the narrow pores (voids formed by the primary nano-spherules) and the acid centres located at the defect surfaces of the primary spherules. The validity of this coupled mechanism for the sorption of organic matter was confirmed by the concomitant blocking of acid centres (129Xe NMR data) and the decrease of the N2-available pore volumes (Vmicro and Vmeso) in the model samples DOM/- and NOM/allophane (DOM = dissolved OM, NOM = natural OM). In the Andosol, the high resistance of SOM against oxidation (OCresist = 15-50%) was combined with preferential accumulation of certain organic compounds, e.g. potentially labile substrates such as carbohydrates, and the low molecular weight species such as amino acids. This feature was attributed to the peculiar microporous tortuous structure of allophane aggregates that likely impose certain criteria for the chemical nature and size of mineral-bound SOM. On the

  18. Preparation of uniform-sized multiple emulsions and micro/nano particulates for drug delivery by membrane emulsification.

    PubMed

    Liu, Wei; Yang, Xiang-Liang; Ho, W S Winston

    2011-01-01

    Much attention has in recent years been paid to fine applications of drug delivery systems, such as multiple emulsions, micro/nano solid lipid and polymer particles (spheres or capsules). Precise control of particle size and size distribution is especially important in such fine applications. Membrane emulsification can be used to prepare uniform-sized multiple emulsions and micro/nano particulates for drug delivery. It is a promising technique because of the better control of size and size distribution, the mildness of the process, the low energy consumption, easy operation and simple equipment, and amendable for large scale production. This review describes the state of the art of membrane emulsification in the preparation of monodisperse multiple emulsions and micro/nano particulates for drug delivery in recent years. The principles, influence of process parameters, advantages and disadvantages, and applications in preparing different types of drug delivery systems are reviewed. It can be concluded that the membrane emulsification technique in preparing emulsion/particulate products for drug delivery will further expand in the near future in conjunction with more basic investigations on this technique. Copyright © 2010 Wiley-Liss, Inc. and the American Pharmacists Association

  19. Physicochemical characterization, and relaxometry studies of micro-graphite oxide, graphene nanoplatelets, and nanoribbons.

    PubMed

    Paratala, Bhavna S; Jacobson, Barry D; Kanakia, Shruti; Francis, Leonard Deepak; Sitharaman, Balaji

    2012-01-01

    The chemistry of high-performance magnetic resonance imaging contrast agents remains an active area of research. In this work, we demonstrate that the potassium permanganate-based oxidative chemical procedures used to synthesize graphite oxide or graphene nanoparticles leads to the confinement (intercalation) of trace amounts of Mn(2+) ions between the graphene sheets, and that these manganese intercalated graphitic and graphene structures show disparate structural, chemical and magnetic properties, and high relaxivity (up to 2 order) and distinctly different nuclear magnetic resonance dispersion profiles compared to paramagnetic chelate compounds. The results taken together with other published reports on confinement of paramagnetic metal ions within single-walled carbon nanotubes (a rolled up graphene sheet) show that confinement (encapsulation or intercalation) of paramagnetic metal ions within graphene sheets, and not the size, shape or architecture of the graphitic carbon particles is the key determinant for increasing relaxivity, and thus, identifies nano confinement of paramagnetic ions as novel general strategy to develop paramagnetic metal-ion graphitic-carbon complexes as high relaxivity MRI contrast agents.

  20. Physicochemical Characterization, and Relaxometry Studies of Micro-Graphite Oxide, Graphene Nanoplatelets, and Nanoribbons

    PubMed Central

    Paratala, Bhavna S.; Jacobson, Barry D.; Kanakia, Shruti; Francis, Leonard Deepak; Sitharaman, Balaji

    2012-01-01

    The chemistry of high-performance magnetic resonance imaging contrast agents remains an active area of research. In this work, we demonstrate that the potassium permanganate-based oxidative chemical procedures used to synthesize graphite oxide or graphene nanoparticles leads to the confinement (intercalation) of trace amounts of Mn2+ ions between the graphene sheets, and that these manganese intercalated graphitic and graphene structures show disparate structural, chemical and magnetic properties, and high relaxivity (up to 2 order) and distinctly different nuclear magnetic resonance dispersion profiles compared to paramagnetic chelate compounds. The results taken together with other published reports on confinement of paramagnetic metal ions within single-walled carbon nanotubes (a rolled up graphene sheet) show that confinement (encapsulation or intercalation) of paramagnetic metal ions within graphene sheets, and not the size, shape or architecture of the graphitic carbon particles is the key determinant for increasing relaxivity, and thus, identifies nano confinement of paramagnetic ions as novel general strategy to develop paramagnetic metal-ion graphitic-carbon complexes as high relaxivity MRI contrast agents. PMID:22685555

  1. Production of zinc and manganese oxide particles by pyrolysis of alkaline and Zn-C battery waste.

    PubMed

    Ebin, Burçak; Petranikova, Martina; Steenari, Britt-Marie; Ekberg, Christian

    2016-05-01

    Production of zinc and manganese oxide particles from alkaline and zinc-carbon battery black mass was studied by a pyrolysis process at 850-950°C with various residence times under 1L/minN2(g) flow rate conditions without using any additive. The particular and chemical properties of the battery waste were characterized to investigate the possible reactions and effects on the properties of the reaction products. The thermodynamics of the pyrolysis process were studied using the HSC Chemistry 5.11 software. The carbothermic reduction reaction of battery black mass takes place and makes it possible to produce fine zinc particles by a rapid condensation, after the evaporation of zinc from a pyrolysis batch. The amount of zinc that can be separated from the black mass is increased by both pyrolysis temperature and residence time. Zinc recovery of 97% was achieved at 950°C and 1h residence time using the proposed alkaline battery recycling process. The pyrolysis residue is mainly MnO powder with a low amount of zinc, iron and potassium impurities and has an average particle size of 2.9μm. The obtained zinc particles have an average particle size of about 860nm and consist of hexagonal crystals around 110nm in size. The morphology of the zinc particles changes from a hexagonal shape to s spherical morphology by elevating the pyrolysis temperature. Copyright © 2015 Elsevier Ltd. All rights reserved.

  2. Associations among environmental exposure to manganese, neuropsychological performance, oxidative damage and kidney biomarkers in children.

    PubMed

    Nascimento, Sabrina; Baierle, Marília; Göethel, Gabriela; Barth, Anelise; Brucker, Natália; Charão, Mariele; Sauer, Elisa; Gauer, Bruna; Arbo, Marcelo Dutra; Altknecht, Louise; Jager, Márcia; Dias, Ana Cristina Garcia; de Salles, Jerusa Fumagalli; Saint' Pierre, Tatiana; Gioda, Adriana; Moresco, Rafael; Garcia, Solange Cristina

    2016-05-01

    Environmental exposure to manganese (Mn) results in several toxic effects, mainly neurotoxicity. This study investigated associations among Mn exposure, neuropsychological performance, biomarkers of oxidative damage and early kidney dysfunction in children aged 6-12 years old. Sixty-three children were enrolled in this study, being 43 from a rural area and 20 from an urban area. Manganese was quantified in blood (B-Mn), hair (H-Mn) and drinking water using inductively coupled plasma mass spectrometry (ICP-MS). The neuropsychological functions assessed were attention, perception, working memory, phonological awareness and executive functions - inhibition. The Intelligence quotient (IQ) was also evaluated. The biomarkers malondialdehyde (MDA), protein carbonyls (PCO), δ-aminolevulinate dehydratase (ALA-D), reactivation indexes with dithiothreitol (ALA-RE/DTT) and ZnCl2 (ALA-RE/ZnCl2), non-protein thiol groups, as well as microalbuminuria (mALB) level and N-acetyl-β-D-glucosaminidase (NAG) activity were assessed. The results demonstrated that Mn levels in blood, hair and drinking water were higher in rural children than in urban children (p<0.01). Adjusted for potential confounding factors, IQ, age, gender and parents' education, significant associations were observed mainly between B-Mn and visual attention (β=0.649; p<0.001). Moreover, B-Mn was negatively associated with visual perception and phonological awareness. H-Mn was inversely associated with working memory, and Mn levels from drinking water with written language and executive functions - inhibition. Rural children showed a significant increase in oxidative damage to proteins and lipids, as well as alteration in kidney function biomarkers (p<0.05). Moreover, significant associations were found between B-Mn, H-Mn and Mn levels in drinking water and biomarkers of oxidative damage and kidney function, besides between some oxidative stress biomarkers and neuropsychological tasks (p<0.05). The findings of this

  3. Non-destructive evaluation of nano-sized structure of thin film devices by using small angle neutron scattering.

    PubMed

    Shin, E J; Seong, B S; Choi, Y; Lee, J K

    2011-01-01

    Nano-sized multi-layers copper-doped SrZrO3, platinum (Pt) and silicon oxide (SiO2) on silicon substrates were prepared by dense plasma focus (DPF) device with the high purity copper anode tip and analyzed by using small angle neutron scattering (SANS) to establish a reliable method for the non-destructive evaluation of the under-layer structure. Thin film was well formed at the time-to-dip of 5 microsec with stable plasma of DPF. Several smooth intensity peaks were periodically observed when neutron beam penetrates the thin film with multi-layers perpendicularly. The platinum layer is dominant to intensity peaks, where the copper-doped SrZnO3 layer next to the platinum layer causes peak broadening. The silicon oxide layer has less effect on the SANS spectra due to its relative thick thickness. The SANS spectra shows thicknesses of platinum and copper-doped SrZnO3 layers as 53 and 25 nm, respectively, which are well agreement with microstructure observation.

  4. Electromagnetic characteristics of manganese oxide-coated Fe3O4 nanoparticles at 2-18 GHz

    NASA Astrophysics Data System (ADS)

    Yang, R. B.; Liang, W. F.; Lin, C. K.

    2011-04-01

    The dielectric and magnetic properties of manganese oxide-coated Fe3O4 nanoparticles (NPs) were measured by the transmission/reflection method in 2-18 GHz. MnOx-coated Fe3O4 NPs were prepared by sol-gel method followed by heat-treating at 300, 400, and 500 °C, respectively. The heat-treated powders were then used as magnetic fillers and added to an epoxy resin to prepare MnOx-coated Fe3O4 composites for the complex permittivity (ɛ'-jɛ″) and permeability (μ'-jμ″) measurements. After the sol-gel process, the coating of manganese oxide (mixture of major Mn2O3 and minor Mn3O4) reduced the value of ɛ'. The lower the heat-treating temperature, the larger the decrease in ɛ'. The relative decrease in ɛ', compared with uncoated Fe3O4 nanoparticles, is 28.7, 23.5, and 20.0% for coated MnOx heat-treated at 300, 400, and 500 °C, respectively, while the relative decrease in ɛ″ is 74.1, 68.8, and 65.2%, respectively. In the present study, MnOx-coated Fe3O4 exhibited a significant decrease in dielectric loss tangent of ˜100% compared to that of uncoated NPs and can be of practical use for microwave components.

  5. Effects of serum on cytotoxicity of nano- and micro-sized ZnO particles

    NASA Astrophysics Data System (ADS)

    Hsiao, I.-Lun; Huang, Yuh-Jeen

    2013-09-01

    Although an increasing number of in vitro studies are being published regarding the cytotoxicity of nanomaterials, the components of the media for toxicity assays have often varied according to the needs of the scientists. Our aim for this study was to evaluate the influence of serum—in this case, fetal bovine serum—in a cell culture medium on the toxicity of nano-sized (50-70 nm) and micro-sized (<1 μm) ZnO on human lung epithelial cells (A549). The nano- and micro-sized ZnO both exhibited their highest toxicity when exposed to serum-free media, in contrast to exposure in media containing 5 or 10 % serum. This mainly comes not only from the fact that ZnO particles in the serum-free media have a higher dosage-per-cell ratio, which results from large aggregates of particles, rapid sedimentation, absence of protein protection, and lower cell growth rate, but also that extracellular Zn2+ release contributes to cytotoxicity. Although more extracellular Zn2+ release was observed in serum-containing media, it did not contribute to nano-ZnO cytotoxicity. Furthermore, non-dissolved particles underwent size-dependent particle agglomeration, resulting in size-dependent toxicity in both serum-containing and serum-free media. A low correlation between cytotoxicity and inflammation endpoints in the serum-free medium suggested that some signaling pathways were changed or induced. Since cell growth, transcription behavior for protein production, and physicochemical properties of ZnO particles all were altered in serum-free media, we recommend the use of a serum-containing medium when evaluating the cytotoxicity of NPs.

  6. Aerosol synthesis of nano and micro-scale zero valent metal particles from oxide precursors

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

    Phillips, Jonathan; Luhrs, Claudia; Lesman, Zayd

    2010-01-01

    In this work a novel aerosol method, derived form the batch Reduction/Expansion Synthesis (RES) method, for production of nano / micro-scale metal particles from oxides and hydroxides is presented. In the Aerosol-RES (A-RES) method, an aerosol, consisting of a physical mixture of urea and metal oxide or hydroxides, is passed through a heated oven (1000 C) with a residence time of the order of 1 second, producing pure (zero valent) metal particles. It appears that the process is flexible regarding metal or alloy identity, allows control of particle size and can be readily scaled to very large throughput. Current workmore » is focused on creating nanoparticles of metal and metal alloy using this method. Although this is primarily a report on observations, some key elements of the chemistry are clear. In particular, the reducing species produced by urea decomposition are the primary agents responsible for reduction of oxides and hydroxides to metal. It is also likely that the rapid expansion that takes place when solid/liquid urea decomposes to form gas species influences the final morphology of the particles.« less

  7. Extremely fine structured cathode for solid oxide fuel cells using Sr-doped LaMnO3 and Y2O3-stabilized ZrO2 nano-composite powder synthesized by spray pyrolysis

    NASA Astrophysics Data System (ADS)

    Shimada, Hiroyuki; Yamaguchi, Toshiaki; Sumi, Hirofumi; Nomura, Katsuhiro; Yamaguchi, Yuki; Fujishiro, Yoshinobu

    2017-02-01

    A solid oxide fuel cell (SOFC) for high power density operation was developed with a microstructure-controlled cathode using a nano-composite powder of Sr-doped LaMnO3 (LSM) and Y2O3-stabilized ZrO2 (YSZ) synthesized by spray pyrolysis. The individual LSM-YSZ nano-composite particles, formed by crystalline and amorphous nano-size LSM and YSZ particles, showed spherical morphology with uniform particle size. The use of this powder for cathode material led to an extremely fine microstructure, in which all the LSM and YSZ grains (approximately 100-200 nm) were highly dispersed and formed their own network structures. This microstructure was due to the two phase electrode structure control using the powder, namely, nano-order level in each particle and micro-order level between particles. An anode-supported SOFC with the LSM-YSZ cathode using humidified H2 as fuel and ambient air as oxidant exhibited high power densities, such as 1.29 W cm-2 under a voltage of 0.75 V and a maximum power density of 2.65 W cm-2 at 800 °C. Also, the SOFC could be stably operated for 250 h with no degradation, even at a high temperature of 800 °C.

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

    NASA Astrophysics Data System (ADS)

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

    2008-08-01

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

  9. Stratigraphy of the pedogenic manganese nodules in the Carletonville area, North West Province of South Africa: A case study of the General Nice Manganese Mine

    NASA Astrophysics Data System (ADS)

    Pharoe, Benedict Kinshasa; Liu, Kuiwu

    2018-07-01

    The lithostratigraphy of pedogenic manganese (Mn) nodules in the Carletonville area is similar to the Klipkuil, Ryedale, Wes Wits, and Houtkoppies deposits in the West Rand region of the Gauteng and North West Provinces and to a lesser extent the Bronkhorstfontein manganese deposit in the Limpopo Province of South Africa. The lithostratigraphy of the ore deposit at the General Nice Manganese Mine consists of a basal manganese wad, preserved in a typical karst setting on top of the underlying Malmani stromatolitic dolomites and Tertiary fluvial and secondary mineral deposits consisting of manganese nodules of variable size in a finer-grained soil matrix. At the top of the deposit is a Mn-depleted Quaternary sand cover. The Tertiary alluvial succession hosting Mn nodules was informally subdivided into A, B, C, D, E, F, G and H zones on the basis of geochemical analyses (XRD, XRF and SEM) of bulk zone samples and the manganese nodule size and concentration.

  10. Support for the initial attachment, growth and differentiation of MG-63 cells: a comparison between nano-size hydroxyapatite and micro-size hydroxyapatite in composites

    PubMed Central

    Filová, Elena; Suchý, Tomáš; Sucharda, Zbyněk; Šupová, Monika; Žaloudková, Margit; Balík, Karel; Lisá, Věra; Šlouf, Miroslav; Bačáková, Lucie

    2014-01-01

    Hydroxyapatite (HA) is considered to be a bioactive material that favorably influences the adhesion, growth, and osteogenic differentiation of osteoblasts. To optimize the cell response on the hydroxyapatite composite, it is desirable to assess the optimum concentration and also the optimum particle size. The aim of our study was to prepare composite materials made of polydimethylsiloxane, polyamide, and nano-sized (N) or micro-sized (M) HA, with an HA content of 0%, 2%, 5%, 10%, 15%, 20%, 25% (v/v) (referred to as N0–N25 or M0–M25), and to evaluate them in vitro in cultures with human osteoblast-like MG-63 cells. For clinical applications, fast osseointegration of the implant into the bone is essential. We observed the greatest initial cell adhesion on composites M10 and N5. Nano-sized HA supported cell growth, especially during the first 3 days of culture. On composites with micro-size HA (2%–15%), MG-63 cells reached the highest densities on day 7. Samples M20 and M25, however, were toxic for MG-63 cells, although these composites supported the production of osteocalcin in these cells. On N2, a higher concentration of osteopontin was found in MG-63 cells. For biomedical applications, the concentration range of 5%–15% (v/v) nano-size or micro-size HA seems to be optimum. PMID:25125978

  11. Thallium-isotopic compositions of euxinic sediments as a proxy for global manganese-oxide burial

    NASA Astrophysics Data System (ADS)

    Owens, Jeremy D.; Nielsen, Sune G.; Horner, Tristan J.; Ostrander, Chadlin M.; Peterson, Larry C.

    2017-09-01

    Thallium (Tl) isotopes are a new and potentially powerful paleoredox proxy that may track bottom water oxygen conditions based on the global burial flux of manganese oxides. Thallium has a residence time of ∼20 thousand years, which is longer than the ocean mixing time, and it has been inferred that modern oxic seawater is conservative with respect to both concentration and isotopes. Marine sources of Tl have nearly identical isotopic values. Therefore, the Tl sinks, adsorption onto manganese oxides and low temperature oceanic crust alteration (the dominant seawater output), are the primary controls of the seawater isotopic composition. For relatively short-term, ∼million years, redox events it is reasonable to assume that the dominant mechanism that alters the Tl isotopic composition of seawater is associated with manganese oxide burial because large variability in low temperature ocean crust alteration is controlled by long-term, multi-million years, average ocean crust production rates. This study presents new Tl isotope data for an open ocean transect in the South Atlantic, and depth transects for two euxinic basins (anoxic and free sulfide in the water column), the Cariaco Basin and Black Sea. The Tl isotopic signature of open ocean seawater in the South Atlantic was found to be homogeneous with ε205Tl = -6.0 ± 0.3 (±2 SD, n = 41) while oxic waters from Cariaco and the Black Sea are -5.6 and -2.2, respectively. Combined with existing data from the Pacific and Arctic Oceans, our Atlantic data establish the conservatism of Tl isotopes in the global ocean. In contrast, partially- and predominantly-restricted basins reveal Tl isotope differences that vary between open-ocean (-6) and continental material (-2) ε205Tl, scaling with the degree of restriction. Regardless of the differences between basins, Tl is quantitatively removed from their euxinic waters below the chemocline. The burial of Tl in euxinic sediments is estimated to be an order of magnitude

  12. In-situ nano-crystal-to-crystal transformation synthesis of energetic materials based on three 5,5′-azotetrazolate Cr(III) salts

    PubMed Central

    Miao, Yu; Qiu, Yanxuan; Cai, Jiawei; Wang, Zizhou; Yu, Xinwei; Dong, Wen

    2016-01-01

    The in-situ nano-crystal-to-crystal transformation (SCCT) synthesis provides a powerful approach for tailoring controllable feature shapes and sizes of nano crystals. In this work, three nitrogen-rich energetic nano-crystals based on 5,5′-azotetrazolate(AZT2−) Cr(III) salts were synthesized by means of SCCT methodology. SEM and TEM analyses show that the energetic nano-crystals feature a composition- and structure-dependent together with size-dependent thermal stability. Moreover, nano-scale decomposition products can be obtained above 500 °C, providing a new method for preparing metallic oxide nano materials. PMID:27869221

  13. Control of arsenic mobilization in paddy soils by manganese and iron oxides.

    PubMed

    Xu, Xiaowei; Chen, Chuan; Wang, Peng; Kretzschmar, Ruben; Zhao, Fang-Jie

    2017-12-01

    Reductive mobilization of arsenic (As) in paddy soils under flooded conditions is an important reason for the relatively high accumulation of As in rice, posing a risk to food safety and human health. The extent of As mobilization varies widely among paddy soils, but the reasons are not well understood. In this study, we investigated As mobilization in six As-contaminated paddy soils (total As ranging from 73 to 122 mg kg -1 ) in flooded incubation and pot experiments. Arsenic speciation in the solution and solid phases were determined. The magnitude of As mobilization into the porewater varied by > 100 times among the six soils. Porewater As concentration correlated closely with the concentration of oxalate-extractable As, suggesting that As associated with amorphous iron (oxyhydr)oxides represents the potentially mobilizable pool of As under flooded conditions. Soil containing a high level of manganese oxides showed the lowest As mobilization, likely because Mn oxides retard As mobilization by slowing down the drop of redox potential upon soil flooding and maintaining a higher arsenate to arsenite ratio in the solid and solution phases. Additions of a synthetic Mn oxide (hausmannite) to two paddy soils increased arsenite oxidation, decreased As mobilization into the porewater and decreased As concentrations in rice grain and straw. Consistent with previous studies using simplified model systems or pure mineral phases, the present study shows that Mn oxides and amorphous Fe (oxyhydr)oxides are important factors controlling reductive As mobilization in As-contaminated paddy soils. In addition, this study also suggests a potential mitigation strategy using exogenous Mn oxides to decrease As uptake by rice in paddy soils containing low levels of indigenous Mn oxides, although further work is needed to verify its efficacy and possible secondary effects under field conditions. Copyright © 2017 Elsevier Ltd. All rights reserved.

  14. Targeted Therapy for Acute Autoimmune Myocarditis with Nano-Sized Liposomal FK506 in Rats.

    PubMed

    Okuda, Keiji; Fu, Hai Ying; Matsuzaki, Takashi; Araki, Ryo; Tsuchida, Shota; Thanikachalam, Punniyakoti V; Fukuta, Tatsuya; Asai, Tomohiro; Yamato, Masaki; Sanada, Shoji; Asanuma, Hiroshi; Asano, Yoshihiro; Asakura, Masanori; Hanawa, Haruo; Hao, Hiroyuki; Oku, Naoto; Takashima, Seiji; Kitakaze, Masafumi; Sakata, Yasushi; Minamino, Tetsuo

    2016-01-01

    Immunosuppressive agents are used for the treatment of immune-mediated myocarditis; however, the need to develop a more effective therapeutic approach remains. Nano-sized liposomes may accumulate in and selectively deliver drugs to an inflammatory lesion with enhanced vascular permeability. The aims of this study were to investigate the distribution of liposomal FK506, an immunosuppressive drug encapsulated within liposomes, and the drug's effects on cardiac function in a rat experimental autoimmune myocarditis (EAM) model. We prepared polyethylene glycol-modified liposomal FK506 (mean diameter: 109.5 ± 4.4 nm). We induced EAM by immunization with porcine myosin and assessed the tissue distribution of the nano-sized beads and liposomal FK506 in this model. After liposomal or free FK506 was administered on days 14 and 17 after immunization, the cytokine expression in the rat hearts along with the histological findings and hemodynamic parameters were determined on day 21. Ex vivo fluorescent imaging revealed that intravenously administered fluorescent-labeled nano-sized beads had accumulated in myocarditic but not normal hearts on day 14 after immunization and thereafter. Compared to the administration of free FK506, FK506 levels were increased in both the plasma and hearts of EAM rats when liposomal FK506 was administered. The administration of liposomal FK506 markedly suppressed the expression of cytokines, such as interferon-γ and tumor necrosis factor-α, and reduced inflammation and fibrosis in the myocardium on day 21 compared to free FK506. The administration of liposomal FK506 also markedly ameliorated cardiac dysfunction on day 21 compared to free FK506. Nano-sized liposomes may be a promising drug delivery system for targeting myocarditic hearts with cardioprotective agents.

  15. 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

  16. Effect of Nano-Al2O3 on the Toxicity and Oxidative Stress of Copper towards Scenedesmus obliquus

    PubMed Central

    Li, Xiaomin; Zhou, Suyang; Fan, Wenhong

    2016-01-01

    Nano-Al2O3 has been widely used in various industries; unfortunately, it can be released into the aquatic environment. Although nano-Al2O3 is believed to be of low toxicity, it can interact with other pollutants in water, such as heavy metals. However, the interactions between nano-Al2O3 and heavy metals as well as the effect of nano-Al2O3 on the toxicity of the metals have been rarely investigated. The current study investigated copper toxicity in the presence of nano-Al2O3 towards Scenedesmus obliquus. Superoxide dismutase activity and concentration of glutathione and malondialdehyde in cells were determined in order to quantify oxidative stress in this study. Results showed that the presence of nano-Al2O3 reduced the toxicity of Cu towards S. obliquus. The existence of nano-Al2O3 decreased the growth inhibition of S. obliquus. The accumulation of copper and the level of oxidative stress in algae were reduced in the presence of nano-Al2O3. Furthermore, lower copper accumulation was the main factor that mitigated copper toxicity with the addition of nano-Al2O3. The decreased copper uptake could be attributed to the adsorption of copper onto nanoparticles and the subsequent decrease of available copper in water. PMID:27294942

  17. Temperature-Driven Structural and Morphological Evolution of Zinc Oxide Nano-Coalesced Microstructures and Its Defect-Related Photoluminescence Properties

    PubMed Central

    Lim, Karkeng; Abdul Hamid, Muhammad Azmi; Shamsudin, Roslinda; Al-Hardan, N.H.; Mansor, Ishak; Chiu, Weesiong

    2016-01-01

    In this paper, we address the synthesis of nano-coalesced microstructured zinc oxide thin films via a simple thermal evaporation process. The role of synthesis temperature on the structural, morphological, and optical properties of the prepared zinc oxide samples was deeply investigated. The obtained photoluminescence and X-ray photoelectron spectroscopy outcomes will be used to discuss the surface structure defects of the prepared samples. The results indicated that the prepared samples are polycrystalline in nature, and the sample prepared at 700 °C revealed a tremendously c-axis oriented zinc oxide. The temperature-driven morphological evolution of the zinc oxide nano-coalesced microstructures was perceived, resulting in transformation of quasi-mountain chain-like to pyramidal textured zinc oxide with increasing the synthesis temperature. The results also impart that the sample prepared at 500 °C shows a higher percentage of the zinc interstitial and oxygen vacancies. Furthermore, the intensity of the photoluminescence emission in the ultraviolet region was enhanced as the heating temperature increased from 500 °C to 700 °C. Lastly, the growth mechanism of the zinc oxide nano-coalesced microstructures is discussed according to the reaction conditions. PMID:28773425

  18. Critical oxide cluster size on Si(111)

    NASA Astrophysics Data System (ADS)

    Shklyaev, A. A.; Aono, M.; Suzuki, T.

    1999-03-01

    The initial stage of oxide growth and subsequent oxide decomposition on Si(111)-7×7 at temperatures between 350 and 720°C are studied with the optical second harmonic generation for O 2 pressures ( Pox) between 5×10 -9 and 4×10 -6 Torr. The obtained pressure dependencies of the initial oxide growth rate ( Rgr) and the subsequent oxide decomposition rate are associated with the cluster-forming nature of the oxidation process. For the model of oxide cluster nucleation and growth, a scaling relationship is derived among the critical oxide cluster size, i, and the experimentally measurable values of Rgr and Pox. The critical oxide cluster size, i, thus obtained from the kinetic data increases with temperature. This correlates with an increase of desorption channels and their rates in that the competition between growth and decomposition requires more stable oxide clusters, i.e. clusters with a larger critical size, for oxide to grow at higher temperatures. The increase of i with decreasing Pox is related with a decrease of Rgr: a decreased Rgr requires critical clusters with a longer lifetime, i.e. clusters with a larger size.

  19. Development of Surface Complexation Models of Cr(VI) Adsorption on Soils, Sediments and Model Mixtures of Kaolinite, Montmorillonite, γ-Alumina, Hydrous Manganese and Ferric Oxides and Goethite

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

    Koretsky, Carla

    Hexavalent chromium is a highly toxic contaminant that has been introduced into aquifers and shallow sediments and soils via many anthropogenic activities. Hexavalent chromium contamination is a problem or potential problem in the shallow subsurface at several DOE sites, including Hanford, Idaho National Laboratory, Los Alamos National Laboratory and the Oak Ridge Reservation (DOE, 2008). To accurately quantify the fate and transport of hexavalent chromium at DOE and other contaminated sites, robust geochemical models, capable of correctly predicting changes in chromium chemical form resulting from chemical reactions occurring in subsurface environments are needed. One important chemical reaction that may greatlymore » impact the bioavailability and mobility of hexavalent chromium in the subsurface is chemical binding to the surfaces of particulates, termed adsorption or surface complexation. Quantitative thermodynamic surface complexation models have been derived that can correctly calculate hexavalent chromium adsorption on well-characterized materials over ranges in subsurface conditions, such pH and salinity. However, models have not yet been developed for hexavalent chromium adsorption on many important constituents of natural soils and sediments, such as clay minerals. Furthermore, most of the existing thermodynamic models have been developed for relatively simple, single solid systems and have rarely been tested for the complex mixtures of solids present in real sediments and soils. In this study, the adsorption of hexavalent chromium was measured as a function of pH (3-10), salinity (0.001 to 0.1 M NaNO3), and partial pressure of carbon dioxide(0-5%) on a suite of naturally-occurring solids including goethite (FeOOH), hydrous manganese oxide (MnOOH), hydrous ferric oxide (Fe(OH)3), γ-alumina (Al2O3), kaolinite (Al2Si2O5(OH)4), and montmorillonite (Na3(Al, Mg)2Si4O10(OH)2-nH2O). The results show that all of these materials can bind substantial quantities

  20. The use of nano-sized eggshell powder for calcium fortification of cow?s and buffalo?s milk yogurts.

    PubMed

    El-Shibiny, Safinaze; El-Gawad, Mona Abd El-Kader Mohamed Abd; Assem, Fayza Mohamed; El-Sayed, Samah Mosbah

    2018-01-01

    Calcium is an essential element for the growth, activity, and maintenance of the human body. Eggshells are a waste product which has received growing interest as a cheap and effective source of dietary calcium. Yogurt is a food which can be fortified with functional additives, including calcium. The aim of this study was to produce yogurt with a high calcium content by fortification with nano-sized eggshell powder (nano-ESP). Nano-sized ESP was prepared from pre-boiled and dried eggshell, using a ball mill. Yogurt was prepared from cow’s milk supplemented with 3% skimmed milk powder, and from buffalo’s milk fortified with 0.1, 0.2 and 0.3% and 0.1, 0.3 and 0.5% nano-ESP respectively. Electron microscopic transmission showed that the powder consisted of nano-sized crystalline struc- tures (~10 nm). Laser scattering showed that particles followed a normal distribution pattern with z-average of 590.5 nm, and had negative zeta-potential of –9.33 ±4.2 mV. Results regarding changes in yogurt composi- tion, acid development, calcium distribution, biochemical changes, textural parameters and sensory attributes have been presented and discussed. The addition of up to 0.3% nano-ESP made cow and buffalo high-calcium yogurts with an acceptable composition and quality. High-calcium yogurt may offer better health benefits, such as combating osteoporosis.

  1. Mesoporous metal oxides and processes for preparation thereof

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

    Suib, Steven L.; Poyraz, Altug Suleyman

    A process for preparing a mesoporous metal oxide, i.e., transition metal oxide. Lanthanide metal oxide, a post-transition metal oxide and metalloid oxide. The process comprises providing an acidic mixture comprising a metal precursor, an interface modifier, a hydrotropic ion precursor, and a surfactant; and heating the acidic mixture at a temperature and for a period of time sufficient to form the mesoporous metal oxide. A mesoporous metal oxide prepared by the above process. A method of controlling nano-sized wall crystallinity and mesoporosity in mesoporous metal oxides. The method comprises providing an acidic mixture comprising a metal precursor, an interface modifier,more » a hydrotropic ion precursor, and a surfactant; and heating the acidic mixture at a temperature and for a period of time sufficient to control nano-sized wall crystallinity and mesoporosity in the mesoporous metal oxides. Mesoporous metal oxides and a method of tuning structural properties of mesoporous metal oxides.« less

  2. Nano-sized Al2O3 reduces acute toxic effects of thiacloprid on the non-biting midge Chironomus riparius

    PubMed Central

    Wicht, Anna-J.; Guluzada, Leyla; Luo, Leilei; Jäger, Leonie; Crone, Barbara; Karst, Uwe; Triebskorn, Rita; Liang, Yucang; Anwander, Reiner; Haderlein, Stefan B.; Huhn, Carolin; Köhler, Heinz-R.

    2017-01-01

    This study focuses on interactions between nanoparticles and a pesticide. The aim was to investigate how nano-sized aluminum oxide (410 nm) can alter the toxic effects of thiacloprid, even if no sorption between particles and the insecticide takes place. Thus, our study investigated a rather unexplored interaction. We conducted our research with larvae of Chironomus riparius and used thiacloprid as test substance as its toxicity to C. riparius is well described. The used nano-Al2O3 particles where chosen due to their suitable properties. For testing the acute effects of the interaction, we exposed larvae to thiacloprid (0.5, 1.0, 2.0, and 5.0 μg/L) and nano-Al2O3 (300 and 1000 mg/L), either solely or in binary mixtures. While thiacloprid resulted in elevated mortality, nano-Al2O3 solely did not exert any effects. Moreover, we observed an aggregation of nano-Al2O3 within the lumen of the intestinal tract of the larvae. Further results showed a significantly reduced mortality of fourth instar larvae when they were exposed to mixtures of nanoparticles and the pesticide, compared to thiacloprid alone. With increasing nano-Al2O3 concentration, this effect became gradually stronger. Additionally, chemical analyses of internal thiacloprid concentrations implicate reduced uptake of thiacloprid in animals exposed to mixtures. However, as larvae exposed to thiacloprid concentrations > 0.5 μg/L showed severe convulsions, independent of the presence or concentration of nano-Al2O3, we assume that nano-Al2O3 leads to a delay of mortality and does not entirely prevent it. As sorption measurements on pristine or defecated nano-Al2O3 did not reveal any sorptive interaction with thiacloprid, we can exclude sorption-based reduction of thiacloprid bioavailability as a mechanism behind our results. Even though we used test substances which might not co-occur in the environment in the tested concentrations, our study gives evidence for an interaction besides adsorption, which is

  3. Tribological Behavior of Nano-Onions in Krytox 143AB Evaluated

    NASA Technical Reports Server (NTRS)

    Street, Kenneth W.; VanderWal, Randy L.; Marchetti, Mario; Tomasek, Aaron J.

    2005-01-01

    Nanoparticles have been developed over the past 10 years and have found several applications. This work presents the use of carbon nano-onions as a potential oil additive for aerospace applications. Researchers at the NASA Glenn Research Center tested lubricant lifetimes in ambient air and ultrahigh vacuum and characterized the breakdown products of the friction and wear. These carbon nanoparticles can provide adequate lubrication very similar to that of graphitic material when run in air. Soot represents one of the very first nanostructured materials, although it has rarely been considered as such. Changes in the carbon nanostructure, resulting in increased graphitic layer plane length, correlate with reactivity loss. Upon heating spherically shaped nanometer-sized carbon black in the absence of oxidant, graphene sheets form, and the initial soot particle templates the growth of a graphitic particle into what is best described as a sphere with many flat sides having a hollow interior. Because there are no edge sites, these polygonal graphitic particles, or nano-onions, are relatively resistant to oxidation. Graphite is used as a solid lubricant because of its stability at moderately high temperatures. However, the temperature at which graphite oxidizes rapidly is strongly influenced by surface area. With the size of particles typically employed in lubrication, a great amount of thermal stability is lost because of size reduction either during preparation or during lubrication of contacting parts. Therefore, we have undertaken a study of the lubricating ability of graphitic nano-onions (ref. 1).

  4. [Catalytic degradation of PCB77 by microwave-induced nano-particle metal oxides in diatomite].

    PubMed

    Huang, Guan-yi; Zhao, Ling; Dong, Yuan-hua

    2009-08-15

    The degradation of PCB77 in diatomite by microwave-induced catalytic oxidation was studied in a sealed vial, including four effects such as microwave (MV) radiating time, addition of different nano-particle metal oxides, concentration and type of acids and dosage of MnO2. The results indicated that PCB77 could be removed significantly by microwave-induced catalytic oxidation. Compared to control reactor (without MV radiation), the removal rate of PCB77 increased by twice after 1 min. In addition, the removal rate of PCB77 under MV radiation was gradually increased with time of radiation and then reached equilibrium after 10 min. The removal rates are about 50% and 20% by addition of H2SO4 and ultrapure water respectively. No significant removal was observed by addition of NaOH and without aqueous media. Moreover, catalytic degradation of PCB77 by microwave-induced nano-particle MnO2 had best removal rate was up to 90% after 1 min, in contrast with addition of nano-particle Fe2O3, CuO and Al2O3. The removal rate raised from 37.0% to 98.5% rapidly with the concentration of H2SO4 ranged from 1 mol/L to 8 mol/L, and H2SO4 mainly played a role of acidification but not oxidation. The addition of 0.01, 0.03 and 0.05 g MnO2 showed the similar result.

  5. Effects of separate and concurrent supplementation of Nano-sized clinoptilolite and Nigella sativa on oxidative stress, anti-oxidative parameters and body weight in rats with type 2 diabetes.

    PubMed

    Omidi, Hossein; Khorram, Sirus; Mesgari, Mehran; Asghari-Jafarabadi, Mohammad; Tarighat-Esfanjani, Ali

    2017-12-01

    The objective of this study was to investigate the effects of separate and concurrent supplementation of natural nano-sized clinoptilolite (NCLN) and Nigella sativa (NS) on oxidative stress (OS), anti-oxidative parameters and body weight (BW) in high-fat-diet (HFD)/streptozotocin (STZ)-induced diabetic rats. In this experimental study, 42 male Wistar rats were divided into diabetic (n=36) and non-diabetic (n=6) groups. The diabetic group (DG) was fed with a HFD for one month, then injected with intra-peritoneal single dose STZ (35 mg/kg BW). The DG was divided into 4 subgroups: [1] control (DC), [2] NS 1%/food, [3] NCLN 2%/food, [4] NS 1%/food + NCLN 2%/food. At the end of the 7th week, malondialdehyde (MDA), superoxide dismutase (SOD), glutathione peroxidase (GPX) levels and total antioxidant capacity (TAC) were measured. The MDA level was decreased in the NCLN (p = 0.011) and NCLN+NS (p = 0.007) groups compared to the DC group. The GPX level increased in the NS and NCLN groups compared to the DC group (p = 0.014 and p = 0.034). In addition, the level of TAC demonstrated increase in the untreated DG and NS groups, as compared to the normal control (NC) group (p DC  = 0.031 and p NS  = 0.024). Moreover, in the NS+NCLN group, the level of SOD decreased in comparison to the NS and NCLN groups (p < 0.01). At the end of the 7th week, BW decreased in the diabetic subgroups in comparison to the NC group. Treatment with NS and/or NS+NCLN insignificantly prevented severe weight loss in the fifth week of the treatment. According to results, separate supplementation of NS and NCLN was more beneficent on anti-oxidative parameters than concurrent supplementation of NS and NCLN. Copyright © 2017 Elsevier Masson SAS. All rights reserved.

  6. An investigation of manganese based electrode materials for use in lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Sengupta, Surajit

    Lithium-based batteries are potential candidates to provide maximum volumetric and gravimetric energy density. One of the most attractive candidates as a cathode material for secondary lithium ion battery systems is the spinel LiMn 2O4 because it is environmentally friendly, less expensive and is capable of providing high energy density as compared to other cathode materials that are currently available. One problem associated with the spinel structure is capacity fading during multiple cycles of charge and discharge operations. This behaviour is due in part to the structural distortion during deep charge and discharge where nearly 100% of the lithium is extracted and inserted inside the spinel structure. Capacity fading can also be caused by dissolution of manganese ions in the electrolyte phase. A solution based method has been adapted for the synthesis of lithium manganese oxide, and chromium and cobalt doped mixed oxide materials using polyvinyl alcohol (PVA) as a chelating agent. It has been found from TGA/DSC analysis that at around 220°C the synthesis reaction is completed. The precursor powders obtained were annealed at different temperatures and times in the range of 250°C to 600°C and from 2 to 8 hours respectively to obtain pure spinel oxides. From X-ray analysis it has been observed that the crystallite size can be controlled in the range of approximately 6 nm to 32 nm depending on the annealing time and the temperature. The morphology of the synthesized materials consisted of submicron sized particles agglomerated with micropores inside the network structure. To observe the effect of physical properties on battery performance cyclic chronopotentiometric evaluation was conducted. It has been found with these synthesized materials that there is an increase in the 1st discharge capacity with an increase in the annealing time and the temperature at both 1C and C/5 rates. This increase is more significant when the annealing temperature is 600°C as

  7. Enzymatic biomarkers can portray nanoCuO-induced oxidative and neuronal stress in freshwater shredders.

    PubMed

    Pradhan, Arunava; Silva, Carla O; Silva, Carlos; Pascoal, Cláudia; Cássio, Fernanda

    2016-11-01

    Commercial applications of nanometal oxides have increased concern about their release into natural waters and consequent risks to aquatic biota and the processes they drive. In forest streams, the invertebrate shredder Allogamus ligonifer plays a key role in detritus food webs by transferring carbon and energy from plant litter to higher trophic levels. We assessed the response profiles of oxidative and neuronal stress enzymatic biomarkers in A. ligonifer after 96h exposure to nanoCuO at concentration ranges nanoCuO-induced stress, Cu 2+ released from nanoCuO was quantified and the enzymatic responses to Cu 2+ exposure at similar effective concentrations were compared. The highest activities of superoxide dismutase (SOD), glutathione peroxidase (GPx) and glutathione reductase (GR) were observed at concentrations oxidative stress at low concentrations (nanoCuO, thereby contributing to the survival of A. ligonifer. At concentrations between LC 10 and LC 30 , effects of nanoparticulate or released ionic copper on enzyme activities were concentration-dependent, and led to oxidative stress and even to animal death. The activity of acetylcholinesterase (AChE) was strongly inhibited even at concentrations

  8. Forging of metallic nano-objects for the fabrication of submicron-size components

    NASA Astrophysics Data System (ADS)

    Rösler, J.; Mukherji, D.; Schock, K.; Kleindiek, S.

    2007-03-01

    In recent years, nanoscale fabrication has developed considerably, but the fabrication of free-standing nanosize components is still a great challenge. The fabrication of metallic nanocomponents utilizing three basic steps is demonstrated here. First, metallic alloys are used as factories to produce a metallic raw stock of nano-objects/nanoparticles in large numbers. These objects are then isolated from the powder containing thousands of such objects inside a scanning electron microscope using manipulators, and placed on a micro-anvil or a die. Finally, the shape of the individual nano-object is changed by nanoforging using a microhammer. In this way free-standing, high-strength, metallic nano-objects may be shaped into components with dimensions in the 100 nm range. By assembling such nanocomponents, high-performance microsystems can be fabricated, which are truly in the micrometre scale (the size ratio of a system to its component is typically 10:1).

  9. A facile method to synthesize boron-doped Ni/Fe alloy nano-chains as electrocatalyst for water oxidation

    NASA Astrophysics Data System (ADS)

    Yang, Yisu; Zhuang, Linzhou; Lin, Rijia; Li, Mengran; Xu, Xiaoyong; Rufford, Thomas E.; Zhu, Zhonghua

    2017-05-01

    We report a novel magnetic field assisted chemical reduction method for the synthesis of boron-doped Ni/Fe nano-chains as promising catalysts for the oxygen evolution reaction (OER). The boron-doped Ni/Fe nano-chains were synthesised in a one step process at room temperature using NaBH4 as a reducing agent. The addition of boron reduced the magnetic moment of the intermediate synthesis products and produced nano-chains with a high specific surface area of 73.4 m2 g-1. The boron-doped Ni/Fe nano-chains exhibited catalytic performance superior to state-of-the-art Ba0.5Sr0.5Co0.8Fe0.2O3-δ perovskite and RuO2 noble metal oxide catalysts. The mass normalized activity of the boron-doped Ni/Fe nano-chains measured at an overpotential of 0.35 V was 64.0 A g-1, with a Tafel slope of only 40 mV dec-1. The excellent performance of the boron-doped Ni/Fe nano-chains can be attributed to the uniform elemental distribution and highly amorphous structure of the B-doped nano-chains. These results provide new insights into the effect of doping transition-metal based OER catalysts with non-metallic elements. The study demonstrates a facile approach to prepare transition metal nano-chains using magnetic field assisted chemical reduction method as cheap and highly active catalysts for electrochemical water oxidation.

  10. Effects of exposure to nano and bulk sized TiO2 and CuO in Lemna minor.

    PubMed

    Dolenc Koce, Jasna

    2017-10-01

    Nanoparticles of TiO 2 and CuO are among most commonly used nanoparticles, and elevated concentrations of them are expected to be found in all environments, including aquatic. A standard growth inhibition test ISO/CD 20079 was used to determine the toxicity of nano sized and larger micro sized (bulk) particles in the concentrations of 0.1, 1, 10, 100 and 1000 μM CuO and TiO 2 on common duckweed (Lemna minor L.). Both nano and bulk CuO particles caused changes in the structure and function of treated plants. The number of fronds and colonies decreased by as much as 78%, the length of roots and fronds decreased by 99% and 14%, respectively. Furthermore, photochemical efficiency was reduced by up to 35%, and the activities of antioxidative enzymes guaiacol peroxidase, ascorbate peroxidase and glutathione reductase increased by more than 240%. The altered physiological state of the CuO exposed plants was also reflected in the elevated occurrence of necrosis and bleaching in the duckweed colonies. Nano sized particles of CuO proved more phytotoxic than bulk particles, and the effects of both studied CuO sizes were concentration dependent. On the other hand, both bulk and nano sized particles of TiO 2 caused no severe phytotoxic effects, there was no concentration dependence and they could be considered as non-harmful to common duckweed. Copyright © 2017 Elsevier Masson SAS. All rights reserved.

  11. Superior model for fault tolerance computation in designing nano-sized circuit systems

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

    Singh, N. S. S., E-mail: narinderjit@petronas.com.my; Muthuvalu, M. S., E-mail: msmuthuvalu@gmail.com; Asirvadam, V. S., E-mail: vijanth-sagayan@petronas.com.my

    2014-10-24

    As CMOS technology scales nano-metrically, reliability turns out to be a decisive subject in the design methodology of nano-sized circuit systems. As a result, several computational approaches have been developed to compute and evaluate reliability of desired nano-electronic circuits. The process of computing reliability becomes very troublesome and time consuming as the computational complexity build ups with the desired circuit size. Therefore, being able to measure reliability instantly and superiorly is fast becoming necessary in designing modern logic integrated circuits. For this purpose, the paper firstly looks into the development of an automated reliability evaluation tool based on the generalizationmore » of Probabilistic Gate Model (PGM) and Boolean Difference-based Error Calculator (BDEC) models. The Matlab-based tool allows users to significantly speed-up the task of reliability analysis for very large number of nano-electronic circuits. Secondly, by using the developed automated tool, the paper explores into a comparative study involving reliability computation and evaluation by PGM and, BDEC models for different implementations of same functionality circuits. Based on the reliability analysis, BDEC gives exact and transparent reliability measures, but as the complexity of the same functionality circuits with respect to gate error increases, reliability measure by BDEC tends to be lower than the reliability measure by PGM. The lesser reliability measure by BDEC is well explained in this paper using distribution of different signal input patterns overtime for same functionality circuits. Simulation results conclude that the reliability measure by BDEC depends not only on faulty gates but it also depends on circuit topology, probability of input signals being one or zero and also probability of error on signal lines.« less

  12. 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

  13. 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

  14. Nasal aerodynamics protects brain and lung from inhaled dust in subterranean diggers, Ellobius talpinus

    PubMed Central

    Moshkin, M. P.; Petrovski, D. V.; Akulov, A. E.; Romashchenko, A. V.; Gerlinskaya, L. A.; Ganimedov, V. L.; Muchnaya, M. I.; Sadovsky, A. S.; Koptyug, I. V.; Savelov, A. A.; Troitsky, S. Yu; Moshkn, Y. M.; Bukhtiyarov, V. I.; Kolchanov, N. A.; Sagdeev, R. Z.; Fomin, V. M.

    2014-01-01

    Inhalation of air-dispersed sub-micrometre and nano-sized particles presents a risk factor for animal and human health. Here, we show that nasal aerodynamics plays a pivotal role in the protection of the subterranean mole vole Ellobius talpinus from an increased exposure to nano-aerosols. Quantitative simulation of particle flow has shown that their deposition on the total surface of the nasal cavity is higher in the mole vole than in a terrestrial rodent Mus musculus (mouse), but lower on the olfactory epithelium. In agreement with simulation results, we found a reduced accumulation of manganese in olfactory bulbs of mole voles in comparison with mice after the inhalation of nano-sized MnCl2 aerosols. We ruled out the possibility that this reduction is owing to a lower transportation from epithelium to brain in the mole vole as intranasal instillations of MnCl2 solution and hydrated nanoparticles of manganese oxide MnO · (H2O)x revealed similar uptake rates for both species. Together, we conclude that nasal geometry contributes to the protection of brain and lung from accumulation of air-dispersed particles in mole voles. PMID:25143031

  15. Developing Sensitive and Selective Nanosensors: A Single Molecule - Multiple Excitation Source Approach. Altairnano Lithium Ion Nano-scaled Titanate Oxide Cell and Module Abuse Testing

    DTIC Science & Technology

    2012-03-13

    Source Approach Part II. Altairnano Lithium Ion Nano-scaled Titanate Oxide Cell and Module Abuse Testing 14. ABSTRACT 16. SECURITY CLASSIFICATION OF...Lithium Ion Nano-scaled Titanate Oxide Cell and Module Abuse Testing Report Title ABSTRACT This final report for Contract W911NF-09-C-0135 transmits the...prototype development. The second (Part II.) is "Altairnano Lithium Ion Nano-scaled Titanate Oxide Cell and Module Abuse Test Report". The

  16. Bio-inspired surfactant assisted nano-catalyst impregnation of Solid-Oxide Fuel Cell (SOFC) electrodes

    DOE PAGES

    Ozmen, Ozcan; Zondlo, John W.; Lee, Shiwoo; ...

    2015-11-02

    A bio-inspired surfactant was utilized to assist in the efficient impregnation of a nano-CeO₂ catalyst throughout both porous Solid Oxide Fuel Cells (SOFC’s) electrodes simultaneously. The process included the initial modification of electrode pore walls with a polydopamine film. The cell was then submersed into a cerium salt solution. The amount of nano-CeO₂ deposited per impregnation step increased by 3.5 times by utilizing this two-step protocol in comparison to a conventional drip impregnation method. The impregnated cells exhibited a 20% higher power density than a baseline cell without the nano-catalyst at 750°C (using humid H₂ fuel).

  17. 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.

  18. The nature of nano-sized precipitates in ferritic/martensitic steel P92 produced by thermomechanical treatment

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

    Shen, Yinzhong, E-mail: shenyz@sjtu.edu.cn

    Thermomechanical treatment (TMT) can effectively improve the mechanical properties of high-Cr ferritic/martensitic (F/M) steels, which has been mainly attributed to a dense dispersion of nano-sized precipitates. Precipitate phases in high-Cr F/M steels produced by TMT require further investigations. Precipitates in commercial F/M steel P92 produced by a TMT process, warm-rolled at 650 °C plus tempered at 650 °C for 1 h, were investigated by transmission electron microscopy. Nano-sized precipitates with a high number density in the steel after the TMT were found to be Cr-rich M{sub 2}(C,N) carbonitride, rather than MX or M{sub 23}C{sub 6} phase. The M{sub 2}(C,N) carbonitridemore » has a hexagonal lattice with the lattice parameters about a/c = 0.299/0.463 nm. These M{sub 2}(C,N) carbonitrides with a typical composition of (Cr{sub 0.85}V{sub 0.06}Fe{sub 0.06}Mo{sub 0.03}){sub 2}(C,N) have an average diameter smaller than 30 nm, and mainly distribute on dislocations and at the boundaries of equiaxed ferrite grains in the TMT steel. The TMT process inhibits the precipitation of M{sub 23}C{sub 6} and M{sub 5}C{sub 2} phases. Enhanced creep properties of the P92 steel after the TMT, as reported previously, were considered to be mainly attributed to plenty of nano-sized Cr-rich M{sub 2}(C,N) carbonitrides produced by the TMT rather than to MX and M{sub 23}C{sub 6} precipitates. - Graphical abstract: TEM micrographs of precipitates on extraction carbon replicas prepared from ferritic/martensitic (F/M) steel P92. (a) After conventional heat treatment, normalized at 1050 °C for 30 min plus tempered at 765 °C for 1 h. (b) After a thermomechanical treatment (TMT), warm-rolled at 650 °C plus tempered at 650 °C for 1 h. Nano-sized precipitates with a high number density in the steel produced by the TMT were found to be Cr-rich M{sub 2}(C,N) carbonitride, rather than MX or M{sub 23}C{sub 6} phase. The TMT process inhibits the precipitation of M{sub 23}C{sub 6} and M

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

    PubMed

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

    2016-04-15

    In the present work, a reduced graphene oxide (RGO) supported manganese tetraphenylporphyrin (Mn-TPP) nanocomposite was electrochemically synthesized and used for the highly selective and sensitive detection of dopamine (DA). The nuclear magnetic resonance, scanning electron microscopy and elemental analysis were confirmed the successful formation of RGO/Mn-TPP nanocomposite. The prepared RGO/Mn-TPP nanocomposite modified electrode exhibited an enhanced electrochemical response to DA with less oxidation potential and enhanced response current. The electrochemical studies revealed that the oxidation of the DA at the composite electrode is a surface controlled process. The cyclic voltammetry, differential pulse voltammetry and amperometry methods were enable to detect DA. The working linear range of the electrode was observed from 0.3 to 188.8 μM, limit of detection was 8 nM and the sensitivity was 2.606 μA μM(-1) cm(-2). Here, the positively charged DA and negatively charged porphyrin modified RGO can accelerate the electrocatalysis of DA via electrostatic attraction, while the negatively charged ascorbic acid (AA) repulsed by the negatively charged electrode surface which supported for good selectivity. The good recovery results obtained for the determination of DA present in DA injection samples and human pathological sample further revealed the good practicality of RGO/Mn-TPP nanocomposite film modified electrode. Copyright © 2016 Elsevier Inc. All rights reserved.

  20. 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.

  1. Room-temperature solution-processed and metal oxide-free nano-composite for the flexible transparent bottom electrode of perovskite solar cells

    NASA Astrophysics Data System (ADS)

    Lu, Haifei; Sun, Jingsong; Zhang, Hong; Lu, Shunmian; Choy, Wallace C. H.

    2016-03-01

    The exploration of low-temperature and solution-processed charge transporting and collecting layers can promote the development of low-cost and large-scale perovskite solar cells (PVSCs) through an all solution process. Here, we propose a room-temperature solution-processed and metal oxide-free nano-composite composed of a silver nano-network and graphene oxide (GO) flawless film for the transparent bottom electrode of a PVSC. Our experimental results show that the amount of GO flakes play a critical role in forming the flawless anti-corrosive barrier in the silver nano-network through a self-assembly approach under ambient atmosphere, which can effectively prevent the penetration of liquid or gaseous halides and their corrosion against the silver nano-network underneath. Importantly, we simultaneously achieve good work function alignment and surface wetting properties for a practical bottom electrode by controlling the degree of reduction of GO flakes. Finally, flexible PVSC adopting the room-temperature and solution-processed nano-composite as the flexible transparent bottom electrode has been demonstrated on a polyethylene terephthalate (PET) substrate. As a consequence, the demonstration of our room-temperature solution-processed and metal oxide-free flexible transparent bottom electrode will contribute to the emerging large-area flexible PVSC technologies.The exploration of low-temperature and solution-processed charge transporting and collecting layers can promote the development of low-cost and large-scale perovskite solar cells (PVSCs) through an all solution process. Here, we propose a room-temperature solution-processed and metal oxide-free nano-composite composed of a silver nano-network and graphene oxide (GO) flawless film for the transparent bottom electrode of a PVSC. Our experimental results show that the amount of GO flakes play a critical role in forming the flawless anti-corrosive barrier in the silver nano-network through a self

  2. 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

  3. Nano- and Micro-Scale Oxidative Patterning of Titanium Implant Surfaces for Improved Surface Wettability.

    PubMed

    Kim, In-hye; Son, Jun Sik; Choi, Seok Hwa; Kim, Kyo-han; Kwon, Tae-yub

    2016-02-01

    A simple and scalable surface modification treatment is demonstrated, in which nano- and microscale features are introduced into the surface of titanium (Ti) substrates by means of a novel and eco-friendly oxidative aqueous solution composed of hydrogen peroxide (H202) and sodium bicarbonate (NaHCO3). By immersing mirror-polished Ti discs in an aqueous mixture of 30 wt% H2O2/5 wt% NaHCO3 at 23 +/- 3 degrees C for 4 h, it was confirmed that this mixture is capable of generating microscale topographies on Ti surfaces. It also simultaneously formed nanochannels that were regularly arranged in a comb-like pattern on the Ti surface, thus forming a hierarchical surface structure. Further, these nano/micro-textured Ti surfaces showed great surface roughness and excellent wettability when compared with control Ti surfaces. This study demonstrates that a H2O2/NaHCO3 mixture can be effectively utilized to create reproducible nano/microscale topographies on Ti implant surfaces, thus providing an economical new oxidative solution that may be used effectively and safely as a Ti surface modification treatment.

  4. Metals, Oxidative Stress and Neurodegeneration: A focus on Iron, Manganese and Mercury

    PubMed Central

    Farina, Marcelo; Avila, Daiana Silva; da Rocha, João Batista Teixeira

    2013-01-01

    Essential metals are crucial for the maintenance of cell homeostasis. Among the 23 elements that have known physiological functions in humans, 12 are metals, including iron (Fe) and manganese (Mn). Nevertheless, excessive exposure to these metals may lead to pathological conditions, including neurodegeneration. Similarly, exposure to metals that do not have known biological functions, such as mercury (Hg), also present great health concerns. This reviews focuses on the neurodegenerative mechanisms and effects of Fe, Mn and Hg. Oxidative stress (OS), particularly in mitochondria, is a common feature of Fe, Mn and Hg toxicity. However, the primary molecular targets triggering OS are distinct. Free cationic iron is a potent pro-oxidant and can initiate a set of reactions that form extremely reactive products, such as OH•. Mn can oxidize dopamine (DA), generating reactive species and also affect mitochondrial function, leading to accumulation of metabolites and culminating with OS. Cationic Hg forms have strong affinity for nucleophiles, such as –SH and –SeH. Therefore, they target critical thiol- and selenol-molecules with antioxidant properties. Finally, we address the main sources of exposure to these metals, their transport mechanisms into the brain, and therapeutic modalities to mitigate their neurotoxic effects. PMID:23266600

  5. Strongly coupled inorganic-nano-carbon hybrid materials for energy storage.

    PubMed

    Wang, Hailiang; Dai, Hongjie

    2013-04-07

    The global shift of energy production from fossil fuels to renewable energy sources requires more efficient and reliable electrochemical energy storage devices. In particular, the development of electric or hydrogen powered vehicles calls for much-higher-performance batteries, supercapacitors and fuel cells than are currently available. In this review, we present an approach to synthesize electrochemical energy storage materials to form strongly coupled hybrids (SC-hybrids) of inorganic nanomaterials and novel graphitic nano-carbon materials such as carbon nanotubes and graphene, through nucleation and growth of nanoparticles at the functional groups of oxidized graphitic nano-carbon. We show that the inorganic-nano-carbon hybrid materials represent a new approach to synthesize electrode materials with higher electrochemical performance than traditional counterparts made by simple physical mixtures of electrochemically active inorganic particles and conducting carbon materials. The inorganic-nano-carbon hybrid materials are novel due to possible chemical bonding between inorganic nanoparticles and oxidized carbon, affording enhanced charge transport and increased rate capability of electrochemical materials without sacrificing specific capacity. Nano-carbon with various degrees of oxidation provides a novel substrate for nanoparticle nucleation and growth. The interactions between inorganic precursors and oxidized-carbon substrates provide a degree of control over the morphology, size and structure of the resulting inorganic nanoparticles. This paper reviews the recent development of inorganic-nano-carbon hybrid materials for electrochemical energy storage and conversion, including the preparation and functionalization of graphene sheets and carbon nanotubes to impart oxygen containing groups and defects, and methods of synthesis of nanoparticles of various morphologies on oxidized graphene and carbon nanotubes. We then review the applications of the SC

  6. 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

  7. To postpone the precipitation of manganese oxides in the degradation of tetrachloroethylene by controlling the permanganate concentration.

    PubMed

    Yang, Weiwei; Qiu, Zhaofu; Zhao, Zhexuan; Lu, Shuguang; Sui, Qian; Gu, Xiaogang

    2017-01-01

    Controlled-release permanganate (CRP) is a relatively new technology used to treat contaminated groundwater. This study tested the encapsulation of permanganate using stearic acid to realize controlled-release properties. Batch experiments were conducted to investigate the performance of manganese oxides (MnO 2 ) in the reaction between CRP and the contaminant of interest: tetrachloroethylene (PCE). The results showed that higher ionic strengths (I = 0.1 mol/L) cause earlier precipitation of MnO 2 colloids. Using CRP to degrade PCE could decrease the amount of MnO 2 colloids produced and postpone precipitation compared to raw potassium permanganate (KMnO 4 ) under high ionic strength conditions by controlling the KMnO 4 concentration in the solution. The amount of MnO 2 colloids produced and the time of precipitation depended more on the CRP grain size than on the CRP mass ratio. Controlling the KMnO 4 concentration used in the reaction could control the formation of MnO 2 precipitates in the premise of guarantee the removal rate of PCE.

  8. Influence of dissolved organic matter and manganese oxides on metal speciation in soil solution: A modelling approach.

    PubMed

    Schneider, Arnaud R; Ponthieu, Marie; Cancès, Benjamin; Conreux, Alexandra; Morvan, Xavier; Gommeaux, Maxime; Marin, Béatrice; Benedetti, Marc F

    2016-06-01

    Trace element (TE) speciation modelling in soil solution is controlled by the assumptions made about the soil solution composition. To evaluate this influence, different assumptions using Visual MINTEQ were tested and compared to measurements of free TE concentrations. The soil column Donnan membrane technique (SC-DMT) was used to estimate the free TE (Cd, Cu, Ni, Pb and Zn) concentrations in six acidic soil solutions. A batch technique using DAX-8 resin was used to fractionate the dissolved organic matter (DOM) into four fractions: humic acids (HA), fulvic acids (FA), hydrophilic acids (Hy) and hydrophobic neutral organic matter (HON). To model TE speciation, particular attention was focused on the hydrous manganese oxides (HMO) and the Hy fraction, ligands not considered in most of the TE speciation modelling studies in soil solution. In this work, the model predictions of free ion activities agree with the experimental results. The knowledge of the FA fraction seems to be very useful, especially in the case of high DOM content, for more accurately representing experimental data. Finally, the role of the manganese oxides and of the Hy fraction on TE speciation was identified and, depending on the physicochemical conditions of the soil solution, should be considered in future studies. Copyright © 2016 Elsevier Ltd. All rights reserved.

  9. Structural changes in the nano-oxide layer with annealing in specular spin valves

    NASA Astrophysics Data System (ADS)

    Jang, S. H.; Kim, Y. W.; Kang, T.; Kim, H. J.; Kim, K. Y.

    2003-05-01

    We investigated microstructural changes in a nano-oxide layer (NOL) with annealing in specular spin valves (SVs) by cross-sectional transmission electron microscopy and x-ray photoelectron spectroscopy analysis. In the SV annealed at high temperature of 400 °C, an increase in thickness and a local breakdown of the NOL were observed. This local coarsening of the NOL is closely related to the formation of Mn oxides in the oxide-rich part of the NOL through Mn diffusion. Thus, the chemical structure of the NOL changes to the structure with Mn oxide-rich content after annealing.

  10. 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.

  11. Characterization of Antimicrobial Poly (Lactic Acid)/Nano-Composite Films with Silver and Zinc Oxide Nanoparticles

    PubMed Central

    Chu, Zhuangzhuang; Zhao, Tianrui; Li, Lin; Fan, Jian; Qin, Yuyue

    2017-01-01

    Antimicrobial active films based on poly (lactic acid) (PLA) were prepared with nano-silver (nano-Ag) and nano-zinc oxide (nano-ZnO) using a solvent volatilizing method. The films were characterized for mechanical, structural, thermal, physical and antimicrobial properties. Scanning electron microscopy (SEM) images characterized the fracture morphology of the films with different contents of nano-Ag and nano-ZnO. The addition of nanoparticles into the pure PLA film decreased the tensile strength and elasticity modulus and increased the elongation of breaks—in other words, the flexibility and extensibility of these composites improved. According to the results of differential scanning calorimetry (DSC), the glass transition temperature of the PLA nano-composite films decreased, and the crystallinity of these films increased; a similar result was apparent from X-ray diffraction (XRD) analysis. The water vapor permeability (WVP) and opacity of the PLA nano-composite films augmented compared with pure PLA film. Incorporation of nanoparticles to the PLA films significantly improved the antimicrobial activity to inhibit the growth of Escherichia coli. The results indicated that PLA films with nanoparticles could be considered a potential environmental-friendly packaging material. PMID:28773018

  12. Structural and Morphological Evaluation of Nano-Sized MoSi2 Powder Produced by Mechanical Milling

    NASA Astrophysics Data System (ADS)

    Sameezadeh, Mahmood; Farhangi, Hassan; Emamy, Masoud

    Nano-sized intermetallic powders have received great attention owing to their property advantages over conventional micro-sized counterparts. In the present study nano-sized MoSi2 powder has been produced successfully from commercially available MoSi2 (3 μm) by a mechanical milling process carried out for a period of 100 hours. The effects of milling time on size and morphology of the powders were studied by SEM and TEM and image analyzing system. The results indicate that the as-received micrometric powder with a wide size distribution of irregular shaped morphology changes to a narrow size distribution of nearly equiaxed particles with the progress of attrition milling up to 100 h, reaching an average particle size of 71 nm. Structural evolution of milled samples was characterized by XRD to determine the crystallite size and lattice microstrain using Williamson-Hall method. According to the results, the crystallite size of the powders decreases continuously down to 23 nm with increasing milling time up to 100 h and this size refinement is more rapid at the early stages of the milling process. On the other hand, the lattice strain increases considerably with milling up to 65 h and further milling causes no significant changes of lattice strain.

  13. Nano Engineered Energetic Materials (NEEM)

    DTIC Science & Technology

    2011-01-12

    Al nanoparticles, owing to the surface oxidation of the unpassivated particles. The major drawback with utilizing organic capping groups is the...increases seen with nano-sized aluminum are promising, there are certain drawbacks . A thin layer of alumina (Al2O3) usually forms on the exterior...rocket motor by lowering the active aluminum content of the particles. Because of these drawbacks , surface protection in the form of coatings is

  14. 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.

  15. 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.

  16. TRANSPORT AND DEPOSITION OF NANO-SIZE PARTICLES IN THE UPPER HUMAN RESPIRATORY AIRWAYS

    EPA Science Inventory

    TRANSPORT AND DEPOSITION OF NANO-SIZE PARTICLES IN THE UPPER HUMAN RESPIRATORY AIRWAYS. Zhe Zhang*, Huawei Shi, Clement Kleinstreuer, Department of Mechanical and Aerospace Engineering, North Carolina State University, Raleigh, NC 27695-7910; Chong S. Kim, National Health and En...

  17. Single Silver Adatoms on Nanostructured Manganese Oxide Surfaces: Boosting Oxygen Activation for Benzene Abatement.

    PubMed

    Chen, Yaxin; Huang, Zhiwei; Zhou, Meijuan; Ma, Zhen; Chen, Jianmin; Tang, Xingfu

    2017-02-21

    The involvement of a great amount of active oxygen species is a crucial requirement for catalytic oxidation of benzene, because complete mineralization of one benzene molecule needs 15 oxygen atoms. Here, we disperse single silver adatoms on nanostructured hollandite manganese oxide (HMO) surfaces by using a thermal diffusion method. The single-atom silver catalyst (Ag 1 /HMO) shows high catalytic activity in benzene oxidation, and 100% conversion is achieved at 220 °C at a high space velocity of 23 000 h -1 . The Mars-van Krevelen mechanism is valid in our case as the reaction orders for both benzene and O 2 approach one, according to reaction kinetics data. Data from H 2 temperature-programmed reduction and O core-level X-ray photoelectron spectra (XPS) reveal that Ag 1 /HMO possesses a great amount of active surface lattice oxygen available for benzene oxidation. Valence-band XPS and density functional theoretical calculations demonstrate that the single Ag adatoms have the upshifted 4d orbitals, thus facilitating the activation of gaseous oxygen. Therefore, the excellent activation abilities of Ag 1 /HMO toward both surface lattice oxygen and gaseous oxygen account for its high catalytic activity in benzene oxidation. This work may assist with the rational design of efficient metal-oxide catalysts for the abatement of volatile organic compounds such as benzene.

  18. Influence of the domain structure of nano-oxide layers on the transport properties of specular spin valves

    NASA Astrophysics Data System (ADS)

    Ventura, J.; Sousa, J. B.; Veloso, A.; Freitas, P. P.

    2007-05-01

    Specular spin valves show enhanced giant magnetoresistive ratio when compared to other simpler, spin valve structures as a result of specular reflection in nano-oxide layers (NOLs) formed by the partial oxidation of the CoFe pinned and free layers. The oxides forming the NOL were recently shown to order antiferromagnetically below T ˜175K. Here we study the training effect in MnIr /CoFe/NOL/CoFe/Cu/CoFe/NOL specular spin valves at low temperatures (15K). We observed that the training effect is related to the nano-oxide layer antiferromagnet ordering and to the evolution of the corresponding domain structure with the number of cycles performed. This allowed us to study the influence of the NOL domain structure on the magnetotransport of specular spin valves.

  19. 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

  20. Formation of brominated phenolic contaminants from natural manganese oxides-catalyzed oxidation of phenol in the presence of Br(.).

    PubMed

    Lin, Kunde; Song, Lianghui; Zhou, Shiyang; Chen, Da; Gan, Jay

    2016-07-01

    Brominated phenolic compounds (BPCs) are a class of persistent and potentially toxic compounds ubiquitously present in the aquatic environment. However, the origin of BPCs is not clearly understood. In this study, we investigated the formation of BPCs from natural manganese oxides (MnOx)-catalyzed oxidation of phenol in the presence of Br(-). Experiments at ambient temperature clearly demonstrated that BPCs were readily produced via the oxidation of phenol by MnOx in the presence of Br(-). In the reaction of MnOx sand with 0.213 μmol/L phenol and 0.34 mmol/L Br(-) for 10 min, more than 60% of phenol and 56% of Br(-) were consumed to form BPCs. The yield of BPCs increased with increasing concentrations of phenol and Br(-). Overall, a total of 14 BPCs including simple bromophenols (4-bromophenol, 2,4-dibromophenol, and 2,4,6-tribromophenol), hydroxylated polybrominated diphenyl ethers (OH-PBDEs), and hydroxylated polybrominated biphenyls (OH-PBBs) were identified. The production of BPCs increased with increasing concentrations of Br(-) or phenol. It was deduced that Br(-) was first oxidized to form active bromine, leading to the subsequent bromination of phenol to form bromophenols. The further oxidation of bromophenols by MnOx resulted in the formation of OH-PBDEs and OH-PBBs. In view of the ubiquity of phenol, Br(-), and MnOx in the environment, MnOx-mediated oxidation may play a role on the natural production of BPCs. Copyright © 2016 Elsevier Ltd. All rights reserved.