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Sample records for nanostructured manganese oxides

  1. Nanostructured manganese oxide thin films as electrode material for supercapacitors

    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.

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

    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.

  3. Bi-template assisted synthesis of mesoporous manganese oxide nanostructures: Tuning properties for efficient CO oxidation.

    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.

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

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

    2012-01-01

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

  5. A microbial-mineralization-inspired approach for synthesis of manganese oxide nanostructures with controlled oxidation states and morphologies

    Oba, Manabu; Oaki, Yuya; Imai, Hiroaki [Department of Applied Chemistry, Faculty of Science and Technology, Keio University, 3-14-1 Hiyoshi, Kohoku-ku, Yokohama 223-8522 (Japan)

    2010-12-21

    Manganese oxide nanostructures are synthesized by a route inspired by microbial mineralization in nature. The combination of organic molecules, which include antioxidizing and chelating agents, facilitates the parallel control of oxidation states and morphologies in an aqueous solution at room temperature. Divalent manganese hydroxide (Mn(OH){sub 2}) is selectively obtained as a stable dried powder by using a combination of ascorbic acid as an antioxidizing agent and other organic molecules with the ability to chelate to manganese ions. The topotactic oxidation of the resultant Mn(OH){sub 2} leads to the selective formation of trivalent manganese oxyhydroxide ({beta}-MnOOH) and trivalent/tetravalent sodium manganese oxide (birnessite, Na{sub 0.55}Mn{sub 2}O{sub 4}.1.5H{sub 2}O). For microbial mineralization in nature, similar synthetic routes via intermediates have been proposed in earlier works. Therefore, these synthetic routes, which include in the present study the parallel control over oxidation states and morphologies of manganese oxides, can be regarded as new biomimetic routes for synthesis of transition metal oxide nanostructures. As a potential application, it is demonstrated that the resultant {beta}-MnOOH nanostructures perform as a cathode material for lithium ion batteries. (Copyright copyright 2010 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  6. An Electrochemical Sensor Based on Nanostructured Hollandite-type Manganese Oxide for Detection of Potassium Ions

    Alex S. Lima

    2009-08-01

    Full Text Available The participation of cations in redox reactions of manganese oxides provides an opportunity for development of chemical sensors for non-electroactive ions. A sensor based on a nanostructured hollandite-type manganese oxide was investigated for voltammetric detection of potassium ions. The detection is based on the measurement of anodic current generated by oxidation of Mn(III to Mn(IV at the surface of the electrode and the subsequent extraction of the potassium ions into the hollandite structure. In this work, an amperometric procedure at an operating potential of 0.80 V (versus SCE is exploited for amperometric monitoring. The current signals are linearly proportional to potassium ion concentration in the range 4.97 × 10−5 to 9.05 × 10−4 mol L−1, with a correlation coefficient of 0.9997.

  7. Manganese Nanostructures and Magnetism

    Simov, Kirie Rangelov

    The primary goal of this study is to incorporate adatoms with large magnetic moment, such as Mn, into two technologically significant group IV semiconductor (SC) matrices, e.g. Si and Ge. For the first time in the world, we experimentally demonstrate Mn doping by embedding nanostructured thin layers, i.e. delta-doping. The growth is observed by in-situ scanning tunneling microscopy (STM), which combines topographic and electronic information in a single image. We investigate the initial stages of Mn monolayer growth on a Si(100)(2x1) surface reconstruction, develop methods for classification of nanostructure types for a range of surface defect concentrations (1.0 to 18.2%), and subsequently encapsulate the thin Mn layer in a SC matrix. These experiments are instrumental in generating a surface processing diagram for self-assembly of monoatomic Mn-wires. The role of surface vacancies has also been studied by kinetic Monte Carlo modeling and the experimental observations are compared with the simulation results, leading to the conclusion that Si(100)(2x1) vacancies serve as nucleation centers in the Mn-Si system. Oxide formation, which happens readily in air, is detrimental to ferromagnetism and lessens the magnetic properties of the nanostructures. Therefore, the protective SC cap, composed of either Si or Ge, serves a dual purpose: it is both the embedding matrix for the Mn nanostructured thin film and a protective agent for oxidation. STM observations of partially deposited caps ensure that the nanostructures remain intact during growth. Lastly, the relationship between magnetism and nanostructure types is established by an in-depth study using x-ray magnetic circular dichroism (XMCD). This sensitive method detects signals even at coverages less than one atomic layer of Mn. XMCD is capable of discerning which chemical compounds contribute to the magnetic moment of the system, and provides a ratio between the orbital and spin contributions. Depending on the amount

  8. High-performance symmetric electrochemical capacitor based on graphene foam and nanostructured manganese oxide

    Bello, A

    2013-01-01

    Full Text Available We have fabricated a symmetric electrochemical capacitor with high energy and power densities based on a composite of graphene foam (GF) with 80 wt% of manganese oxide (MnO(sub2)) deposited by hydrothermal synthesis. Raman spectroscopy and X...

  9. Noncollinear magnetism in manganese nanostructures

    Zelený, Martin; Šob, Mojmír; Hafner, J.

    2009-01-01

    Roč. 80, č. 14 (2009), 144414/1-144414/19 ISSN 1098-0121 R&D Projects: GA AV ČR IAA100100920; GA MŠk OC09011 Institutional research plan: CEZ:AV0Z20410507 Keywords : magnetism of nanostructures * nanowires * noncollinear magnetism * manganese Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 3.475, year: 2009

  10. High-performance symmetric electrochemical capacitor based on graphene foam and nanostructured manganese oxide

    Abdulhakeem Bello

    2013-08-01

    Full Text Available We have fabricated a symmetric electrochemical capacitor with high energy and power densities based on a composite of graphene foam (GF with ∼80 wt% of manganese oxide (MnO2 deposited by hydrothermal synthesis. Raman spectroscopy and X-ray diffraction measurements showed the presence of nanocrystalline MnO2 on the GF, while scanning and transmission electron microscopies showed needle-like manganese oxide coated and anchored onto the surface of graphene. Electrochemical measurements of the composite electrode gave a specific capacitance of 240 Fg−1 at a current density of 0.1 Ag−1 for symmetric supercapacitors using a two-electrode configuration. A maximum energy density of 8.3 Whkg−1 was obtained, with power density of 20 kWkg−1 and no capacitance loss after 1000 cycles. GF is an excellent support for pseudo-capacitive oxide materials such as MnO2, and the composite electrode provided a high energy density due to a combination of double-layer and redox capacitance mechanisms.

  11. Synthesis of single crystal manganese oxide octahedral molecular sieve (OMS) nanostructures with tunable tunnels and shapes.

    Li, Wei-Na; Yuan, Jikang; Gomez-Mower, Sinue; Sithambaram, Shantakumar; Suib, Steven L

    2006-02-23

    A new and facile route is reported to manipulate the self-assembly synthesis of hierarchically ordered Rb-OMS-2 and pyrolusite with an interesting flowerlike morphology by a direct and mild reaction between rubidium chromateand manganese sulfate without any organic templates. The crystal forms, morphologies, and tunnel sizes of the obtained OMS materials can be controlled. A mechanism for the growth of manganese dioxides with flowerlike architectures was proposed. The obtained products exhibit potential for use in catalysis and other applications.

  12. Morphology and crystallinity-controlled synthesis of manganese cobalt oxide/manganese dioxides hierarchical nanostructures for high-performance supercapacitors

    Li, Fei; Li, Gang; Chen, Hao; Jia, Jia Qi; Dong, Fan; Hu, Yao Bo; Shang, Zheng Guo; Zhang, Yu Xin

    2015-11-01

    We demonstrate a novel preparative strategy for the well-controlled MnCo2O4.5@MnO2 hierarchical nanostructures. Both δ-MnO2 nanosheets and α-MnO2 nanorods can uniformly decorate the surface of MnCo2O4.5 nanowires to form core-shell heterostructures. Detailed electrochemical characterization reveals that MnCo2O4.5@δ-MnO2 pattern exhibits not only high specific capacitance of 357.5 F g-1 at a scan rate of 0.5 A g-1, but also good cycle stability (97% capacitance retention after 1000 cycles at a scan rate of 5 A g-1), which make it have a promising application as a supercapacitor electrode material.

  13. Nanostructured manganese oxide/carbon nanotubes, graphene and graphene oxide as water-oxidizing composites in artificial photosynthesis.

    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.

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

    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

  15. Synthesis of nanostructured mixed oxide CeO2-Mn2O3 and investigation of their sorption ability for arsenic, ammoniac, iron, manganese

    Luu Minh Dai; Dao Ngoc Nhiem; Duong Thi Lim

    2012-01-01

    The nanostrutured mixed oxide CeO 2 -Mn 2 O 3 have been synthesised at low temperature (350 o C) by the combustion of gel prepared from polyvinyl alcohol (PVA), Ce (NO 3 ) 4 and Mn(No 3 ) 3 , CeO 2 -Mn 2 O 3 characterizations were examined by X-ray diffraction (XRD), scanning electron microscopy (SEM) and BET (Brunauce-Emmet-Teller) measurements. The phase of CeO 2 -Mn 2 O 3 , with large specific surface ares 65.3 m 2 /g was obtained at 350 o C for 2 hours. The nanostructured CeO 2 -Mn 2 O 3 has been investigated for removing iron, manganese, arsenic and ammoniac from water. The sorption characteristics of the nanostrutured CeO 2 -Mn 2 O 3 for AS(V), NH4 + , Fe(III), Mn(II) according to the langmuir isotherm. The sorption capacities of nanostrutured CeO 2 -Mn 2 O 3 are 57.10 mg As(V)g; 154.54 mg NH4 + /g; 72.97 mg Fe(III)/g; 60.27 Mn(II) / g. (author)

  16. Manganese oxide/graphene oxide composites for high-energyaqueous asymmetric electrochemical capacitors

    Jafta, CJ

    2013-11-01

    Full Text Available A high-energy aqueous asymmetric electrochemical capacitor was developed using manganese diox-ide ( -MnO2)/graphene oxide (GO) nanocomposites. The nanostructured -MnO2was prepared frommicron-sized commercial electrolytic manganese dioxide (EMD) via...

  17. Hydrothermal Synthesis of Nanostructured Manganese Oxide as Cathodic Catalyst in a Microbial Fuel Cell Fed with Leachate

    Haoran, Yuan; Lifang, Deng; Tao, Lu; Yong, Chen

    2014-01-01

    Much effort has been devoted to the synthesis of novel nanostructured MnO2 materials because of their unique properties and potential applications as cathode catalyst in Microbial fuel cell. Hybrid MnO2 nanostructures were fabricated by a simple hydrothermal method in this study. Their crystal structures, morphology, and electrochemical characters were carried out by FESEM, N2-adsorption-desorption, and CV, indicating that the hydrothermally synthesized MnO2 (HSM) was structured by nanorods of high aspect ratio and multivalve nanoflowers and more positive than the naturally synthesized MnO2 (NSM), accompanied by a noticeable increase in oxygen reduction peak current. When the HSM was employed as the cathode catalyst in air-cathode MFC which fed with leachate, a maximum power density of 119.07 mW/m2 was delivered, 64.68% higher than that with the NSM as cathode catalyst. Furthermore, the HSM via a 4-e pathway, but the NSM via a 2-e pathway in alkaline solution, and as 4-e pathway is a more efficient oxygen reduction reaction, the HSM was more positive than NSM. Our study provides useful information on facile preparation of cost-effective cathodic catalyst in air-cathode MFC for wastewater treatment. PMID:24723824

  18. Manganese Oxidation by Bacteria: Biogeochemical Aspects

    Sujith, P.P.; LokaBharathi, P.A.

    Manganese is an essential trace metal that is not as readily oxidizable like iron. Several bacterial groups posses the ability to oxidize Mn effectively competing with chemical oxidation. The oxides of Mn are the strongest of the oxidants, next...

  19. Nanostructured manganese oxides in supercapacitors

    Makgopa, K

    2016-07-01

    Full Text Available of environmental pollution. Hence there is an urgent need for clean, cheap, efficient and sustainable sources of energy, as well as new technologies associated with energy storage and conversion. The electrochemical capacitor (EC), also known as ultracapacitor...

  20. Manganese oxide-based materials as electrochemical supercapacitor electrodes.

    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).

  1. Ternary manganese ferrite/graphene/polyaniline nanostructure with enhanced electrochemical capacitance performance

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

    2014-11-01

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

  2. Manganese oxide nanoparticles, methods and applications

    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.

  3. Preparation of the electrochemically formed spinel-lithium manganese oxides

    Katakura, Katsumi; Wada, Kohei; Kajiki, Yoshiyuki; Yamamoto, Akiko [Department of Chemical Engineering, Nara National College of Technology, 22 Yata-cho Yamotokoriyama, Nara 639-1080 (Japan); Ogumi, Zempachi [Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto 615-8510 (Japan)

    2009-04-01

    Electrochemically formed spinel-lithium manganese oxides were synthesized from manganese hydroxides prepared by a cathodic electrochemical precipitation from various concentrations of manganese nitrate solutions. Two types of manganese hydroxides were formed from diluted and concentrated Mn(NO{sub 3}){sub 2} aqueous solutions. Uniform and equi-sized disk shaped Mn(OH){sub 2} crystals of 0.2-5 {mu}m in diameter were obtained on a Pt substrate after the electrochemical precipitation from lower concentration of ranging from 2 mmol dm{sup -3} to 2 mol dm{sup -3} Mn(NO{sub 3}){sub 2} aq., while the grass blade-like precipitate which is ascribed to manganese hydroxide with 20-80 {mu}m long and 1-5 {mu}m wide were formed from concentrated Mn(NO{sub 3}){sub 2} aq. Both manganese hydroxides gave the electrochemically formed spinel-LiMn{sub 2}O{sub 4} onto a Pt sheet, which is ready for electrochemical measurement, after calcination of the Li incorporated precipitate at 750 C without any additives. While the shape and size of the secondary particle frameworks (aggregates) of the electrochemically formed spinel-LiMn{sub 2}O{sub 4} can be controlled by the electrolysis conditions, the nanostructured primary crystals of 200 nm in diameter were obtained in all cases except that the fiber-like nanostructured spinel-LiMn{sub 2}O{sub 4} crystals with 200 nm in diameter were obtained from concentrated Mn(NO{sub 3}){sub 2} aq. Though these two types of electrochemically formed spinel-LiMn{sub 2}O{sub 4} showed well-shaped CVs even in higher scan rates, it would be suitable for high power density battery applications. These behaviors are assumed to be ascribed to the crystal size and shape of the processed spinel-LiMn{sub 2}O{sub 4}. (author)

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

    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 p...

  5. Synthesis of vertically aligned metal oxide nanostructures

    Roqan, Iman S.

    2016-03-03

    Metal oxide nanostructure and methods of making metal oxide nanostructures are provided. The metal oxide nanostructures can be 1 -dimensional nanostructures such as nanowires, nanofibers, or nanotubes. The metal oxide nanostructures can be doped or undoped metal oxides. The metal oxide nanostructures can be deposited onto a variety of substrates. The deposition can be performed without high pressures and without the need for seed catalysts on the substrate. The deposition can be performed by laser ablation of a target including a metal oxide and, optionally, a dopant. In some embodiments zinc oxide nanostructures are deposited onto a substrate by pulsed laser deposition of a zinc oxide target using an excimer laser emitting UV radiation. The zinc oxide nanostructure can be doped with a rare earth metal such as gadolinium. The metal oxide nanostructures can be used in many devices including light-emitting diodes and solar cells.

  6. Silver manganese oxide electrodes for lithium batteries

    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.

  7. Synthesis, structure, and optical properties of manganese phthalocyanine thin films and nanostructures

    Lu Meng

    2017-06-01

    Full Text Available Manganese phthalocyanine (MnPc nanostructures with different morphologies were prepared on porous anodic alumina oxide (AAO at different substrate temperature (Ts=50 ℃, 80 ℃, 120 ℃, 180 ℃, 240 ℃ in an organic molecular beam deposition (OMBD system. The nanostructures morphologies were studied using scanning electron microscopy (SEM and the results showed that the nanostructures morphologies could be modulated by the control of Ts, as a result, the continuous film was obtained at 50 ℃, whereas the nanorods (NRs, nanoribbons (NBs, nanowires (NWs, nanosheets (NSs and nanoparticles (NPs were facilely generated as Ts increased. At the same time, the density and the uniformity of the nanostructures decreased. The results of X-ray diffraction (XRD indicated that only the β-phase polymorph formed throughout the growth process irrelevant to the Ts. Additionally, the ultraviolet visible (UV–Vis absorption spectra demonstrated that the main absorption bands of MnPc nanostructures showed a remarkable band broadening as the Ts was increased.

  8. Effects of electrochemical-deposition method and microstructure on the capacitive characteristics of nano-sized manganese oxide

    Shinomiya, Takuya; Gupta, Vinay; Miura, Norio

    2006-01-01

    The amorphous nano-structured manganese oxide was electrochemically deposited onto a stainless-steel electrode. The structure and surface morphology of the obtained manganese oxide were studied by means of X-ray diffraction analysis and scanning electron microscopy. The capacitive characteristics of the manganese oxide electrodes were investigated by means of cyclic voltammetry and constant current charge-discharge cycling. The morphological and capacitive characteristics of the hydrous manganese oxide was found to be strongly influenced by the electrochemical deposition conditions. The highest specific capacitance value of ca. 410 F g -1 and the specific power of ca. 54 kW kg -1 were obtained at 400 mV s -1 sweep rate of potentiodynamic deposition condition. The cyclic-life data showed that the specific capacitance was highly stable up to 10,000 cycles examined. This suggests the excellent cyclic stability of the obtained amorphous hydrous manganese oxide for supercapacitor application

  9. Effects of electrochemical-deposition method and microstructure on the capacitive characteristics of nano-sized manganese oxide

    Shinomiya, Takuya; Gupta, Vinay; Miura, Norio [Art, Science and Technology Center for Cooperative Research, Kyushu University, Kasuga-shi, Fukuoka 816-8580 (Japan)

    2006-06-01

    The amorphous nano-structured manganese oxide was electrochemically deposited onto a stainless-steel electrode. The structure and surface morphology of the obtained manganese oxide were studied by means of X-ray diffraction analysis and scanning electron microscopy. The capacitive characteristics of the manganese oxide electrodes were investigated by means of cyclic voltammetry and constant current charge-discharge cycling. The morphological and capacitive characteristics of the hydrous manganese oxide was found to be strongly influenced by the electrochemical deposition conditions. The highest specific capacitance value of ca. 410Fg{sup -1} and the specific power of ca. 54kWkg{sup -1} were obtained at 400mVs{sup -1} sweep rate of potentiodynamic deposition condition. The cyclic-life data showed that the specific capacitance was highly stable up to 10,000 cycles examined. This suggests the excellent cyclic stability of the obtained amorphous hydrous manganese oxide for supercapacitor application. (author)

  10. A Review on the Synthesis of Manganese Oxide Nanomaterials and Their Applications on Lithium-Ion Batteries

    Xiaodi Liu

    2013-01-01

    Full Text Available Most recently, manganese oxides nanomaterials, including MnO and MnO2, have attracted great interest as anode materials in lithium-ion batteries (LIBs for their high theoretical capacity, environmental benignity, low cost, and special properties. Up to now, manganese oxides nanostructures with excellent properties and various morphologies have been successfully synthesized. Herein, we provide an in-depth discussion of recent development of the synthesis of manganese oxides nanomaterials and their application in the field of LIBs.

  11. Modeling Manganese Sorption and Surface Oxidation During Filtration

    Bierlein, Kevin Andrew

    2012-01-01

    Soluble manganese (Mn) is a common contaminant in drinking water sources. High levels of Mn can lead to aesthetic water quality problems, necessitating removal of Mn during treatment to minimize consumer complaints. Mn may be removed during granular media filtration by the â natural greensand effect,â in which soluble Mn adsorbs to manganese oxide-coated (MnOx(s)) media and is then oxidized by chlorine, forming more manganese oxide. This research builds on a previous model developed by Mer...

  12. Electrodeposited manganese dioxide nanostructures on electro-etched carbon fibers: High performance materials for supercapacitor applications

    Kazemi, Sayed Habib, E-mail: habibkazemi@iasbs.ac.ir [Department of Chemistry, Institute for Advanced Studies in Basic Sciences (IASBS), Zanjan 45137-66731 (Iran, Islamic Republic of); Center for Research in Climate Change and Global Warming (CRCC), Institute for Advanced Studies in Basic Sciences (IASBS), Zanjan 45137-66731 (Iran, Islamic Republic of); Maghami, Mostafa Ghaem [Department of Chemistry, Institute for Advanced Studies in Basic Sciences (IASBS), Zanjan 45137-66731 (Iran, Islamic Republic of); Kiani, Mohammad Ali [Chemistry and Chemical Engineering Research Center of Iran, P.O. Box 14335-186, Tehran (Iran, Islamic Republic of)

    2014-12-15

    Highlights: • We report a facile method for fabrication of MnO{sub 2} nanostructures on electro-etched carbon fiber. • MnO{sub 2}-ECF electrode shows outstanding supercapacitive behavior even at high discharge rates. • Exceptional cycle stability was achieved for MnO{sub 2}-ECF electrode. • The coulombic efficiency of MnO{sub 2}-ECF electrode is nearly 100%. - Abstract: In this article we introduce a facile, low cost and additive/template free method to fabricate high-rate electrochemical capacitors. Manganese oxide nanostructures were electrodeposited on electro-etched carbon fiber substrate by applying a constant anodic current. Nanostructured MnO{sub 2} on electro-etched carbon fiber was characterized by scanning electron microscopy, X-ray diffraction and energy dispersive X-ray analysis. The electrochemical behavior of MnO{sub 2} electro-etched carbon fiber electrode was investigated by electrochemical techniques including cyclic voltammetry, galvanostatic charge/discharge, and electrochemical impedance spectroscopy. A maximum specific capacitance of 728.5 F g{sup −1} was achieved at a scan rate of 5 mV s{sup −1} for MnO{sub 2} electro-etched carbon fiber electrode. Also, this electrode showed exceptional cycle stability, suggesting that it can be considered as a good candidate for supercapacitor electrodes.

  13. Electrodeposited manganese dioxide nanostructures on electro-etched carbon fibers: High performance materials for supercapacitor applications

    Kazemi, Sayed Habib; Maghami, Mostafa Ghaem; Kiani, Mohammad Ali

    2014-01-01

    Highlights: • We report a facile method for fabrication of MnO 2 nanostructures on electro-etched carbon fiber. • MnO 2 -ECF electrode shows outstanding supercapacitive behavior even at high discharge rates. • Exceptional cycle stability was achieved for MnO 2 -ECF electrode. • The coulombic efficiency of MnO 2 -ECF electrode is nearly 100%. - Abstract: In this article we introduce a facile, low cost and additive/template free method to fabricate high-rate electrochemical capacitors. Manganese oxide nanostructures were electrodeposited on electro-etched carbon fiber substrate by applying a constant anodic current. Nanostructured MnO 2 on electro-etched carbon fiber was characterized by scanning electron microscopy, X-ray diffraction and energy dispersive X-ray analysis. The electrochemical behavior of MnO 2 electro-etched carbon fiber electrode was investigated by electrochemical techniques including cyclic voltammetry, galvanostatic charge/discharge, and electrochemical impedance spectroscopy. A maximum specific capacitance of 728.5 F g −1 was achieved at a scan rate of 5 mV s −1 for MnO 2 electro-etched carbon fiber electrode. Also, this electrode showed exceptional cycle stability, suggesting that it can be considered as a good candidate for supercapacitor electrodes

  14. Microwave Production of Manganese from Manganese (IV) Oxide ...

    Michael O. Mensah

    2015-12-02

    Dec 2, 2015 ... energy consumption occurs in the upper part of the ferromanganese furnace ... The pre-reduction of manganese ores by carbon has been investigated by Abdel ..... Awaso Bauxite Ore using Waste Pure Water. Sachets as ...

  15. Recovery of manganese from manganese oxide ores in the EDTA solution

    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.

  16. Self-assembled manganese oxide structures through direct oxidation

    Zhao, Chao; Wang, Qingxiao; Yang, Yang; Zhang, Bei; Zhang, Xixiang

    2012-01-01

    The morphology and phase of self-assembled manganese oxides during different stages of thermal oxidation were studied. Very interesting morphological patterns of Mn oxide films were observed. At the initial oxidation stage, the surface was characterized by the formation of ring-shaped patterns. As the oxidation proceeded to the intermediate stage, concentric plates formed to relax the compressive stress. Our experimental results gave a clear picture of the evolution of the structures. We also examined the properties of the structures. © 2012 Elsevier B.V.

  17. Self-assembled manganese oxide structures through direct oxidation

    Zhao, Chao

    2012-12-01

    The morphology and phase of self-assembled manganese oxides during different stages of thermal oxidation were studied. Very interesting morphological patterns of Mn oxide films were observed. At the initial oxidation stage, the surface was characterized by the formation of ring-shaped patterns. As the oxidation proceeded to the intermediate stage, concentric plates formed to relax the compressive stress. Our experimental results gave a clear picture of the evolution of the structures. We also examined the properties of the structures. © 2012 Elsevier B.V.

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

    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.

  19. Biological Superoxide In Manganese Oxide Formation

    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.

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

    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...

  1. Chemical Sensors Based on Metal Oxide Nanostructures

    Hunter, Gary W.; Xu, Jennifer C.; Evans, Laura J.; VanderWal, Randy L.; Berger, Gordon M.; Kulis, Mike J.; Liu, Chung-Chiun

    2006-01-01

    This paper is an overview of sensor development based on metal oxide nanostructures. While nanostructures such as nanorods show significan t potential as enabling materials for chemical sensors, a number of s ignificant technical challenges remain. The major issues addressed in this work revolve around the ability to make workable sensors. This paper discusses efforts to address three technical barriers related t o the application of nanostructures into sensor systems: 1) Improving contact of the nanostructured materials with electrodes in a microse nsor structure; 2) Controling nanostructure crystallinity to allow co ntrol of the detection mechanism; and 3) Widening the range of gases that can be detected by using different nanostructured materials. It is concluded that while this work demonstrates useful tools for furt her development, these are just the beginning steps towards realizati on of repeatable, controlled sensor systems using oxide based nanostr uctures.

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

    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.

  3. Manganese oxidation by bacterial isolates from the Indian Ridge System

    Fernandes, S.O.; Krishnan, K.P.; Khedekar, V.D.; LokaBharathi, P.A.

    The abundance and activity of culturable manganese-oxidizing bacteria were assessed from near-bottom water samples of the tectonically active Carlsberg Ridge. Retrievable counts as colony forming units (CFU) on dilute nutrient agar medium (dilNA = 2...

  4. Anodically generated manganese(III) sulphate for the oxidation of ...

    Unknown

    oxidation of dipeptides in aqueous sulphuric acid medium: A kinetic study ... acetic acid (TFA) and N-methylmorpholine (NMM) were purchased ... and chloroform–methanol– acetic acid .... tion), manganese(II) sulphate and water (to keep the.

  5. Manganese and iron oxidation by fungi isolated from building stone.

    de la Torre, M A; Gomez-Alarcon, G

    1994-01-01

    Acid and nonacid generating fungal strains isolated from weathered sandstone, limestone, and granite of Spanish cathedrals were assayed for their ability to oxidize iron and manganese. In general, the concentration of the different cations present in the mineral salt media directly affected Mn(IV) oxide formation, although in some cases, the addition of glucose and nitrate to the culture media was necessary. Mn(II) oxidation in acidogenic strains was greater in a medium containing the highest concentrations of glucose, nitrate, and manganese. High concentrations of Fe(II), glucose, and mineral salts were optimal for iron oxidation. Mn(IV) precipitated as oxides or hydroxides adhered to the mycelium. Most of the Fe(III) remained in solution by chelation with organic acids excreted by acidogenic strains. Other metabolites acted as Fe(III) chelators in nonacidogenic strains, although Fe(III) deposits around the mycelium were also detected. Both iron and manganese oxidation were shown to involve extracellular, hydrosoluble enzymes, with maximum specific activities during exponential growth. Strains able to oxidize manganese were also able to oxidize iron. It is concluded that iron and manganese oxidation reported in this work were biologically induced by filamentous fungi mainly by direct (enzymatic) mechanisms.

  6. Directed spatial organization of zinc oxide nanostructures

    Hsu, Julia [Albuquerque, NM; Liu, Jun [Richland, WA

    2009-02-17

    A method for controllably forming zinc oxide nanostructures on a surface via an organic template, which is formed using a stamp prepared from pre-defined relief structures, inking the stamp with a solution comprising self-assembled monolayer (SAM) molecules, contacting the stamp to the surface, such as Ag sputtered on Si, and immersing the surface with the patterned SAM molecules with a zinc-containing solution with pH control to form zinc oxide nanostructures on the bare Ag surface.

  7. Synthesis of vertically aligned metal oxide nanostructures

    Roqan, Iman S.; Flemban, Tahani H.

    2016-01-01

    ablation of a target including a metal oxide and, optionally, a dopant. In some embodiments zinc oxide nanostructures are deposited onto a substrate by pulsed laser deposition of a zinc oxide target using an excimer laser emitting UV radiation. The zinc

  8. Evidence for polaron conduction in nanostructured manganese ferrite

    Gopalan, E Veena; Anantharaman, M R; Malini, K A; Saravanan, S; Kumar, D Sakthi; Yoshida, Yasuhiko

    2008-01-01

    Nanoparticles of manganese ferrite were prepared by the chemical co-precipitation technique. The dielectric parameters, namely, real and imaginary dielectric permittivity (ε' and ε-prime), ac conductivity (σ ac ) and dielectric loss tangent (tanδ), were measured in the frequency range of 100 kHz-8 MHz at different temperatures. The variations of dielectric dispersion (ε') and dielectric absorption (ε-prime) with frequency and temperature were also investigated. The variation of dielectric permittivity with frequency and temperature followed the Maxwell-Wagner model based on interfacial polarization in consonance with Koops phenomenological theory. The dielectric loss tangent and hence ε-prime exhibited a relaxation at certain frequencies and at relatively higher temperatures. The dispersion of dielectric permittivity and broadening of the dielectric absorption suggest the possibility of a distribution of relaxation time and the existence of multiple equilibrium states in manganese ferrite. The activation energy estimated from the dielectric relaxation is found to be high and is characteristic of polaron conduction in the nanosized manganese ferrite. The ac conductivity followed a power law dependence σ ac = Bω n typical of charge transport assisted by a hopping or tunnelling process. The observed minimum in the temperature dependence of the frequency exponent n strongly suggests that tunnelling of the large polarons is the dominant transport process

  9. Hydrometallurgical Process and Kinetics of Leaching Manganese from Semi-Oxidized Manganese Ores with Sucrose

    Yuhong Wang

    2017-02-01

    Full Text Available The extraction of manganese from a semi-oxidized manganese ore was investigated with sucrose as the reducing agent in dilute sulfuric acid medium. The kinetics of leaching manganese from the complex ore containing MnCO3 and MnO2 was also investigated. The effects of sucrose and sulfuric acid concentrations, leaching temperature and reaction time on the total Mn (TMn, MnO2 and MnCO3 leaching were investigated. Results showed that MnCO3 could more easily react with hydrogen ions than MnO2 in ores, and MnO2 decomposition could be advantageous for MnCO3 leaching. The leaching efficiencies of 91.8% for total Mn, 91.4% for MnO2 and 96.9% for MnCO3 were obtained under the following optimized conditions: 0.035 mol/L sucrose concentration, 5 mol/L sulfuric acid concentration, 60 min of reaction time and 363.2 K of leaching temperature. In addition, it was found that the leaching process of semi-oxidized manganese ore follows the shrinking core model and the leaching rate was controlled by chemical reaction and diffusion. The apparent activation energy of the total manganese, MnO2, and MnCO3 leaching were 40.83, 40.59, and 53.33 kJ·mol−1, respectively.

  10. Metal oxide nanostructures as gas sensing devices

    Eranna, G

    2016-01-01

    Metal Oxide Nanostructures as Gas Sensing Devices explores the development of an integrated micro gas sensor that is based on advanced metal oxide nanostructures and is compatible with modern semiconductor fabrication technology. This sensor can then be used to create a compact, low-power, handheld device for analyzing air ambience. The book first covers current gas sensing tools and discusses the necessity for miniaturized sensors. It then focuses on the materials, devices, and techniques used for gas sensing applications, such as resistance and capacitance variations. The author addresses the issues of sensitivity, concentration, and temperature dependency as well as the response and recovery times crucial for sensors. He also presents techniques for synthesizing different metal oxides, particularly those with nanodimensional structures. The text goes on to highlight the gas sensing properties of many nanostructured metal oxides, from aluminum and cerium to iron and titanium to zinc and zirconium. The final...

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

    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.

  12. The sorption of silver by poorly crystallized manganese oxides

    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.

  13. Nanostructured transparent conducting oxide electrochromic device

    Milliron, Delia; Tangirala, Ravisubhash; Llordes, Anna; Buonsanti, Raffaella; Garcia, Guillermo

    2016-05-17

    The embodiments described herein provide an electrochromic device. In an exemplary embodiment, the electrochromic device includes (1) a substrate and (2) a film supported by the substrate, where the film includes transparent conducting oxide (TCO) nanostructures. In a further embodiment, the electrochromic device further includes (a) an electrolyte, where the nanostructures are embedded in the electrolyte, resulting in an electrolyte, nanostructure mixture positioned above the substrate and (b) a counter electrode positioned above the mixture. In a further embodiment, the electrochromic device further includes a conductive coating deposited on the substrate between the substrate and the mixture. In a further embodiment, the electrochromic device further includes a second substrate positioned above the mixture.

  14. Permanganate-based synthesis of manganese oxide nanoparticles in ferritin

    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.

  15. Condensation on Superhydrophobic Copper Oxide Nanostructures

    Enright, Ryan; Miljkovic, Nenad; Dou, Nicholas; Nam, Youngsuk; Wang, Evelyn N.

    2013-01-01

    Condensation is an important process in both emerging and traditional power generation and water desalination technologies. Superhydrophobic nanostructures promise enhanced condensation heat transfer by reducing the characteristic size of departing droplets via a surface-tension-driven mechanism [1]. In this work, we investigated a scalable synthesis technique to produce oxide nanostructures on copper surfaces capable of sustaining superhydrophobic condensation and characterized the growth an...

  16. Factors affecting radium removal using mixed iron-manganese oxides

    Mott, H.V. Singh, S.; Kondapally, V.R.

    1993-01-01

    Batch experiments confirmed that sorption of radium by a mixed iron-manganese oxide solid phase shows promise for treating radium-contaminated water. The capacities of these mixed oxides for sorption of radium depend on the composition of the solid phase, the pH of the aqueous solution, and the presence of competing cations. The removal of the oxide-radium complexes from aqueous suspension by manganese greensand filtration was also investigated. It was found that influent radium concentrations of 100 pCi/L were reduced to 2--9 pCi/L by this process. Additional study of the fate of radium in manganese greensand filters is recommended before this procedure is used for drinking water treatment

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

    Tao Li; Sun Chenggao; Fan Meilian; Huang Caijuan; Wu Hailong; Chao Zisheng; Zhai Hesheng

    2006-01-01

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

  18. Factors affecting radium removal using mixed iron-manganese oxides

    Mott, H.V. Singh, S.; Kondapally, V.R. (South Dakota School of Mines and Technology, Rapid City, SD (United States))

    1993-10-01

    Batch experiments confirmed that sorption of radium by a mixed iron-manganese oxide solid phase shows promise for treating radium-contaminated water. The capacities of these mixed oxides for sorption of radium depend on the composition of the solid phase, the pH of the aqueous solution, and the presence of competing cations. The removal of the oxide-radium complexes from aqueous suspension by manganese greensand filtration was also investigated. It was found that influent radium concentrations of 100 pCi/L were reduced to 2--9 pCi/L by this process. Additional study of the fate of radium in manganese greensand filters is recommended before this procedure is used for drinking water treatment.

  19. Building Composite Fe-Mn Oxide Flower-Like Nanostructures: A Detailed Magnetic Study

    Zuddas, Efisio; Lentijo Mozo, Sergio; Casu, Alberto; Deiana, Davide; Falqui, Andrea

    2017-01-01

    Here we show that it’s possible to produce different magnetic core-multiple shells heterostructures from monodispersed iron oxide spherical magnetic seeds by finely controlling the amount of a manganese precursor and using in a smart and simple way a cation exchange synthetic approach. In particular, by increasing the amount of precursor we were able to produce nanostructures ranging from Fe3O4/Mn-ferrite core/single shell nanospheres to larger, flower-like Fe3O4/Mn-ferrite/Mn3O4 core-double shell nanoparticles. We first demonstrate how the formation of the initial thin manganese-ferrite shell determines a dramatic reduction of the superficial disorder in the starting iron oxide, bringing to nanomagnets with lower hardness. Then, the growth of the second and most external manganese oxide shell causes the magnetical hardening of the heterostructures, while its magnetic exchange coupling with the rest of the heterostructure can be antiferromagentic or ferromagnetic, depending on the strength of the applied external magnetic field. This response is similar to that of an iron oxide-manganese oxide core-shell system but differs from what observed in multiple-shell heterostructures. Finally, we report as the most external shell becomes magnetically irrelevant above the ferrimagnetic-paramagnetic transition of the manganese oxide and the resulting magnetic behavior of the flower-like structures is then studied in-depth.

  20. Building Composite Fe-Mn Oxide Flower-Like Nanostructures: A Detailed Magnetic Study

    Zuddas, Efisio

    2017-07-21

    Here we show that it’s possible to produce different magnetic core-multiple shells heterostructures from monodispersed iron oxide spherical magnetic seeds by finely controlling the amount of a manganese precursor and using in a smart and simple way a cation exchange synthetic approach. In particular, by increasing the amount of precursor we were able to produce nanostructures ranging from Fe3O4/Mn-ferrite core/single shell nanospheres to larger, flower-like Fe3O4/Mn-ferrite/Mn3O4 core-double shell nanoparticles. We first demonstrate how the formation of the initial thin manganese-ferrite shell determines a dramatic reduction of the superficial disorder in the starting iron oxide, bringing to nanomagnets with lower hardness. Then, the growth of the second and most external manganese oxide shell causes the magnetical hardening of the heterostructures, while its magnetic exchange coupling with the rest of the heterostructure can be antiferromagentic or ferromagnetic, depending on the strength of the applied external magnetic field. This response is similar to that of an iron oxide-manganese oxide core-shell system but differs from what observed in multiple-shell heterostructures. Finally, we report as the most external shell becomes magnetically irrelevant above the ferrimagnetic-paramagnetic transition of the manganese oxide and the resulting magnetic behavior of the flower-like structures is then studied in-depth.

  1. 40 CFR 721.10010 - Barium manganese oxide (BaMnO3).

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Barium manganese oxide (BaMnO3). 721... Substances § 721.10010 Barium manganese oxide (BaMnO3). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as barium manganese oxide (BaMnO3) (PMN P-00...

  2. Manganese

    ... research suggests that taking a specific product (7-Keto Naturalean) containing manganese, 7-oxo-DHEA, L-tyrosine, ... can absorb.Milk proteinAdding milk protein to the diet might increase the amount of manganese the body ...

  3. Manganese

    Fayziev, A.R.

    2002-01-01

    Present article is devoted to manganese content in fluoride. The manganese content of some geologic deposits of Tajikistan was determined by means of chemical analysis. The mono mineral samples of fluorite of 5 geologic deposits of various mineralogical and genetic type was studied. The manganese content in fluorite of geologic deposits of various mineralogical and genetic type was defined.

  4. Bentonite Modification with Manganese Oxides and Its Characterization

    Dolinská, S.; Schütz, T.; Znamenáčková, I.; Lovás, M.; Vaculíková, Lenka

    2015-01-01

    Roč. 35, č. 1 (2015), s. 213-218 ISSN 1640-4920 Institutional support: RVO:68145535 Keywords : bentonite * natrification * manganese oxide Subject RIV: CB - Analytical Chemistry, Separation http://www.potopk.com.pl/ Full _text/2015_full/IM%202-2015-a35.pdf

  5. Identifying active surface phases for metal oxide electrocatalysts: a study of manganese oxide bi-functional catalysts for oxygen reduction and water oxidation catalysis

    Su, Hai-Yan; Gorlin, Yelena; Man, Isabela Costinela

    2012-01-01

    Progress in the field of electrocatalysis is often hampered by the difficulty in identifying the active site on an electrode surface. Herein we combine theoretical analysis and electrochemical methods to identify the active surfaces in a manganese oxide bi-functional catalyst for the oxygen...... reduction reaction (ORR) and the oxygen evolution reaction (OER). First, we electrochemically characterize the nanostructured α-Mn2O3 and find that it undergoes oxidation in two potential regions: initially, between 0.5 V and 0.8 V, a potential region relevant to the ORR and, subsequently, between 0.8 V...

  6. Determination of the oxidizing capacity of manganese ores.

    Prasad, R

    1974-09-01

    An accurate method is described for determining the amount of active oxygen in manganese ores, based on the oxidation-reduction reaction between the ore and arsenic(III) in presence of ammonium molybdate, followed by the back-titration of excess of arsenic(III) with cerium(IV), using osmium tetroxide as catalyst and Disulphine Blue V as indicator. A survey has been made of the applicability of this method to various pyrolusite ores containing less than 0.2% phosphorus. Aluminium(III), copper(II), iron(III), manganese(II), and molybdenum(VI) do not interfere. Up to 30% phosphorus(V) causes no interference.

  7. Reduction of ripening time of full-scale manganese removal filters with manganese oxide-coated media

    Bruins, J.H.; Petrusevski, B.; Slokar, Y.M.; Huysman, K.; Joris, K.; Kruithof, J.C.; Kennedy, M.D.

    2015-01-01

    Effective manganese removal by conventional aeration-filtration with virgin filter media requires a long ripening time. The aim of this study was to assess the potential of manganese oxide-coated media to shorten the ripening time of filters with virgin media, under practical conditions. A full

  8. Manganese oxidation state mediates toxicity in PC12 cells

    Reaney, S.H.; Smith, D.R.

    2005-01-01

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

  9. Homoepitaxial Nanostructures of Zinc Oxide

    Tatiana V. Plakhova

    2015-01-01

    Full Text Available The homoepitaxial ZnO nanostructures (HENS were obtained on different substrates using various techniques. The first type of homoepitaxial ZnO nanorod arrays was grown on Si or ITO substrates by using two alternative sequences: (a seeding → growth from solution → growth from vapor and contrariwise (b seeding → growth from vapor → growth from solution. As follows from transport and cathode luminescence measurements homoepitaxial growth allows enhancing electrical or luminescence properties. The second type of HENS was prepared by growth of vertically or horizontally oriented ZnO nanorod arrays depending on monocrystalline ZnO wafers with [0001] and [10-10] orientation. In all cases the growth occurs along the c-axis of fast growth.

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

    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.

  11. In Situ Atom Probe Deintercalation of Lithium-Manganese-Oxide.

    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.

  12. Laser-driven coating of vertically aligned carbon nanotubes with manganese oxide from metal organic precursors for energy storage

    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).

  13. Iron and manganese oxides modified maize straw to remove tylosin from aqueous solutions.

    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 oxides 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.

  14. Selective Oxidations using Nanostructured Heterogeneous Catalysts

    Mielby, Jerrik Jørgen

    and because they produce H2O as the only by-product. Chapter 1 gives a short introduction to basic concepts in heterogeneous catalysis and green chemistry. Furthermore, the chapter gives an overview of the most important strategies to synthesise functional nanostructured materials and highlights how detailed......The aim of this thesis is to investigate and develop new efficient methods to oxidise alcohols and amines using heterogeneous catalysts and either O2 or H2O2 as oxidants. From an economic and environmental point of view, these oxidants are ideal, because they are cheap and readily available...... understanding of size, shape and structure can help in the development of new and more efficient heterogeneous catalysts. The chapter is not intended to give a complete survey, but rather to introduce some of the recent developments in the synthesis of nanostructured heterogeneous catalysts. Finally...

  15. Tailor-made ultrathin manganese oxide nanostripes: ‘magic widths’ on Pd(1 1 N) terraces

    Franchini, C.; Li, F.; Surnev, S.; Podloucky, R.; Allegretti, F.; Netzer, F. P.

    2012-02-01

    The growth of ultrathin two-dimensional manganese oxide nanostripes on vicinal Pd(1 1 N) surfaces leads to particular stable configurations for certain combinations of oxide stripe and substrate terrace widths. Scanning tunneling microscopy and high-resolution low-energy electron diffraction measurements reveal highly ordered nanostructured surfaces with excellent local and long-range order. Density functional theory calculations provide the physical origin of the stabilization mechanism of ‘magic width’ stripes in terms of a finite-size effect, caused by the significant relaxations observed at the stripe boundaries.

  16. Laser microstructuring and annealing processes for lithium manganese oxide cathodes

    Proell, J.; Kohler, R.; Torge, M.; Ulrich, S.; Ziebert, C.; Bruns, M.; Seifert, H.J.; Pfleging, W.

    2011-01-01

    It is expected that cathodes for lithium-ion batteries (LIB) composed out of nano-composite materials lead to an increase in power density of the LIB due to large electrochemically active surface areas but cathodes made of lithium manganese oxides (Li-Mn-O) suffer from structural instabilities due to their sensitivity to the average manganese oxidation state. Therefore, thin films in the Li-Mn-O system were synthesized by non-reactive radiofrequency magnetron sputtering of a spinel lithium manganese oxide target. For the enhancement of the power density and cycle stability, large area direct laser patterning using UV-laser radiation with a wavelength of 248 nm was performed. Subsequent laser annealing processes were investigated in a second step in order to set up a spinel-like phase using 940 nm laser radiation at a temperature of 680 deg. C. The interaction processes between UV-laser radiation and the material was investigated using laser ablation inductively coupled plasma mass spectroscopy. The changes in phase, structure and grain shape of the thin films due to the annealing process were recorded using Raman spectroscopy, X-ray diffraction and scanning electron microscopy. The structured cathodes were cycled using standard electrolyte and a metallic lithium anode. Different surface structures were investigated and a significant increase in cycling stability was found. Surface chemistry of an as-deposited as well as an electrochemically cycled thin film was investigated via X-ray photoelectron spectroscopy.

  17. Diode laser heat treatment of lithium manganese oxide films

    Pröll, J.; Kohler, R.; Mangang, A.; Ulrich, S.; Bruns, M.; Seifert, H.J.; Pfleging, W.

    2012-01-01

    The crystallization of lithium manganese oxide thin films prepared by radio frequency magnetron sputtering on stainless steel substrates under 10 Pa argon pressure is demonstrated by a laser annealing technique. Laser annealing processes were developed as a function of annealing time and temperature with the objective to form an electrochemically active lithium manganese oxide cathode. It is demonstrated, that laser annealing with 940 nm diode laser radiation and an annealing time of 2000 s at 600 °C delivers appropriate parameters for formation of a crystalline spinel-like phase. Characteristic features of this phase could be detected via Raman spectroscopy, showing the characteristic main Raman band at 627 cm -1 . Within cyclic voltammetric measurements, the two characteristic redox pairs for spinel lithium manganese oxide in the 4 V region could be detected, indicating that the film was well-crystallized and de-/intercalation processes were reversible. Raman post-analysis of a cycled cathode showed that the spinel-like structure was preserved within the cycling process but mechanical degradation effects such as film cracking were observed via scanning electron microscopy. Typical features for the formation of an additional surface reaction layer could be detected using X-ray photoelectron spectroscopy.

  18. Impedance analysis of nanostructured iridium oxide electrocatalysts

    Sunde, Svein; Lervik, Ingrid Anne; Tsypkin, Mikhail; Owe, Lars-Erik

    2010-01-01

    Impedance data were collected for nanostructured iridium oxide (NIROF) at potentials below those at which the oxygen evolution reaction commences. The measurements included thin oxide films covered by a protective Nafion TM layer and thicker composite Nafion TM -oxide electrodes. The time constants for the low-frequency diffusion process were approximately the same for both types of electrodes, indicating diffusion in individual particles in the porous electrode rather than across the film. The diffusion process involves trapping of the diffusion species. The impedance data indicated that there were no significant variations in conductivity of the oxides with potential, as opposed to what appears to be the case for anodically formed iridium oxide films (AIROF). This is interpreted to reflect differences in electronic structure between NIROF and AIROF.

  19. Influence of oxalic acid on the dissolution kinetics of manganese oxide

    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.

  20. Manganese

    Cannon, William F.; Kimball, Bryn E.; Corathers, Lisa A.; Schulz, Klaus J.; DeYoung,, John H.; Seal, Robert R.; Bradley, Dwight C.

    2017-12-19

    Manganese is an essential element for modern industrial societies. Its principal use is in steelmaking, where it serves as a purifying agent in iron-ore refining and as an alloy that converts iron into steel. Although the amount of manganese consumed to make a ton of steel is small, ranging from 6 to 9 kilograms, it is an irreplaceable component in the production of this fundamental material. The United States has been totally reliant on imports of manganese for many decades and will continue to be so for at least the near future. There are no domestic reserves, and although some large low-grade resources are known, they are far inferior to manganese ores readily available on the international market. World reserves of manganese are about 630 million metric tons, and annual global consumption is about 16 million metric tons. Current reserves are adequate to meet global demand for several decades. Global resources in traditional land-based deposits, including both reserves and rocks sufficiently enriched in manganese to be ores in the future, are much larger, at about 17 billion metric tons. Manganese resources in seabed deposits of ferromanganese nodules and crusts are larger than those on land and have not been fully quantified. No production from seabed deposits has yet been done, but current research and development activities are substantial and may bring parts of these seabed resources into production in the future. The advent of economically successful seabed mining could substantially alter the current scenario of manganese supply by providing a large new source of manganese in addition to traditional land-based deposits.From a purely geologic perspective, there is no global shortage of proven ores and potential new ores that could be developed from the vast tonnage of identified resources. Reserves and resources are very unevenly distributed, however. The Kalahari manganese district in South Africa contains 70 percent of the world’s identified resources

  1. Synthesis and Characterization of Mixed Iron-Manganese Oxide Nanoparticles and Their Application for Efficient Nickel Ion Removal from Aqueous Samples

    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

  2. Synthesis and Characterization of Mixed Iron-Manganese Oxide Nanoparticles and Their Application for Efficient Nickel Ion Removal from Aqueous Samples

    Alessandro Buccolieri

    2017-01-01

    Full Text Available 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.

  3. Highly Conductive One-Dimensional Manganese Oxide Wires by Coating with Graphene Oxides

    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.

  4. Constraints on superoxide mediated formation of manganese oxides

    Deric R. Learman

    2013-09-01

    Full Text Available 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, 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.

  5. Advanced manganese oxide material for rechargeable lithium cells

    Atwater, Terrill B.; Salkind, Alvin J. [Rutgers University, Piscataway, NJ (United States)

    2006-11-22

    A family of potassium-doped manganese oxide materials were synthesized with the stoichiometric formula Li{sub 0.9-X}K{sub X}Mn{sub 2}O{sub 4}, where X=0.0-0.25 and evaluated for their viability as a cathode material for a rechargeable lithium battery. A performance maximum was found at X=0.1 where the initial specific capacity for the lithium-potassium-doped manganese dioxide electrochemical couple was 130mAhg{sup -1} of active cathode material. The discharge capacity of the system was maintained through 90 cycles (95% initial capacity). Additionally, the capacity was maintained at greater than 90% initial discharge through 200 cycles. Other variants demonstrated greater than 75% initial discharge through 200 cycles at comparable capacity. (author)

  6. An engineered polypeptide around nano-sized manganese-calcium oxide: copying plants for water oxidation.

    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.

  7. Fast degradation of dyes in water using manganese-oxide-coated diatomite for environmental remediation

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

    2016-11-01

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

  8. Interfaces and nanostructures of oxide octahedral frameworks

    Felip eSandiumenge

    2014-08-01

    Full Text Available In the past decade, the rich physics exhibited by solid interfaces combining octahedral framework structures of transition metal oxides has fascinated the materials science community. However, the behavior of these materials still elude the current understanding of classical semiconductor and metal epitaxy. The reason for that is rooted in the surprising versatility of linked coordination units to adapt to a dissimilar substrate and the strong sensitivity of correlated oxides to external perturbations. The confluence of atomic control in oxide thin film epitaxy, state of the art high spatial resolution characterization techniques, and electronic structure computations, has allowed in recent years to obtain first insights on the underlying microscopic mechanisms governing the epitaxy of these fascinating materials. Here, we shortly review these mechanisms and highlight their potential in the design of novel nanostructures with enhanced functionalities.

  9. Nanorods of manganese oxides: Synthesis, characterization and catalytic application

    Yang, Zeheng; Zhang, Yuancheng; Zhang, Weixin; Wang, Xue; Qian, Yitai; Wen, Xiaogang; Yang, Shihe

    2006-03-01

    Single-crystalline nanorods of β-MnO 2, α-Mn 2O 3 and Mn 3O 4 were successfully synthesized via the heat-treatment of γ-MnOOH nanorods, which were prepared through a hydrothermal method in advance. The calcination process of γ-MnOOH nanorods was studied with the help of Thermogravimetric analysis and X-ray powder diffraction. When the calcinations were conducted in air from 250 to 1050 °C, the precursor γ-MnOOH was first changed to β-MnO 2, then to α-Mn 2O 3 and finally to Mn 3O 4. When calcined in N 2 atmosphere, γ-MnOOH was directly converted into Mn 3O 4 at as low as 500 °C. Transmission electron microscopy (TEM) and high-resolution TEM were also used to characterize the products. The obtained manganese oxides maintain the one-dimensional morphology similar to the precursor γ-MnOOH nanorods. Further experiments show that the as-prepared manganese oxide nanorods have catalytic effect on the oxidation and decomposition of the methylene blue (MB) dye with H 2O 2.

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

    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

  11. Study of nitric oxide catalytic oxidation on manganese oxides-loaded activated carbon at low temperature

    You, Fu-Tian [Key Laboratory of Urban Pollutant Conversion, Institute of Urban Environment, Chinese Academy of Sciences, Xiamen (China); University of Chinese Academy of Sciences, Beijing (China); Yu, Guang-Wei, E-mail: gwyu@iue.ac.cn [Key Laboratory of Urban Pollutant Conversion, Institute of Urban Environment, Chinese Academy of Sciences, Xiamen (China); Wang, Yin, E-mail: yinwang@iue.ac.cn [Key Laboratory of Urban Pollutant Conversion, Institute of Urban Environment, Chinese Academy of Sciences, Xiamen (China); Xing, Zhen-Jiao [Key Laboratory of Urban Pollutant Conversion, Institute of Urban Environment, Chinese Academy of Sciences, Xiamen (China); Liu, Xue-Jiao; Li, Jie [Key Laboratory of Urban Pollutant Conversion, Institute of Urban Environment, Chinese Academy of Sciences, Xiamen (China); University of Chinese Academy of Sciences, Beijing (China)

    2017-08-15

    Highlights: • Loading manganese oxides on activated carbon effectively promotes NO oxidation. • NO adsorption-desorption on activated carbon is fundamental to NO oxidation. • A high Mn{sup 4+}/Mn{sup 3+} ratio contributes to NO oxidation by promoting lattice O transfer. - Abstract: Nitric oxide (NO) is an air pollutant that is difficult to remove at low concentration and low temperature. Manganese oxides (MnO{sub x})-loaded activated carbon (MLAC) was prepared by a co-precipitation method and studied as a new catalyst for NO oxidation at low temperature. Characterization of MLAC included X-ray diffraction (XRD), scanning electron microscopy (SEM), N{sub 2} adsorption/desorption and X-ray photoelectron spectroscopy (XPS). Activity tests demonstrated the influence of the amount of MnO{sub x} and the test conditions on the reaction. MLAC with 7.5 wt.% MnO{sub x} (MLAC003) exhibits the highest NO conversion (38.7%) at 1000 ppm NO, 20 vol.% O{sub 2}, room temperature and GHSV ca. 16000 h{sup −1}. The NO conversion of MLAC003 was elevated by 26% compared with that of activated carbon. The results of the MLAC003 activity test under different test conditions demonstrated that NO conversion is also influenced by inlet NO concentration, inlet O{sub 2} concentration, reaction temperature and GHSV. The NO adsorption-desorption process in micropores of activated carbon is fundamental to NO oxidation, which can be controlled by pore structure and reaction temperature. The activity elevation caused by MnO{sub x} loading is assumed to be related to Mn{sup 4+}/Mn{sup 3+} ratio. Finally, a mechanism of NO catalytic oxidation on MLAC based on NO adsorption-desorption and MnO{sub x} lattice O transfer is proposed.

  12. Population structure of manganese-oxidizing bacteria in stratified soils and properties of manganese oxide aggregates under manganese-complex medium enrichment.

    Weihong Yang

    Full Text Available 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

  13. 76 FR 47996 - Cobalt Lithium Manganese Nickel Oxide; Significant New Use Rule

    2011-08-08

    ... Safety and Health Administration (OSHA) Permissible Exposure Level (PEL) of 0.1 mg/m\\3\\ for nickel. The... 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...

  14. Field-induced resistance switching at metal/perovskite manganese oxide interface

    Ohkubo, I.; Tsubouchi, K.; Harada, T.; Kumigashira, H.; Itaka, K.; Matsumoto, Y.; Ohnishi, T.; Lippmaa, M.; Koinuma, H.; Oshima, M.

    2008-01-01

    Planar type metal/insulator/metal structures composed of an epitaxial perovskite manganese oxide layer and various metal electrodes were prepared for electric-field-induced resistance switching. Only the electrode pairs including Al show good resistance switching and the switching ratio reaches its maximum of 1000. This resistance switching occurs around the interface between Al electrodes and epitaxial perovskite manganese oxide thin films

  15. Adsorption behavior of lithium from seawater using manganese oxide adsorbent

    Wajima, Takaaki; Munakata, Kenzo; Uda, Tatsuhiko

    2012-01-01

    The deuterium-tritium (D-T) fusion reactor system is expected to provide the main source of electricity in the future. Large amounts of lithium will be required, dependent on the reactor design concept, and alternative resources should be found to provide lithium inventories for nuclear fusion plants. Seawater has recently become an attractive source of this element and the separation and recovery of lithium from seawater by co-precipitation, solvent extraction and adsorption have been investigated. Amongst these techniques, the adsorption method is suitable for recovery of lithium from seawater, because certain inorganic ion-exchange materials, especially spinel-type manganese oxides, show extremely high selectivity for the lithium ion. In this study, we prepared a lithium adsorbent (HMn 2 O 4 ) by elution of spinel-type lithium di-manganese-tetra-oxide (LiMn 2 O 4 ) and examined the kinetics of the adsorbent for lithium ions in seawater using a pseudo-second-order kinetic model. The intermediate, LiMn 2 O 4 , can be synthesized from LiOH·H 2 O and Mn 3 O 4 , from which the lithium adsorbent can subsequently be prepared via acid treatment., The adsorption kinetics become faster and the amount of lithium adsorbed on the adsorbent increases with increasing solution temperature. The thermodynamic values, ΔG 0 , ΔH 0 and ΔS 0 , indicate that adsorption is an endothermic and spontaneous process. (author)

  16. Manganese Oxide on Carbon Fabric for Flexible Supercapacitors

    Jianfeng Zhang

    2016-01-01

    Full Text Available We report the fabrication of uniform large-area manganese oxide (MnO2 nanosheets on carbon fabric which oxidized using O2 plasma treatment (MnO2/O2-carbon fabric via electrodeposition process and their implementation as supercapacitor electrodes. Electrochemical measurements demonstrated that MnO2/O2-carbon fabric exhibited capacitance as high as 275 F/g at a scan rate of 5 mV/s; in addition, it showed an excellent cycling performance (less than 20% capacitance loss after 10,000 cycles. All the results suggest that MnO2/O2-carbon fabric is a promising electrode material which has great potential for application on flexible supercapacitors.

  17. Electrosynthesis of Biomimetic Manganese-Calcium Oxides for Water Oxidation Catalysis--Atomic Structure and Functionality.

    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.

  18. Significant enhancement in thermoelectric performance of nanostructured higher manganese silicides synthesized employing a melt spinning technique.

    Muthiah, Saravanan; Singh, R C; Pathak, B D; Avasthi, Piyush Kumar; Kumar, Rishikesh; Kumar, Anil; Srivastava, A K; Dhar, Ajay

    2018-01-25

    The limited thermoelectric performance of p-type Higher Manganese Silicides (HMS) in terms of their low figure-of-merit (ZT), which is far below unity, is the main bottle-neck for realising an efficient HMS based thermoelectric generator, which has been recognized as the most promising material for harnessing waste-heat in the mid-temperature range, owing to its thermal stability, earth-abundant and environmentally friendly nature of its constituent elements. We report a significant enhancement in the thermoelectric performance of nanostructured HMS synthesized using rapid solidification by optimizing the cooling rates during melt-spinning followed by spark plasma sintering of the resulting melt-spun ribbons. By employing this experimental strategy, an unprecedented ZT ∼ 0.82 at 800 K was realized in spark plasma sintered 5 at% Al-doped MnSi 1.73 HMS, melt spun at an optimized high cooling rate of ∼2 × 10 7 K s -1 . This enhancement in ZT represents a ∼25% increase over the best reported values thus far for HMS and primarily originates from a nano-crystalline microstructure consisting of a HMS matrix (20-40 nm) with excess Si (3-9 nm) uniformly distributed in it. This nanostructure, resulting from the high cooling rates employed during the melt-spinning of HMS, introduces a high density of nano-crystallite boundaries in a wide spectrum of nano-scale dimensions, which scatter the low-to-mid-wavelength heat-carrying phonons. This abundant phonon scattering results in a significantly reduced thermal conductivity of ∼1.5 W m -1 K -1 at 800 K, which primarily contributes to the enhancement in ZT.

  19. Nanostructured Solid Oxide Fuel Cell Electrodes

    Sholklapper, Tal Zvi [Univ. of California, Berkeley, CA (United States)

    2007-01-01

    The ability of Solid Oxide Fuel Cells (SOFC) to directly and efficiently convert the chemical energy in hydrocarbon fuels to electricity places the technology in a unique and exciting position to play a significant role in the clean energy revolution. In order to make SOFC technology cost competitive with existing technologies, the operating temperatures have been decreased to the range where costly ceramic components may be substituted with inexpensive metal components within the cell and stack design. However, a number of issues have arisen due to this decrease in temperature: decreased electrolyte ionic conductivity, cathode reaction rate limitations, and a decrease in anode contaminant tolerance. While the decrease in electrolyte ionic conductivities has been countered by decreasing the electrolyte thickness, the electrode limitations have remained a more difficult problem. Nanostructuring SOFC electrodes addresses the major electrode issues. The infiltration method used in this dissertation to produce nanostructure SOFC electrodes creates a connected network of nanoparticles; since the method allows for the incorporation of the nanoparticles after electrode backbone formation, previously incompatible advanced electrocatalysts can be infiltrated providing electronic conductivity and electrocatalysis within well-formed electrolyte backbones. Furthermore, the method is used to significantly enhance the conventional electrode design by adding secondary electrocatalysts. Performance enhancement and improved anode contamination tolerance are demonstrated in each of the electrodes. Additionally, cell processing and the infiltration method developed in conjunction with this dissertation are reviewed.

  20. Preparation and performance of manganese-oxide-coated zeolite for the removal of manganese-contamination in groundwater.

    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.

  1. Carbon and oxide nanostructures. Synthesis, characterisation and applications

    Yahya, Noorhana [Universiti Teknologi PETRONAS, Tronoh, Perak (Malaysia). Dept. of Fundamental and Applied Sciences

    2010-07-01

    This volume covers all aspects of carbon and oxide based nanostructured materials. The topics include synthesis, characterization and application of carbon-based namely carbon nanotubes, carbon nanofibres, fullerenes, carbon filled composites etc. In addition, metal oxides namely, ZnO, TiO2, Fe2O3, ferrites, garnets etc., for various applications like sensors, solar cells, transformers, antennas, catalysts, batteries, lubricants, are presented. The book also includes the modeling of oxide and carbon based nanomaterials. The book covers the topics: - Synthesis, characterization and application of carbon nanotubes, carbon nanofibres, fullerenes - Synthesis, characterization and application of oxide based nanomaterials. - Nanostructured magnetic and electric materials and their applications. - Nanostructured materials for petro-chemical industry. - Oxide and carbon based thin films for electronics and sustainable energy. - Theory, calculations and modeling of nanostructured materials. (orig.)

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

    Naa, Christian Fredy, E-mail: chris@cphys.fi.itb.ac.id [Physics Department, Faculty of Mathematics and Natural Science, Institut Teknologi Bandung, Jalan Ganesha 10 Bandung (Indonesia); Unité de Dynamique et Structure des Matérioux Moléculaires, Université Littoral Côte d’Opale, Maison de la Reserche Blaise Pascal 50, rue Ferdinand Buisson, Calais, France email (France); Suprijadi,, E-mail: supri@fi.itb.ac.id; Viridi, Sparisoma, E-mail: dudung@fi.itb.ac.id; Djamal, Mitra, E-mail: mitra@fi.itb.ac.id [Physics Department, Faculty of Mathematics and Natural Science, Institut Teknologi Bandung, Jalan Ganesha 10 Bandung (Indonesia); Fasquelle, Didier, E-mail: didier.fasquelle@univ-littoral.fr [Unité de Dynamique et Structure des Matérioux Moléculaires, Université Littoral Côte d’Opale, Maison de la Reserche Blaise Pascal 50, rue Ferdinand Buisson, Calais, France email (France)

    2015-09-30

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

  3. A magnetic route to measure the average oxidation state of mixed-valent manganese in manganese oxide octahedral molecular sieves (OMS).

    Shen, Xiong-Fei; Ding, Yun-Shuang; Liu, Jia; Han, Zhao-Hui; Budnick, Joseph I; Hines, William A; Suib, Steven L

    2005-05-04

    A magnetic route has been applied for measurement of the average oxidation state (AOS) of mixed-valent manganese in manganese oxide octahedral molecular sieves (OMS). The method gives AOS measurement results in good agreement with titration methods. A maximum analysis deviation error of +/-7% is obtained from 10 sample measurements. The magnetic method is able to (1) confirm the presence of mixed-valent manganese and (2) evaluate AOS and the spin states of d electrons of both single oxidation state and mixed-valent state Mn in manganese oxides. In addition, the magnetic method may be extended to (1) determine AOS of Mn in manganese oxide OMS with dopant "diamagnetic" ions, such as reducible V5+ (3d0) ions, which is inappropriate for the titration method due to interference of redox reactions between these dopant ions and titration reagents, such as KMnO4, (2) evaluate the dopant "paramagnetic" ions that are present as clusters or in the OMS framework, and (3) determine AOS of other mixed-valent/single oxidation state ion systems, such as Mo3+(3d3)-Mo4+(3d2) systems and Fe3+ in FeCl3.

  4. Synthesis and characterization of cobalt-manganese oxides

    Valencia, J. [Laboratorio de Magnetismo y Materiales Avanzados, Facultad de Ciencias Exactas y Naturales, Universidad Nacional de Colombia, Sede Manizales, Manizales (Colombia); Department of Aerospace Engineering and Mechanics, University of Minnesota, Minneapolis 55455-0153 (United States); Arias, N.P. [Laboratorio de Materiales Nanoestructurados y Funcionales, Facultad de Ciencias Exactas y Naturales, Universidad Nacional de Colombia, Sede Manizales, Manizales (Colombia); Departamento de Ingenieria Electrica, Electronica y Computacion, Facultad de Ingenieria y Arquitectura, Universidad Nacional de Colombia, Sede Manizales, Manizales (Colombia); Giraldo, O. [Laboratorio de Materiales Nanoestructurados y Funcionales, Facultad de Ciencias Exactas y Naturales, Universidad Nacional de Colombia, Sede Manizales, Manizales (Colombia); Rosales-Rivera, A., E-mail: arosalesr@unal.edu.co [Laboratorio de Magnetismo y Materiales Avanzados, Facultad de Ciencias Exactas y Naturales, Universidad Nacional de Colombia, Sede Manizales, Manizales (Colombia)

    2012-08-15

    Cobalt doped/un-doped manganese oxides materials were synthesized at various doping rates by soft chemical reactions, oxidation-reduction method, which allows generating a metal-mixed oxide. The synthesized materials were characterized using several techniques including chemical analysis, X-rays diffraction (XRD), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), and vibrating sample magnetometer (VSM). The chemical analysis confirmed the presence of cobalt in the samples. XRD patterns reveal mainly a spinel-like structure and SEM micrographs exhibited morphology with fine aggregate of particles. TGA profiles showed weight loss due to loss of water in a first step, followed by a loss of oxygen from the lattice associated with partial reduction of Mn{sup 4+} to Mn{sup 3+}. VSM was used to measure the magnetization as a function of the applied magnetic field at temperatures T=50 and 300 K. Different magnetic behaviors were observed when cobalt percentage changed in the samples. These behaviors are considered to be related to the size of the particles and composition of the materials. Higher coercive field and lesser magnetization were observed for the sample with higher cobalt content.

  5. Oxidative damage and neurodegeneration in manganese-induced neurotoxicity

    Milatovic, Dejan; Zaja-Milatovic, Snjezana; Gupta, Ramesh C.; Yu, Yingchun; Aschner, Michael

    2009-01-01

    Exposure to excessive manganese (Mn) levels results in neurotoxicity to the extrapyramidal system and the development of Parkinson's disease (PD)-like movement disorder, referred to as manganism. Although the mechanisms by which Mn induces neuronal damage are not well defined, its neurotoxicity appears to be regulated by a number of factors, including oxidative injury, mitochondrial dysfunction and neuroinflammation. To investigate the mechanisms underlying Mn neurotoxicity, we studied the effects of Mn on reactive oxygen species (ROS) formation, changes in high-energy phosphates (HEP), neuroinflammation mediators and associated neuronal dysfunctions both in vitro and in vivo. Primary cortical neuronal cultures showed concentration-dependent alterations in biomarkers of oxidative damage, F 2 -isoprostanes (F 2 -IsoPs) and mitochondrial dysfunction (ATP), as early as 2 h following Mn exposure. Treatment of neurons with 500 μM Mn also resulted in time-dependent increases in the levels of the inflammatory biomarker, prostaglandin E 2 (PGE 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 2 -IsoPs and PGE 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.

  6. Synthesis and characterization of cobalt-manganese oxides

    Valencia, J.; Arias, N.P.; Giraldo, O.; Rosales-Rivera, A.

    2012-01-01

    Cobalt doped/un-doped manganese oxides materials were synthesized at various doping rates by soft chemical reactions, oxidation-reduction method, which allows generating a metal-mixed oxide. The synthesized materials were characterized using several techniques including chemical analysis, X-rays diffraction (XRD), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), and vibrating sample magnetometer (VSM). The chemical analysis confirmed the presence of cobalt in the samples. XRD patterns reveal mainly a spinel-like structure and SEM micrographs exhibited morphology with fine aggregate of particles. TGA profiles showed weight loss due to loss of water in a first step, followed by a loss of oxygen from the lattice associated with partial reduction of Mn 4+ to Mn 3+ . VSM was used to measure the magnetization as a function of the applied magnetic field at temperatures T=50 and 300 K. Different magnetic behaviors were observed when cobalt percentage changed in the samples. These behaviors are considered to be related to the size of the particles and composition of the materials. Higher coercive field and lesser magnetization were observed for the sample with higher cobalt content.

  7. Effect of mass density on surface morphology of electrodeposited manganese oxide films

    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.

  8. Correlation among physical and electrochemical behaviour of nanostructured electrolytic manganese dioxide from leach liquor and synthetic for aqueous asymmetric capacitor.

    Minakshi Sundaram, Manickam; Biswal, Avijit; Mitchell, David; Jones, Rob; Fernandez, Carlos

    2016-02-14

    An attempt has been made to correlate the differences in structural parameters, surface areas, morphology etc. with the electrochemical capacitive behaviour of the EMDs. The nanostructured electrolytic manganese dioxides (EMD) have been synthesized through electrodepositing MnO2 from two different leach liquors and a synthetic analogue thereof. The structural and chemical state was determined using X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) respectively. Multiplet structure determination led to estimates of the manganese valence states present in the EMD. The EMDs have been tested in an asymmetric capacitor which we have developed. This used activated carbon as the negative electrode and the various EMDs as the positive electrode. Aqueous 2 M NaOH solution was used as the electrolyte. The capacitor achieved 1.6 V corresponding to a capacitance of ∼50 F g(-1) of the EMDs from leach liquors. The EMD derived from the synthetic solution showed an inferior capacitance of 25 F g(-1). Extended cycling (2000 cycles), showed 100% capacity retention was achieved for one EMD produced from the leach liquor derived from low-grade manganese ore/residue. This outstanding capacitor performance was correlated with the presence of a nanofibrous morphology. These findings open up the possibility of extracting a high performance EMD product from a low cost, low-grade source of manganese.

  9. Stability of a novel synthetic amorphous manganese oxide in contrasting soils

    Ettler, V.; Knytl, V.; Komárek, M.; Della Puppa, L.; Bordas, F.; Mihaljevič, M.; Klementová, Mariana; Šebek, O.

    2014-01-01

    Roč. 214, FEB (2014), s. 2-9 ISSN 0016-7061 Institutional support: RVO:61388980 Keywords : Amorphous manganese oxide * Stability * Soils * Chemical stabilization * Pollution Subject RIV: CA - Inorganic Chemistry Impact factor: 2.772, year: 2014

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

    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.

  11. The origin of ferro-manganese oxide coated pumice from the Central Indian Ocean Basin

    Pattan, J.N.; Pearce, N.J.G.; Parthiban, G.; Smith, V.C.; Mudholkar, A.V.; Rao, N.R

    Pumice clasts, partially and fully coated with ferro-manganese oxide from the Central Indian Ocean Basin (CIOB) were analysed for major, trace and rare earth elements; and glass and mineral grain chemistry to assess their possible source...

  12. Preparation of the Nanostructured Radioisotope Metallic Oxide by Neutron Irradiation for Use as Radiotracers

    Sang-Ei Seo

    2017-10-01

    Full Text Available Metallic oxides manganese dioxide (MnO2, samarium oxide (Sm2O3, and dysprosium oxide (Dy2O3 with nanorod-like structures were synthesized by the hydrothermal synthesis method, respectively. Subsequently, the nanostructured radioisotopes MnO2 with Mn-56, Sm2O3 with Sm-153, and Dy2O3 with Dy-165 were prepared by neutron irradiation from the HANARO research reactor, respectively. The three different elements, Mn, Sm, and Dy, were selected as radiotracers because these elements can be easily gamma-activated from neutrons (activation limits: 1 picogram (Dy, 1–10 picogram (Mn, 10–100 picogram (Sm. Furthermore, the synthesized radioisotopes can be used as radiotracers in Prompt Gamma Neutron Activation Analysis as the rare earth metals Dy and Sm were not present in the Korean environment. The successful synthesis of the radioisotope metallic oxides was confirmed by Transmission Electron Microscopy (TEM, Energy Dispersive X-ray Spectrometry (EDS, X-ray Diffraction (XRD analysis, and gamma spectroscopy analysis. The synthesized nanostructured radioisotope metallic oxides may be used as radiotracers in scientific, environmental, engineering, and industrial fields.

  13. Ytterbia doped nickel–manganese mixed oxide catalysts for liquid phase oxidation of benzyl alcohol

    S.S.P. Sultana

    2017-11-01

    Full Text Available Nickel–manganese mixed oxides doped with 1, 3, 5 mol% ytterbia have been prepared by co-precipitation method and used in the catalytic oxidation of benzyl alcohol. Catalytic activity of these oxides calcined at 400 °C and 500 °C was studied for selective oxidation of benzyl alcohol to the corresponding aldehyde using molecular oxygen as an oxidizing agent. The results showed that thermally stable 5 mol% ytterbia doped nickel–manganese oxide [Yb2O3-(5%-Ni6MnO8] exhibited highest catalytic performance when it was calcined at 400 °C. A 100% conversion of the benzyl alcohol was achieved with >99% selectivity to benzaldehyde within a reaction period of 5 h at 100 °C. The mixed oxide prepared has been characterized by scanning election microscopy (SEM and energy dispersive X-ray analysis (EDXA, X-ray diffraction (XRD, Fourier transform infrared spectroscopy (FT-IR, thermogravimetric analysis (TGA, Brunauer–Emmett–Teller (BET and temperature programed reduction (H2-TPR.

  14. Oxidation of bisphenol F (BPF) by manganese dioxide

    Lu Zhijiang; Lin Kunde; Gan, Jay

    2011-01-01

    Bisphenol F (BPF), an environmental estrogen, is used as a monomer in plastic industry and its environmental fate and decontamination are emerging concern. This study focused on the kinetics, influencing factors and pathways of its oxidation by MnO 2 . At pH 5.5, about 90% of BPF was oxidized in 20 min in a solution containing 100 μM MnO 2 and 4.4 μM BPF. The reaction was pH-dependent, following an order of pH 4.5 > pH 5.5 > pH 8.6 > pH 7.5 > pH 6.5 > pH 9.6. Humic acids inhibited the reaction at low (≤pH 5.5) and high pH (≥pH 8.6) at high concentrations. In addition, metal ions and anions also suppressed the reaction, following the order Mn 2+ > Ca 2+ > Mg 2+ > Na + and HPO 4 2- > Cl - > NO 3 - ∼ SO 4 2- , respectively. A total of 5 products were identified, from which a tentative pathway was proposed. - Highlights: → Manganese dioxide oxidizes bisphenol F rapidly at ambient temperature. → pH and co-solutes such as humic acids, metal ions and anions affect the reaction. → Identification of 5 reaction intermediates points to a tentative pathway involving free radicals. → The commonly occurring MnO 2 may be important in the natural attenuation of bisphenol F or used for its decontamination. - The commonly occurring MnO 2 shows a high reactivity toward bisphenol F, which may account for its natural attenuation and suggest a beneficial use of MnO 2 for managed removal of bisphenol F.

  15. Oxidation of bisphenol F (BPF) by manganese dioxide

    Lu Zhijiang [Department of Environmental Sciences, University of California, Riverside, CA 92521 (United States); Lin Kunde [College of Biological and Environmental Engineering Zhejiang University of Technology, Hangzhou 310032 (China); Gan, Jay, E-mail: jgan@ucr.edu [Department of Environmental Sciences, University of California, Riverside, CA 92521 (United States)

    2011-10-15

    Bisphenol F (BPF), an environmental estrogen, is used as a monomer in plastic industry and its environmental fate and decontamination are emerging concern. This study focused on the kinetics, influencing factors and pathways of its oxidation by MnO{sub 2}. At pH 5.5, about 90% of BPF was oxidized in 20 min in a solution containing 100 {mu}M MnO{sub 2} and 4.4 {mu}M BPF. The reaction was pH-dependent, following an order of pH 4.5 > pH 5.5 > pH 8.6 > pH 7.5 > pH 6.5 > pH 9.6. Humic acids inhibited the reaction at low ({<=}pH 5.5) and high pH ({>=}pH 8.6) at high concentrations. In addition, metal ions and anions also suppressed the reaction, following the order Mn{sup 2+} > Ca{sup 2+} > Mg{sup 2+} > Na{sup +} and HPO{sub 4}{sup 2-} > Cl{sup -} > NO{sub 3}{sup -} {approx} SO{sub 4}{sup 2-}, respectively. A total of 5 products were identified, from which a tentative pathway was proposed. - Highlights: > Manganese dioxide oxidizes bisphenol F rapidly at ambient temperature. > pH and co-solutes such as humic acids, metal ions and anions affect the reaction. > Identification of 5 reaction intermediates points to a tentative pathway involving free radicals. > The commonly occurring MnO{sub 2} may be important in the natural attenuation of bisphenol F or used for its decontamination. - The commonly occurring MnO{sub 2} shows a high reactivity toward bisphenol F, which may account for its natural attenuation and suggest a beneficial use of MnO{sub 2} for managed removal of bisphenol F.

  16. Structural and surface changes of cobalt modified manganese oxide during activation and ethanol steam reforming reaction

    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.

  17. Morphology evolution and nanostructure of chemical looping transition metal oxide materials upon redox processes

    Qin, Lang; Cheng, Zhuo; Guo, Mengqing; Fan, Jonathan A.; Fan, Liang-Shih

    2017-01-01

    Transition metal are heavily used in chemical looping technologies because of their high oxygen carrying capacity and high thermal reactivity. These oxygen activities result in the oxide formation and oxygen vacancy formation that affect the nanoscale crystal phase and morphology within these materials and their subsequent bulk chemical behavior. In this study, two selected earlier transition metals manganese and cobalt as well as two selected later transition metals copper and nickel that are important to chemical looping reactions are investigated when they undergo cyclic redox reactions. We found Co microparticles exhibited increased CoO impurity presence when oxidized to Co_3O_4 upon cyclic oxidation; CuO redox cycles prefer to be limited to a reduced form of Cu_2O and an oxidized form of CuO; Mn microparticles were oxidized to a mixed phases of MnO and Mn_3O_4, which causes delamination during oxidation. For Ni microparticles, a dense surface were observed during the redox reaction. The atomistic thermodynamics methods and density functional theory (DFT) calculations are carried out to elucidate the effect of oxygen dissociation and migration on the morphological evolution of nanostructures during the redox processes. Our results indicate that the earlier transition metals (Mn and Co) tend to have stronger interaction with O_2 than the later transition metals (Ni and Cu). Also, our modified Brønsted−Evans−Polanyi (BEP) relationship for reaction energies and total reaction barriers reveals that reactions of earlier transition metals are more exergonic and have lower oxygen dissociation barriers than those of later transition metals. In addition, it was found that for these transition metal oxides the oxygen vacancy formation energies increase with the depth. The oxide in the higher oxidation state of transition metal has lower vacancy formation energy, which can facilitate forming the defective nanostructures. The fundamental understanding of these metal

  18. Nanostructured Metal Oxides for Stoichiometric Degradation of Chemical Warfare Agents

    Štengl, Václav; Henych, Jiří; Janos, P.; Skoumal, M.

    2016-01-01

    Roč. 236, č. 2016 (2016), s. 239-258 ISSN 0179-5953 R&D Projects: GA ČR(CZ) GAP106/12/1116 Institutional support: RVO:61388980 Keywords : chemical warfare agent * metal nanoparticle * unique surface- chemistry * mesoporous manganese oxide Subject RIV: CA - Inorganic Chemistry Impact factor: 3.930, year: 2016

  19. A General and Mild Approach to Controllable Preparation of Manganese-Based Micro- and Nanostructured Bars for High Performance Lithium-Ion Batteries.

    Ma, Guo; Li, Sheng; Zhang, Weixin; Yang, Zeheng; Liu, Shulin; Fan, Xiaoming; Chen, Fei; Tian, Yuan; Zhang, Weibo; Yang, Shihe; Li, Mei

    2016-03-07

    One-dimensional (1D) micro- and nanostructured electrode materials with controllable phase and composition are appealing materials for use in lithium-ion batteries with high energy and power densities, but they are challenging to prepare. Herein, a novel ethanol-water mediated co-precipitation method by a chimie douce route (synthesis conducted under mild conditions) has been exploited to selectively prepare an extensive series of manganese-based electrode materials, manifesting the considerable generalizability and efficacy of the method. Moreover, by simply tuning the mixed solvent and reagents, transition metal oxide bars with differing aspect ratios and compositions were prepared with an unprecedented uniformity. Application prospects are demonstrated by Li-rich 0.5 Li2 MnO3 ⋅0.5 LiNi1/3 Co1/3 Mn1/3 O2 bars, which demonstrate excellent reversible capacity and rate capability thanks to the steerable nature of the synthesis and material quality. This work opens a new route to 1D micro- and nanostructured materials by customizing the precipitating solvent to orchestrate the crystallization process. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  20. Preparation and capacitive properties of lithium manganese oxide intercalation compound

    Tian, Fang; Xie, Yibing, E-mail: ybxie@seu.edu.cn [Southeast University, School of Chemistry and Chemical Engineering (China)

    2015-12-15

    Lithium manganese oxide intercalation compound (Li{sub 0.7}MnO{sub 2}) supported on titanium nitride nanotube array (TiN NTA) was applied as cathode electrode material for lithium-ion supercapacitor application. Li{sub 0.7}MnO{sub 2}/TiN NTA was fabricated through electrochemical deposition and simultaneous intercalation process using TiN NTA as a substrate, Mn(CH{sub 3}COO){sub 2} as manganese source, and Li{sub 2}SO{sub 4} as lithium source. The morphology and microstructure of the Li{sub 0.7}MnO{sub 2}/TiN NTA were characterized by scanning electron microscopy and X-ray diffraction analysis. The electrochemical performance of the Li{sub 0.7}MnO{sub 2}/TiN NTA was investigated by electrochemical impedance spectroscopy, cyclic voltammetry, and galvanostatic charge/discharge measurements. Li{sub 0.7}MnO{sub 2}/TiN NTA exhibited higher capacitive performance in Li{sub 2}SO{sub 4} electrolyte solution rather than that in Na{sub 2}SO{sub 4} electrolyte solution, which was due to the different intercalation effects of lithium-ion and sodium-ion. The specific capacitance was improved from 503.3 F g{sup −1} for MnO{sub 2}/TiN NTA to 595.0 F g{sup −1} for Li{sub 0.7}MnO{sub 2}/TiN NTA at a current density of 2 A g{sup −1} in 1.0 M Li{sub 2}SO{sub 4} electrolyte solution, which was due to the intercalation of lithium-ion for Li{sub 0.7}MnO{sub 2}. Li{sub 0.7}MnO{sub 2}/TiN NTA also kept 90.4 % capacity retention after 1000 cycles, presenting a good cycling stability. An all-solid-state lithium-ion supercapacitor was fabricated and showed an energy density of 82.5 Wh kg{sup −1} and a power density of 10.0 kW kg{sup −1}.

  1. Hydrothermal manganese oxide deposits from the Izu-Ogasawara (Bonin)-Mariana Arc and adjacent areas

    Usui, A.; Nishimura, A. (Geological Survey of Japan, Tsukuba (Japan))

    1992-04-27

    Modern and fossil hydrothermal manganese oxide deposits were discovered from a number of locations in the Izu-Ogasawara(Bonin)-Mariana Arc and adjacent areas during the Hakurei-Maru cruises from 1984 to 1989. This paper describes the occurrence and characteristics of these manganese deposits and their geological significance. It was found that the mineralogical and chemical composition and microstructure of the deposits are typically different from manganese nodules and crusts of hydrogenetic or diagenetic origin. Hardpans, veinlets, sheets, and irregular mass of the hydrothermal manganese deposits often cover a large area of sea bed, which suggests possible high-temperature hydrothermal sulfide deposits in their vicinity. On the other hand, the manganese minerals sometimes occur as substrate of younger hydrogenetic crusts and as nucleus of hydrogenetic nodules, which can provide a geological history of low-temperature hydrothermal activity on the past island arcs. 45 refs., 19 figs., 3 tabs.

  2. Synthesis of nanostructured catalysts based on Mn oxide for n-hexane elimination

    Picasso, Gino; Salazar, Ivonne; Lopez, Alcides

    2011-01-01

    Nanostructured Mn oxide based catalysts were synthesized by sol-gel method and corresponding bulk samples were prepared by precipitation procedure. In addition, some nanostructured samples based on Mn oxide supported on bentonite (montmorillonite) were prepared by incipient impregnation. Prior to calcination, the system was submitted by TEM analysis in order to study the peptization effect of acetic acid. The micrographs revealed that the sample prepared from nitrate precursor (0,06 M) achieved the highest monodispersion. After calcination of nanoparticles, TEM analysis has been performed in order to evaluate how extent the peptization agent is able to disperse. TEM micrographs of samples prepared from nitrate precursor revealed that the peptization effect increased with the concentration of acetic acid. XRD difractograms of Mn oxide samples showed characteristic well-defined diffraction peaks associated to Mn species as Mn 2 O 3 , Mn 3 O 4 and MnO 2 with more relative intensive signals in Mn 2 O 3 and Mn 3 O 4 spinel. Finally, synthesized manganese oxide nanoparticles were incorpored into layered structure of purified bentonite (montmorillonite) by incipient impregnation. Some essays with the unsupported and supported samples were performed for n-hexane combustion in a fixed bed reactor. Activity of bentonite supported sample was lower than its unsupported bulk sample counterpart; however the performance was higher than the corresponding to the support without active component probably due to more suitable structure position of nanoparticles into layered framework of starting bentonite. (author).

  3. Fabrication of Nanostructured PLGA Scaffolds Using Anodic Aluminum Oxide Templates

    Hsueh , Cheng-Chih; Wang , Gou-Jen; Hsu , Shan-Hui; Hung , Huey-Shan

    2008-01-01

    Submitted on behalf of EDA Publishing Association (http://irevues.inist.fr/handle/2042/16838); International audience; PLGA (poly(lactic-co-glycolic acid)) is one of the most used biodegradable and biocompatible materials. Nanostructured PLGA even has great application potentials in tissue engineering. In this research, a fabrication technique for nanostructured PLGA membrane was investigated and developed. In this novel fabrication approach, an anodic aluminum oxide (AAO) film was use as the...

  4. Contribution to the study of iron-manganese alloy oxidation in oxygen at high temperatures

    Olivier, Francoise

    1972-01-01

    This research thesis reports a systematic investigation of the oxidation of three relatively pure iron-manganese alloys in oxygen, under atmospheric pressure, and between 400 and 1000 C, these alloys being annealed as well as work-hardened. It also compares their behaviour with that of non-alloyed iron oxidized under the same conditions. The author describes the experimental techniques and installations, discusses the morphology of oxide films formed under the experimental conditions, discusses the film growth kinetics which is studied by thermogravimetry, proposes interpretations of results, and outlines the influence of manganese addition to iron on iron oxidation

  5. Fabrication of birnessite-type layered manganese oxide films for super capacitors

    Zhou, Y.K.; Dorval-Douville, G.; Favier, F. [Montpellier-2 Univ., LAMMI, UMR CNRS 5072, 34 (France)

    2004-07-01

    Birnessite-type layered manganese oxide films were anodically deposited at the surface of an inexpensive stainless steel. MnSO{sub 4} plating solutions were used at various potentials and for various durations. X-ray diffraction and scanning electron microscopy were used to examine the material structure and surface morphologies of obtained manganese oxide films. The capacitive characteristics and stability of these oxides were systematically investigated by means of cyclic voltammetry method in aqueous electrolytes. Deposition conditions affected the oxides structure and morphologies, and consequently greatly affected their electrochemical capacitance performance. (authors)

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

    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.

  7. Electrodeposition of Manganese-Nickel Oxide Films on a Graphite Sheet for Electrochemical Capacitor Applications

    Hae-Min Lee

    2014-01-01

    Full Text Available 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.

  8. Iron and manganese oxide mineralization in the Pacific

    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.

  9. Porous nickel hydroxide-manganese dioxide-reduced graphene oxide ternary hybrid spheres as excellent supercapacitor electrode materials.

    Chen, Hao; Zhou, Shuxue; Wu, Limin

    2014-06-11

    This paper reports the first nickel hydroxide-manganese dioxide-reduced graphene oxide (Ni(OH)2-MnO2-RGO) ternary hybrid sphere powders as supercapacitor electrode materials. Due to the abundant porous nanostructure, relatively high specific surface area, well-defined spherical morphology, and the synergetic effect of Ni(OH)2, MnO2, and RGO, the electrodes with the as-obtained Ni(OH)2-MnO2-RGO ternary hybrid spheres as active materials exhibited significantly enhanced specific capacitance (1985 F·g(-1)) and energy density (54.0 Wh·kg(-1)), based on the total mass of active materials. In addition, the Ni(OH)2-MnO2-RGO hybrid spheres-based asymmetric supercapacitor also showed satisfying energy density and electrochemical cycling stability.

  10. Self-assembled nanostructures in oxide ceramics

    Ansari, Haris Masood

    Self-assembled nanoislands in the gadolinia-doped ceria (GDC)/ yttria-stabilized zirconia (YSZ) system have recently been discovered. This dissertation is an attempt to study the mechanism by which these nanoislands form. Nanoislands in the GDC/YSZ system form via a strain based mechanism whereby the stress accumulated in the GDC-doped surface layer on the YSZ substrate is relieved by creation of self-assembled nanoislands by a mechanism similar to the ATG instability. Unlike what was previously believed, a modified surface layer is not required prior to annealing, that is, this modification can occur during annealing by surface diffusion of dopants from the GDC sources (distributed on the YSZ surface in either lithographically defined patch or powder form) with simultaneous breakup, which occurs at the hold temperature independent of the subsequent cooling. Additionally, we have developed a simple powder based process of producing nanoislands which bypasses lithography and thin film deposition setups. The versatility of the process is apparent in the fact that it allows us to study the effect of experimental parameters such as soak time, temperature, cooling rate and the effect of powder composition on nanoisland properties in a facile way. With the help of this process, we have shown that nanoislands are not peculiar to Gd containing oxide source materials on YSZ substrates and can also be produced with other source materials such as La2O3, Nd2O3, Sm 2O3, Eu2O3, Tb2O3 and even Y2O3, which is already present in the substrate and hence simplifies the system further. We have extended our work to include YSZ substrates of the (110) surface orientation and have found that instead of nanoisland arrays, we obtain an array of parallel nanobars which have their long axes oriented along the [1-10] direction on the YSZ-(110) surface. STEM EDS performed on both the bars and the nanoislands has revealed that they are solid YSZ-rich solid solutions with the dopant species and

  11. Biomimetic oxidation of carbamazepine with hydrogen peroxide catalyzed by a manganese porphyrin

    Cláudia M. B. Neves

    2012-01-01

    Full Text Available This laboratory project is planned for an undergraduate chemistry laboratory in which students prepare a manganese porphyrin able to mimic the oxidative metabolism of carbamazepine, one of the most frequently prescribed drugs in the treatment of epilepsy. The in vitro oxidation of carbamazepine results in the formation of the corresponding 10,11-epoxide, the main in vivo metabolite. The reaction is catalyzed by manganese porphyrin in the presence of H2O2, an environmentally-friendly oxidant. Through this project students will develop their skills in organic synthesis, coordination chemistry, chromatographic techniques such as TLC and HPLC, UV-visible spectrophotometry, and NMR spectroscopy.

  12. Biomimetic oxidation of carbamazepine with hydrogen peroxide catalyzed by a manganese porphyrin

    Neves, Claudia M.B.; Simoes, Mario M.Q.; Domingues, Fernando M.J.; Neves, M. Graca P.M.S.; Cavaleiro, Jose A.S., E-mail: msimoes@ua.pt [Dept. de Quimica, QOPNA, Universidade de Aveiro (Portugal)

    2012-07-01

    This laboratory project is planned for an undergraduate chemistry laboratory in which students prepare a manganese porphyrin able to mimic the oxidative metabolism of carbamazepine, one of the most frequently prescribed drugs in the treatment of epilepsy. The in vitro oxidation of carbamazepine results in the formation of the corresponding 10,11-epoxide, the main in vivo metabolite. The reaction is catalyzed by manganese porphyrin in the presence of H{sub 2}O{sub 2}, an environmentally-friendly oxidant. Through this project students will develop their skills in organic synthesis, coordination chemistry, chromatographic techniques such as TLC and HPLC, UV-visible spectrophotometry, and NMR spectroscopy. (author)

  13. Lithium containing manganese dioxide (composite dimensional manganese oxide-CDMO) as a cathod active material for lithium secondary batteries

    Furukawa, Nobuhiro; Noma, Toshiyuki; Teraji, Kazuo; Nakane, Ikuo; Yamamoto, Yuji; Saito, Toshihiko (Sanyo Electric Co., Ltd., Osaka, Japan)

    1989-06-05

    Manganese dioxide containing lithium ions in a solid matrix was investigated in the lithium nonaqueous cell. Li/sub x/MnO/sub 2+{delta}/ material prepared, with the thermal treatment, by the solid state reaction of manganese dioxide and lithium hydroxide, 7 to 3 in molar ratio, at the temperature of 375{sup 0}C in air for 20 hours, exhibited the rechargeability in the lithium nonaqueous cell. A discharging and changing cycle test, 0.14 or 0.26e/Mn in each of both the discharge and charge, was also made, with the use of a flat type cell, to demonstrate it in performance. Synthetic Li/sub x/MnO/sub 2+{delta}/ was discussed, in advantageous use for the secondary lithium cell, based on the discharging and charging characteristics. As a conclusion of the foregoing, composite dimensional manganese oxide is expected to be good as active material of positive electrode for the secondary lithium cell use. 11 refs., 11 figs., 3 tabs.

  14. Microwave synthesis of nanostructured oxide sorbents doped with lanthanides

    Mitrofanov, Andrey A., E-mail: mitrofanov-a@icloud.com; Silyavka, Elena S.; Shilovskikh, Vladimir V.; Kolonitckii, Petr D.; Sukhodolov, Nikolai G.; Selyutin, Artem A., E-mail: selutin@inbox.ru [Saint Petersburg State University, 7/9, Universitetskaya nab., St. Petersburg, 199034 (Russian Federation)

    2016-06-17

    A number of nanostructured mesoporous oxide systems based on aluminum oxide, doped with lanthanide ions have been obtained in this study. Structure and morphology of oxides obtained have been examined by X-ray diffraction analysis, thermogravimetric analysis, scanning electron microscopy. The surface area of the samples was determined by the BET method. The dependence of the adsorption of insulin on synthesized oxides from the concentration was investigated. The containing of insulin in solutions after adsorption was determined by the Bradford method. The isotherms of adsorption of insulin on resulting oxide sorbents were plotted, the dependence capacity of the sorption of insulin from the lanthanide dopant was determined.

  15. Chemical solution route to self-assembled epitaxial oxide nanostructures.

    Obradors, X; Puig, T; Gibert, M; Queraltó, A; Zabaleta, J; Mestres, N

    2014-04-07

    Self-assembly of oxides as a bottom-up approach to functional nanostructures goes beyond the conventional nanostructure formation based on lithographic techniques. Particularly, chemical solution deposition (CSD) is an ex situ growth approach very promising for high throughput nanofabrication at low cost. Whereas strain engineering as a strategy to define nanostructures with tight control of size, shape and orientation has been widely used in metals and semiconductors, it has been rarely explored in the emergent field of functional complex oxides. Here we will show that thermodynamic modeling can be very useful to understand the principles controlling the growth of oxide nanostructures by CSD, and some attractive kinetic features will also be presented. The methodology of strain engineering is applied in a high degree of detail to form different sorts of nanostructures (nanodots, nanowires) of the oxide CeO2 with fluorite structure which then is used as a model system to identify the principles controlling self-assembly and self-organization in CSD grown oxides. We also present, more briefly, the application of these ideas to other oxides such as manganites or BaZrO3. We will show that the nucleation and growth steps are essentially understood and manipulated while the kinetic phenomena underlying the evolution of the self-organized networks are still less widely explored, even if very appealing effects have been already observed. Overall, our investigation based on a CSD approach has opened a new strategy towards a general use of self-assembly and self-organization which can now be widely spread to many functional oxide materials.

  16. High-performance binder-free supercapacitor electrode by direct growth of cobalt-manganese composite oxide nansostructures on nickel foam

    Jiang, Shulan; Shi, Tielin; Long, Hu; Sun, Yongming; Zhou, Wei; Tang, Zirong

    2014-01-01

    A facile approach composed of hydrothermal process and annealing treatment is proposed to directly grow cobalt-manganese composite oxide ((Co,Mn)3O4) nanostructures on three-dimensional (3D) conductive nickel (Ni) foam for a supercapacitor electrode. The as-fabricated porous electrode exhibits excellent rate capability and high specific capacitance of 840.2 F g-1 at the current density of 10 A g-1, and the electrode also shows excellent cycling performance, which retains 102% of its initial d...

  17. High-performance binder-free supercapacitor electrode by direct growth of cobalt-manganese composite oxide nansostructures on nickel foam

    Jiang, Shulan; Shi, Tielin; Long, Hu; Sun, Yongming; Zhou, Wei; Tang, Zirong

    2014-09-01

    A facile approach composed of hydrothermal process and annealing treatment is proposed to directly grow cobalt-manganese composite oxide ((Co,Mn)3O4) nanostructures on three-dimensional (3D) conductive nickel (Ni) foam for a supercapacitor electrode. The as-fabricated porous electrode exhibits excellent rate capability and high specific capacitance of 840.2 F g-1 at the current density of 10 A g-1, and the electrode also shows excellent cycling performance, which retains 102% of its initial discharge capacitance after 7,000 cycles. The fabricated binder-free hierarchical composite electrode with superior electrochemical performance is a promising candidate for high-performance supercapacitors.

  18. Nanostructured Transparent Conducting Oxides for Device Applications

    Dutta, Titas

    2011-12-01

    Research on transparent conducting oxides (TCOs) alternative to indium tin oxide (ITO) has attracted a lot of attention due to the serious concern related to cost and chemical stability of indium tin oxide. The primary aim of this research is to develop low cost alternative transparent conducting oxides with an eye towards (1) increasing the organic solar cell efficiency and (2) fabricating transparent electronic devices utilizing p-type TCOs. To investigate the fundamental properties, the novel TCO films have been grown on sapphire and economical glass substrates using pulsed laser deposition (PLD) technique. The films were also grown under different deposition conditions in order to understand the effect of processing parameters on the film properties. The characteristics of the thin films have been investigated in detail using (X-ray diffraction, TEM, X-ray photoelectron spectroscopy (XPS), UV- photoelectron spectroscopy (UPS), four probe resistivity and UV-Vis transmittance measurements) in order to establish processing-structure-property correlation. ZnO doped with group III elements is a promising candidate because of its superior stability in hydrogen environment, benign nature and relatively inexpensive supply. However, ZnO based TCO films suffer from low work function (4.4 eV, compared to that of 4.8 eV for ITO), which increases the energy barrier and affects the carrier transport across ZnGa0.05O/organic layer interface. To overcome this issue of ZnO based TCOs, the growth of bilayered structure consisting of very thin MoOx (2.0 target composition. These optimized bilayer films exhibited good optical transmittance (≥ 80%) and low resistivity of ˜ 10-4 O-cm. The optimized NiO1+x / GZO and MoOx / GZO bilayers showed significant increase in work function values (˜5.3 eV). The work function of the bilayer films was tuned by varying the processing conditions and doping of over layers. Preliminary test device results of the organic photovoltaic cells (OPVs

  19. Optical properties of tetrapod nanostructured zinc oxide by chemical ...

    ... deposited onto indium tin oxide (ITO) coated glass substrate by thermal chemical vapor deposition (TCVD) technique. This work studies the effects of annealing temperature ranging from 100–500 ºC towards its physical and optical properties. FESEM images showed that the structural properties of tetrapod nanostructured ...

  20. Zinc oxide's hierarchical nanostructure and its photocatalytic properties

    Kanjwal, Muzafar Ahmed; Sheikh, Faheem A.; Barakat, Nasser A. M.

    2012-01-01

    In this study, a new hierarchical nanostructure that consists of zinc oxide (ZnO) was produced by the electrospinning process followed by a hydrothermal technique. First, electrospinning of a colloidal solution that consisted of zinc nanoparticles, zinc acetate dihydrate and poly(vinyl alcohol...

  1. Nanostructured Metal Oxides for Stoichiometric Degradation of Chemical Warfare Agents.

    Štengl, Václav; Henych, Jiří; Janoš, Pavel; Skoumal, Miroslav

    2016-01-01

    Metal oxides have very important applications in many areas of chemistry, physics and materials science; their properties are dependent on the method of preparation, the morphology and texture. Nanostructured metal oxides can exhibit unique characteristics unlike those of the bulk form depending on their morphology, with a high density of edges, corners and defect surfaces. In recent years, methods have been developed for the preparation of metal oxide powders with tunable control of the primary particle size as well as of a secondary particle size: the size of agglomerates of crystallites. One of the many ways to take advantage of unique properties of nanostructured oxide materials is stoichiometric degradation of chemical warfare agents (CWAs) and volatile organic compounds (VOC) pollutants on their surfaces.

  2. Manganese oxide-based multifunctionalized mesoporous silica nanoparticles for pH-responsive MRI, ultrasonography and circumvention of MDR in cancer cells.

    Chen, Yu; Yin, Qi; Ji, Xiufeng; Zhang, Shengjian; Chen, Hangrong; Zheng, Yuanyi; Sun, Yang; Qu, Haiyun; Wang, Zheng; Li, Yaping; Wang, Xia; Zhang, Kun; Zhang, Linlin; Shi, Jianlin

    2012-10-01

    Nano-biotechnology has been introduced into cancer theranostics by engineering a new generation of highly versatile hybrid mesoporous composite nanocapsules (HMCNs) for manganese-based pH-responsive dynamic T(1)-weighted magnetic resonance imaging (MRI) to efficiently respond and detect the tumor acidic microenvironment, which was further integrated with ultrasonographic function based on the intrinsic unique hollow nanostructures of HMCNs for potentially in vitro and in vivo dual-modality cancer imaging. The manganese oxide-based multifunctionalization of hollow mesoporous silica nanoparticles was achieved by an in situ redox reaction using mesopores as the nanoreactors. Due to the dissolution nature of manganese oxide nanoparticles under weak acidic conditions, the relaxation rate r(1) of manganese-based mesoporous MRI-T(1) contrast agents (CAs) could reach 8.81 mM(-1)s(-1), which is a 11-fold magnitude increase compared to the neutral condition, and is almost two times higher than commercial Gd(III)-based complex agents. This is also the highest r(1) value ever reported for manganese oxide nanoparticles-based MRI-T(1) CAs. In addition, the hollow interiors and thin mesoporous silica shells endow HMCNs with the functions of CAs for efficient in vitro and in vivo ultrasonography under both harmonic- and B-modes. Importantly, the well-defined mesopores and large hollow interiors of HMCNs could encapsulate and deliver anticancer agents (doxorubicin) intracellularly to circumvent the multidrug resistance (MDR) of cancer cells and restore the anti-proliferative effect of drugs by nanoparticle-mediated endocytosis process, intracellular drug release and P-gp inhibition/ATP depletion in cancer cells. Copyright © 2012 Elsevier Ltd. All rights reserved.

  3. Effects of manganese oxide and sulphate on the olefin selectivity of iron catalysts in the Fischer Tropsch reaction

    Dijk, van W.L.; Niemantsverdriet, J.W.; Kraan, van der A.M.; van der Baan, Hessel

    1982-01-01

    Although it has been claimed by various authors that the addition of manganese oxide, MnO, to an iron catalyst gives a marked increase in the olefin selectivity of iron catalysts, we have been unable to confirm these claims in Fischer Tropsch experiments at 513 K for an iron manganese oxide catalyst

  4. Thermodynamics of manganese oxides: Sodium, potassium, and calcium birnessite and cryptomelane

    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

  5. Biomimetic oxidation of piperine and piplartine catalyzed by iron(III) and manganese(III) porphyrins.

    Schaab, Estela Hanauer; Crotti, Antonio Eduardo Miller; Iamamoto, Yassuko; Kato, Massuo Jorge; Lotufo, Letícia Veras Costa; Lopes, Norberto Peporine

    2010-01-01

    Synthetic metalloporphyrins, in the presence of monooxygen donors, are known to mimetize various reactions of cytochrome P450 enzymes systems in the oxidation of drugs and natural products. The oxidation of piperine and piplartine by iodosylbenzene using iron(III) and manganese(III) porphyrins yielded mono- and dihydroxylated products, respectively. Piplartine showed to be a more reactive substrate towards the catalysts tested. The structures of the oxidation products were proposed based on electrospray ionization tandem mass spectrometry.

  6. Nanostructured Thermoelectric Oxides for Energy Harvesting Applications

    Abutaha, Anas I.

    2015-01-01

    of thermoelectrics are still limited to one materials system, namely SiGe, since the traditional thermoelectric materials degrade and oxidize at high temperature. Therefore, oxide thermoelectrics emerge as a promising class of materials since they can operate

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

    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.

  8. Metal oxide nanostructures and their gas sensing properties: a review.

    Sun, Yu-Feng; Liu, Shao-Bo; Meng, Fan-Li; Liu, Jin-Yun; Jin, Zhen; Kong, Ling-Tao; Liu, Jin-Huai

    2012-01-01

    Metal oxide gas sensors are predominant solid-state gas detecting devices for domestic, commercial and industrial applications, which have many advantages such as low cost, easy production, and compact size. However, the performance of such sensors is significantly influenced by the morphology and structure of sensing materials, resulting in a great obstacle for gas sensors based on bulk materials or dense films to achieve highly-sensitive properties. Lots of metal oxide nanostructures have been developed to improve the gas sensing properties such as sensitivity, selectivity, response speed, and so on. Here, we provide a brief overview of metal oxide nanostructures and their gas sensing properties from the aspects of particle size, morphology and doping. When the particle size of metal oxide is close to or less than double thickness of the space-charge layer, the sensitivity of the sensor will increase remarkably, which would be called "small size effect", yet small size of metal oxide nanoparticles will be compactly sintered together during the film coating process which is disadvantage for gas diffusion in them. In view of those reasons, nanostructures with many kinds of shapes such as porous nanotubes, porous nanospheres and so on have been investigated, that not only possessed large surface area and relatively mass reactive sites, but also formed relatively loose film structures which is an advantage for gas diffusion. Besides, doping is also an effective method to decrease particle size and improve gas sensing properties. Therefore, the gas sensing properties of metal oxide nanostructures assembled by nanoparticles are reviewed in this article. The effect of doping is also summarized and finally the perspectives of metal oxide gas sensor are given.

  9. Synthesis of electro-active manganese oxide thin films by plasma enhanced chemical vapor deposition

    Merritt, Anna R. [Energetics Research Division, Naval Air Warfare Center Weapons Division, China Lake, CA 93555 (United States); Rajagopalan, Ramakrishnan [Department of Engineering, The Pennsylvania State University, Dubois, PA 15801 (United States); Materials Research Institute, The Pennsylvania State University, University Park, PA 16802 (United States); Carter, Joshua D. [Energetics Research Division, Naval Air Warfare Center Weapons Division, China Lake, CA 93555 (United States)

    2014-04-01

    The good stability, cyclability and high specific capacitance of manganese oxide (MnO{sub x}) has recently promoted a growing interest in utilizing MnO{sub x} in asymmetric supercapacitor electrodes. Several literature reports have indicated that thin film geometries of MnO{sub x} provide specific capacitances that are much higher than bulk MnO{sub x} powders. Plasma enhanced chemical vapor deposition (PECVD) is a versatile technique for the production of metal oxide thin films with high purity and controllable thickness. In this work, MnO{sub x} thin films deposited by PECVD from a methylcyclopentadienyl manganese tricarbonyl precursor are presented and the effect of processing conditions on the quality of MnO{sub x} films is described. The film purity and oxidation state of the MnO{sub x} films were studied by Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy. Preliminary electrochemical testing of MnO{sub x} films deposited on carbon fiber electrodes in aqueous electrolytes indicates that the PECVD synthesized films are electrochemically active. - Highlights: • Plasma enhanced chemical vapor deposition of manganese oxide thin films. • Higher plasma power and chamber pressure increase deposition rate. • Manganese oxide thin films are electrochemically active. • Best electrochemical performance observed for pure film with low stress • Lower capacitance observed at higher scan rates despite thin film geometry.

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

    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.

  11. Enhanced methanol electro-oxidation activity of Pt/MWCNTs electro-catalyst using manganese oxide deposited on MWCNTs

    Nouralishahi, Amideddin; Khodadadi, Abbas Ali; Mortazavi, Yadollah; Rashidi, Alimorad; Choolaei, Mohammadmehdi

    2014-01-01

    Highlights: • Promoting effects of manganese oxide (MnO x ) on methanol electro-oxidation over Pt/MWCNTs are studied. • 3.3 times higher activity and improved stability are observed on Pt/MnO x -MWCNTs in MOR. • Both hydrogen spill over and bi-functional mechanism are facilitated in presence of MnO x . • MnO x significantly enhances electrochemical active surface area and dispersion of Pt nanoparticles. • Proton conductivity of electrocatalyst layer is improved upon MnO x incorporation. - Abstract: Electro-oxidation of methanol on platinum nanoparticles supported on a nanocomposite of manganese oxide (MnO x ) and multi-wall carbon nanotubes (MWCNTs) is investigated. The morphology, structure, and chemical composition of the electro-catalysts are characterized by TEM, XRD, EDS, TGA, and H 2 -TPR. The electro-catalytic properties of electrodes are examined by cyclic voltammetry, CO-stripping, electrochemical impedance spectroscopy (EIS), and linear sweep voltammetry (LSV). Compared to Pt/MWCNTs, the Pt/MnO x -MWCNTs electro-catalyst exhibits about 3.3 times higher forward peak current density, during cyclic voltammetry, and 4.6 times higher exchange current density in methanol electro-oxidation reaction. In addition, deposition of manganese oxide onto MWCNTs dramatically increases the electrochemical active surface area from 29.7 for Pt/MWCNTs to 89.4 m 2 g −1 Pt for Pt/MnO x -MWCNTs. The results of long-term cyclic voltammetry show superior stability of Pt nanoparticles upon addition of manganese oxide to the support. Furthermore, the kinetics of formation of the chemisorbed OH groups improves upon manganese oxide incorporation. This leads to a lower onset potential of CO ads oxidation on Pt/MnO x -MWCNTs than on Pt/MWCNTs

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

    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.

  13. Zinc-oxide-based nanostructured materials for heterostructure solar cells

    Bobkov, A. A.; Maximov, A. I.; Moshnikov, V. A.; Somov, P. A.; Terukov, E. I.

    2015-01-01

    Results obtained in the deposition of nanostructured zinc-oxide layers by hydrothermal synthesis as the basic method are presented. The possibility of controlling the structure and morphology of the layers is demonstrated. The important role of the procedure employed to form the nucleating layer is noted. The faceted hexagonal nanoprisms obtained are promising for the fabrication of solar cells based on oxide heterostructures, and aluminum-doped zinc-oxide layers with petal morphology, for the deposition of an antireflection layer. The results are compatible and promising for application in flexible electronics

  14. Crystal and fine structural transformation of Heat-treated biogenic manganese oxide

    Kimura, N.; Hashimoto, H.; Miyata, N.; Nishina, Y.; Kusano, Y.; Ikeda, Y.; Nakanishi, Y.; Fujii, T.; Šafařík, Ivo; Šafaříková, Miroslava; Takada, J.

    2013-01-01

    Roč. 60, č. 3 (2013), s. 92-98 ISSN 0532-8799 R&D Projects: GA MŠk(CZ) LH11111 Institutional support: RVO:67179843 Keywords : microorganisms * biogenic manganese oxides * phase transitions * nano-sheets * microstructures Subject RIV: EH - Ecology, Behaviour

  15. Cycle aging studies of lithium nickel manganese cobalt oxide-based batteries using electrochemical impedance spectroscopy

    Maheshwari, Arpit; Heck, Michael; Santarelli, Massimo

    2018-01-01

    The cycle aging of a commercial 18650 lithium-ion battery with graphite anode and lithium nickel manganese cobalt (NMC) oxide-based cathode at defined operating conditions is studied by regular electrochemical characterization, electrochemical impedance spectroscopy (EIS) and post-mortem analysis.

  16. Carbon/manganese oxide based fuel cell electrocatalyst using "Flywheel" principle

    Vondrák, Jiří; Klápště, Břetislav; Velická, Jana; Sedlaříková, M.; Novák, V.; Reiter, Jakub

    2005-01-01

    Roč. 8, č. 1 (2005), s. 1-4 ISSN 1480-2422 Institutional research plan: CEZ:AV0Z40320502 Keywords : manganese oxide * oxygen electrode * bifunctional electrode Subject RIV: CA - Inorganic Chemistry Impact factor: 0.772, year: 2005

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

    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

  18. Cobalt immobilization by manganese oxidizing bacteria from the Indian ridge system

    Antony, R.; Sujith, P.P.; Fernandes, S.O.; Verma, P.; Khedekar, V.D.; LokaBharathi, P.A.

    Co immobilization by two manganese oxidizing isolates from Carlsberg Ridge waters (CR35 and CR48) was compared with that of Mn at same molar concentrations. At a lower concentration of 10 mu M, CR35 and CR48 immobilized 22 and 23 fM Co cell-1...

  19. Fabrication of ultrafine manganese oxide-decorated carbon nanofibers for high-performance electrochemical capacitors

    Yang, Ying; Lee, Sungsik; Brown, Dennis E.; Zhao, Hairui; Li, Xinsong; Jiang, Daqiang; Hao, Shijie; Zhao, Yongxiang; Cong, Daoyong; Zhang, Xin; Ren, Yang

    2016-09-01

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

  20. Mechanisms in manganese catalysed oxidation of alkenes with H2O2

    Saisaha, Pattama; de Boer, Johannes W.; Browne, Wesley R.

    2013-01-01

    The development of new catalytic systems for cis-dihydroxylation and epoxidation of alkenes, based on atom economic and environmentally friendly concepts, is a major contemporary challenge. In recent years, several systems based on manganese catalysts using H2O2 as the terminal oxidant have been

  1. Synthesis of lithium-manganese-oxide spinels: A study by thermal analysis

    Thackeray, MM

    1994-12-01

    Full Text Available The synthesis of lithium-manganese-oxide spinels by reaction of Li2CO3 and MnCO3 in air and under nitrogen to T(max) = 600°C has been investigated by thermogravimetric analysis and differential scanning calorimetry. When the reaction is conducted...

  2. Synthesis and structural characterization of defect spinels in the Lithium-Manganese-Oxide system

    Thackeray, MM

    1993-10-01

    Full Text Available Lithium-manganese-oxides prepared at moderate temperatures are under investigation as insertion electrodes for rechargeable lithium batteries. The structures of two defect-spinel compounds synthesised by the reaction of MnCO3 and Li2CO3 at 400...

  3. Synthesis and structural characterization of defect spinels in the lithium-manganese-oxide system

    Thackeray, MM

    1993-10-01

    Full Text Available Lithium-manganese-oxides prepared at moderate temperatures are under investigation as insertion electrodes for rechargeable lithium batteries. The structures of two defect-spinel compounds synthesized by the reaction of MnCO3 and Li2CO3 at 400°C...

  4. Synthesis engineering of iron oxide raspberry-shaped nanostructures.

    Gerber, O; Pichon, B P; Ihiawakrim, D; Florea, I; Moldovan, S; Ersen, O; Begin, D; Grenèche, J-M; Lemonnier, S; Barraud, E; Begin-Colin, S

    2017-01-07

    Magnetic porous nanostructures consisting of oriented aggregates of iron oxide nanocrystals display very interesting properties such as a lower oxidation state of magnetite, and enhanced saturation magnetization in comparison with individual nanoparticles of similar sizes and porosity. However, the formation mechanism of these promising nanostructures is not well understood, which hampers the fine tuning of their magnetic properties, for instance by doping them with other elements. Therefore the formation mechanism of porous raspberry shaped nanostructures (RSNs) synthesized by a one-pot polyol solvothermal method has been investigated in detail from the early stages by using a wide panel of characterization techniques, and especially by performing original in situ HR-TEM studies in temperature. A time-resolved study showed the intermediate formation of an amorphous iron alkoxide phase with a plate-like lamellar structure (PLS). Then, the fine investigation of PLS transformation upon heating up to 500 °C confirmed that the synthesis of RSNs involves two iron precursors: the starting one (hydrated iron chlorides) and the in situ formed iron alkoxide precursor which decomposes with time and heating and contributes to the growth step of nanostructures. Such an understanding of the formation mechanism of RSNs is necessary to envision efficient and rational enhancement of their magnetic properties.

  5. Biodiesel production using calcium manganese oxide as catalyst and different raw materials

    Dias, Joana Maia; Conceição Machado Alvim-Ferraz, Maria; Fonseca Almeida, Manuel; Méndez Díaz, José Diego; Sánchez Polo, Manuel; Rivera Utrilla, José

    2013-01-01

    Highlights: ► Biodiesel production using a calcium manganese oxide catalyst was studied. ► The active specie was Ca 0.9 Mn 0.1 O and its deactivation occurred by hydration. ► The studied catalyst presented lower activation temperature than CaO. ► Biodiesel production and quality using different raw materials is reported. ► Compared to the conventional process, biodiesel water content improved. - Abstract: The use of heterogeneous catalysts for biodiesel production aims to simplify the production process as well as to reduce purification costs and related environmental impacts. Calcium manganese oxide was recently identified by the authors as an interesting heterogeneous catalyst for biodiesel production from animal fat; however, the difference between this and other catalysts, the catalyst activation/deactivation mechanisms, its behaviour in the synthesis using different raw materials as well as the impacts of its use on product quality remained unclear. Therefore, the present work: (i) compared biodiesel production using calcium manganese oxide and other catalysts (CaO and NaOH); (ii) studied the reasons leading to activation/deactivation of the heterogeneous catalyst; (iii) analysed biodiesel heterogeneous synthesis using calcium manganese oxide and different raw materials (lard, waste frying oil and a mixture); and (iv) evaluated raw material and catalyst impact on the product quality. Considering the use of different catalysts, the results showed that, after 8 h of reaction, product purity was similar using the different catalysts, being 92.5 wt.% using both NaOH and calcium manganese oxide and 93.8 wt.% using CaO. The active species of the heterogeneous catalysts were CaO, in the case of calcinated calcium carbonate, and Ca 0.9 Mn 0.1 O, in the case of calcinated calcium manganese oxide. Because the deactivating species were different for both catalysts, the calcium manganese oxide required lower activation temperature, which should be an advantage

  6. As(III) oxidation by MnO{sub 2} coated PEEK-WC nanostructured capsules

    Criscuoli, Alessandra, E-mail: a.criscuoli@itm.cnr.it [Institute on Membrane Technology, ITM-CNR, Via P. Bucci Cubo 17/C, 87030 Rende (CS) (Italy); Majumdar, Swachchha [Central Glass and Ceramic Research Institute, 196, Raja S. C. Mullick Rd., 700032 Kolkata (India); Figoli, Alberto, E-mail: a.figoli@itm.cnr.it [Institute on Membrane Technology, ITM-CNR, Via P. Bucci Cubo 17/C, 87030 Rende (CS) (Italy); Sahoo, Ganesh C. [Central Glass and Ceramic Research Institute, 196, Raja S. C. Mullick Rd., 700032 Kolkata (India); Bafaro, Patrizia [Institute on Membrane Technology, ITM-CNR, Via P. Bucci Cubo 17/C, 87030 Rende (CS) (Italy); Department of Chemical Engineering and Materials, University of Calabria, Via P. Bucci Cubo 42/A, 87030 Rende (CS) (Italy); Bandyopadhyay, Sibdas [Central Glass and Ceramic Research Institute, 196, Raja S. C. Mullick Rd., 700032 Kolkata (India); Drioli, Enrico [Institute on Membrane Technology, ITM-CNR, Via P. Bucci Cubo 17/C, 87030 Rende (CS) (Italy); Department of Chemical Engineering and Materials, University of Calabria, Via P. Bucci Cubo 42/A, 87030 Rende (CS) (Italy)

    2012-04-15

    Highlights: Black-Right-Pointing-Pointer Successful preparation of PEEK-WC nanostructured capsules coated by MnO{sub 2}. Black-Right-Pointing-Pointer Preliminary tests of As(III) oxidation carried out in batch. Black-Right-Pointing-Pointer Complete oxidation obtained for feed concentrations of 0.1 and 0.3 ppm. - Abstract: PEEK-WC nanostructured capsules were prepared by the phase inversion technique and used as support for the coating of a manganese dioxide layer. The coating was done by a chemical treatment of the capsules followed by a thermal one. The presence of the MnO{sub 2} layer was confirmed by scanning electron microscopy (SEM), back scattering electron (BSE), energy dispersive X-ray (EDX) and X-ray diffraction (XRD) analysis. The produced capsules were, then, tested for As(III) oxidation in batch. The experiments consisted in treating 165 ml of As(III) solution with 1 g of coated capsules at fixed temperature (15 Degree-Sign C) and pH (5.7-5.8). In particular, the efficiency of the system was investigated for different As(III) concentrations (0.1, 0.3, 0.7 and 1 ppm). For feeds at lower As(III) content (0.1-0.3 ppm), tests lasted for 8 h, while prolonged runs (up to 48 h) were carried out on more concentrated solutions (0.7 and 1 ppm). The produced capsules were able to oxidize As(III) into As(V) leading to complete conversion after 3 and 4 h for feed concentrations of 0.1 and 0.3 ppm, respectively.

  7. Synthesis, characterization and photocatalytic activity of porous manganese oxide doped titania for toluene decomposition

    Jothiramalingam, R.; Wang, M.K.

    2007-01-01

    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 R 2 and standard error. The goodness to the linear fit was observed for Elovich model with high R 2 (≥0.9477) value

  8. Sol-gel preparation of cobalt manganese mixed oxides for their use as electrode materials in lithium cells

    Lavela, P.; Tirado, J.L.; Vidal-Abarca, C.

    2007-01-01

    An ethanol dehydration procedure has been used to precipitate gel-like citrate precursors containing cobalt and manganese transition metal ions. Further annealing led to the Mn x Co 3-x O 4 spinel oxide series (x: 1, 1.5, 2, 3). Annealing temperature and treatment time were also evaluated to optimize the performance of the oxides as active electrode materials in lithium cells. The manganese-cobalt mixed oxides obtained by this procedure were cubic or tetragonal phases depending on the cobalt content. SEM images showed spherical macroporous aggregates for MnCo 2 O 4 and hollow spheres for manganese oxides. The galvanostatic cycling of lithium cells assembled with these materials demonstrated a simultaneous reduction of cobalt and manganese during the first discharge and separation of cobalt- and manganese-based products on further cycling. As compared with binary manganese oxides, a notorious electrochemical improvement was observed in the mixed oxides. This behavior is a consequence of the synergistic effect of both transition metal elements, associated with the in-situ formation of a nanocomposite electrode material when cobalt is introduced in the manganese oxide composition. Values higher than 400 mAh/g were sustained after 50 cycles for MnCo 2 O 4

  9. Oxidative Ce"3"+ sequestration by fungal manganese oxides with an associated Mn(II) oxidase activity

    Zheng, Haisu; Tani, Yukinori; Naitou, Hirotaka; Miyata, Naoyuki; Tojo, Fuyumi

    2016-01-01

    Sequestration of Ce"3"+ by biogenic manganese oxides (BMOs) formed by a Mn(II)-oxidizing fungus, Acremonium strictum strain KR21-2, was examined at pH 6.0. In anaerobic Ce"3"+ solution, newly formed BMOs exhibited stoichiometric Ce"3"+ oxidation, where the molar ratio of Ce"3"+ sequestered (Ce_s_e_q) relative to Mn"2"+ released (Mn_r_e_l) was maintained at approximately two throughout the reaction. A similar Ce"3"+ sequestration trend was observed in anaerobic treatment of BMOs in which the associated Mn(II) oxidase was completely inactivated by heating at 85 °C for 1 h or by adding 50 mM NaN_3. Aerobic Ce"3"+ treatment of newly formed BMO (enzymatically active) resulted in excessive Ce"3"+ sequestration over Mn"2"+ release, yielding Ce_s_e_q/Mn_r_e_l > 200, whereas heated or poisoned BMOs released a significant amount of Mn"2"+ with lower Ce"3"+ sequestration efficiency. Consequently, self-regeneration by the Mn(II) oxidase in newly formed BMO effectively suppressed Mn"2"+ release and enhanced oxidative Ce"3"+ sequestration under aerobic conditions. Repeated treatments of heated or poisoned BMOs under aerobic conditions confirmed that oxidative Ce"3"+ sequestration continued even after most Mn oxide was released from the solid phase, indicating auto-catalytic Ce"3"+ oxidation at the solid phase produced through primary Ce"3"+ oxidation by BMO. From X-ray diffraction analysis, the resultant solid phases formed through Ce"3"+ oxidation by BMO under both aerobic and anaerobic conditions consisted of cerianite with crystal sizes of 5.00–7.23 Å. Such nano-sized CeO_2 (CeO_2_,_B_M_O) showed faster auto-catalytic Ce"3"+ oxidation than that on well-crystalized cerianite under aerobic conditions, where the normalized pseudo-first order rate constants for auto-catalytic Ce"3"+ oxidation on CeO_2_,_B_M_O was two orders of magnitude higher. Consequently, we concluded that Ce"3"+ contact with BMOs sequesters Ce"3"+ through two oxidation paths: primary Ce"3

  10. Biphase Cobalt-Manganese Oxide with High Capacity and Rate Performance for Aqueous Sodium-Ion Electrochemical Energy Storage

    Shan, Xiaoqiang [Univ. of New Hampshire, Durham, NH (United States). Dept. of Chemical Engineering; Charles, Daniel S. [Univ. of New Hampshire, Durham, NH (United States). Dept. of Chemical Engineering; Xu, Wenqian [Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS). X-ray Science Division; Feygenson, Mikhail [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical and Engineering Materials Division and Spallation Neutron Source (SNS) outstation Juelich Centre for Neutron Science (JCNS), Forschungszentrum Juelich GmbH; Su, Dong [Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN); Teng, Xiaowei [Univ. of New Hampshire, Durham, NH (United States). Dept. of Chemical Engineering

    2017-11-22

    Manganese-based metal oxide electrode materials are of great importance in electrochemical energy storage for their favorable redox behavior, low cost and environmental-friendliness. However, their storage capacity and cycle life in aqueous Na-ion electrolytes is not satisfactory. In this paper, we report the development of a bi-phase cobalt-manganese oxide (Co-Mn-O) nanostructured electrode material, comprised of a layered MnO2.H2O birnessite phase and a (Co0.83Mn0.13Va0.04)tetra(Co0.38Mn1.62)octaO3.72 (Va: vacancy; tetra: tetrahedral sites; octa: octahedral sites) spinel phase, verified by neutron total scattering and pair distribution function analyses. The bi-phase Co-Mn-O material demonstrates an excellent storage capacity towards Na-ions in an aqueous electrolyte (121 mA h g-1 at a scan rate of 1 mV s-1 in the half-cell and 81 mA h g-1 at a current density of 2 A g-1 after 5000 cycles in full-cells), as well as high rate performance (57 mA h g-1 a rate of 360 C). Electro-kinetic analysis and in situ X-ray diffraction measurements further confirm that the synergistic interaction between the spinel and layered phases, as well as the vacancy of the tetrahedral sites of spinel phase, contribute to the improved capacity and rate performance of the Co-Mn-O material by facilitating both diffusion-limited redox and capacitive charge storage processes.

  11. Activity and selectivity of manganese oxides in alcohols Conversion as influenced by gamma-irradiation

    Doheim, M.M.; Ahmed, A.S.; El-Shobaky, G.A.

    2002-01-01

    Manganese oxide samples obtained from thermal decomposition of manganese carbonate at 400 and 600 deg C were subjected to different doses of g-irradiation within the range 0.2 to 1.6 MGy. The surface and catalytic properties of the above samples were studied using nitrogen adsorption isotherms measured at -196 deg C and catalytic conversion of ethanol and isopropanol at 300-400 deg C using micropulse technique. The results obtained revealed that manganese oxides obtained at 400 deg C consisted of a mixture of Mn 2 O 3 and MnO 2 while the samples calcined at 600 deg C composed entirely of Mn 2 O 3 . Gamma-irradiation resulted in a decrease in the particle size of manganese oxide phases with subsequent increase in their specific surface areas. Gamma-irradiation with 0.2 and 0.8 MGy effected a measurable progressive decrease in the catalytic activity in dehydration and dehydrogenation of both alcohols. However, the treated catalyst retained their initial activity upon exposure to a dose of 1.6 MGy. Also, g-irradiation increased the selectivities of the investigated solids towards dehydrogenation of both alcohols. The catalyst samples precalcined at 600 deg C exhibited higher catalytic activities than those precalcined at 400 deg C. (author)

  12. The effect of Pseudoxanthomonas sp. as manganese oxidizing bacterium on the corrosion behavior of carbon steel

    Ashassi-Sorkhabi, H.; Moradi-Haghighi, M.; Zarrini, G.

    2012-01-01

    The present study investigated the role of manganese oxidizing bacterium (MOB), namely Pseudoxanthomonas sp. on the corrosion behavior of carbon steel. This bacterium was isolated from sewage treatment plants and identified by biochemical and molecular methods. The electrochemical techniques such as open circuit potentiometry, electrochemical impedance spectroscopy, potentiodynamic and cyclic polarization were used to measure the corrosion rate and observe the corrosion mechanism. Also, scanning electron microscopy and X-ray diffraction studies were applied to surface analysis. This study revealed the strong adhesion of the biofilm on the metal surface in the presence of Pseudoxanthomonas sp. that enhanced the corrosion of carbon steel. X-ray diffraction patterns identified a high content of MnO 2 deposition within these biofilms. This is the first report that discloses the involvement of Pseudoxanthomonas sp. as manganese oxidizing bacteria on the corrosion of carbon steel. - Highlights: ► A new type of manganese oxidizing bacteria, namely Pseudoxanthomonas sp. was indicated. ► This bacterium can create a biofilm on the part of metal surface and affect localized corrosion. ► In the presence of biofilm, the diffusion of oxygen vacancies and manganese ions has occurred.

  13. The effect of Pseudoxanthomonas sp. as manganese oxidizing bacterium on the corrosion behavior of carbon steel

    Ashassi-Sorkhabi, H., E-mail: habib_ashassi@yahoo.com [Electrochemistry Research Laboratory, Physical Chemistry Department, Faculty of Chemistry, University of Tabriz, Tabriz (Iran, Islamic Republic of); Moradi-Haghighi, M. [Electrochemistry Research Laboratory, Physical Chemistry Department, Faculty of Chemistry, University of Tabriz, Tabriz (Iran, Islamic Republic of); Zarrini, G. [Microbiology laboratory, Biology Department, Science Faculty, University of Tabriz, Tabriz (Iran, Islamic Republic of)

    2012-02-01

    The present study investigated the role of manganese oxidizing bacterium (MOB), namely Pseudoxanthomonas sp. on the corrosion behavior of carbon steel. This bacterium was isolated from sewage treatment plants and identified by biochemical and molecular methods. The electrochemical techniques such as open circuit potentiometry, electrochemical impedance spectroscopy, potentiodynamic and cyclic polarization were used to measure the corrosion rate and observe the corrosion mechanism. Also, scanning electron microscopy and X-ray diffraction studies were applied to surface analysis. This study revealed the strong adhesion of the biofilm on the metal surface in the presence of Pseudoxanthomonas sp. that enhanced the corrosion of carbon steel. X-ray diffraction patterns identified a high content of MnO{sub 2} deposition within these biofilms. This is the first report that discloses the involvement of Pseudoxanthomonas sp. as manganese oxidizing bacteria on the corrosion of carbon steel. - Highlights: Black-Right-Pointing-Pointer A new type of manganese oxidizing bacteria, namely Pseudoxanthomonas sp. was indicated. Black-Right-Pointing-Pointer This bacterium can create a biofilm on the part of metal surface and affect localized corrosion. Black-Right-Pointing-Pointer In the presence of biofilm, the diffusion of oxygen vacancies and manganese ions has occurred.

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

    Staiti, P.; Lufrano, F. [CNR-ITAE, Istituto di Tecnologie Avanzate per l' Energia ' ' Nicola Giordano' ' , Via Salita S. Lucia n. 5, 98126 S. Lucia, Messina (Italy)

    2009-02-01

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

  15. Topotactic oxidative and reductive control of the structures and properties of layered manganese oxychalcogenides.

    Hyett, Geoffrey; Barrier, Nicolas; Clarke, Simon J; Hadermann, Joke

    2007-09-12

    Topotactic modification, by both oxidation and reduction, of the composition, structures, and magnetic properties of the layered oxychalcogenides Sr4Mn3O7.5Cu2Ch2 (Ch=S, Se) is described. These Mn3+ compounds are composed of alternating perovskite-type strontium manganese oxide slabs separated by anti-fluorite-type copper chalcogenide layers and are intrinsically oxide deficient in the central layer of the perovskite slabs. The systems are unusual examples of perovskite-related compounds that may topotactically be both oxidized by fluorination and reduced by deintercalation of oxygen from the oxide-deficient part of the structure. The compounds exhibit antiferromagnetic ordering of the manganese magnetic moments in the outer layers of the perovskite slabs, while the other moments, in the central layers, exhibit spin-glass-like behavior. Fluorination has the effect of increasing the antiferromagnetic ordering temperature and the size of the ordered moment, whereas reduction destroys magnetic long-range order by introducing chemical disorder which leads to both further disorder and frustration of the magnetic interactions in the manganese oxide slab.

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

    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. The calcium oxide influence on formation of manganese, calcium pyrovanadate solid solutions

    Vatolin, N.A.; Volkova, P.I.; Sapozhnikova, T.V.; Ovchinnikova, L.A.

    1988-01-01

    The X-ray graphic, derivatographic, microscopic and chemical methods are used to study solid solutions of manganese, calcium pyrovanadates containing 1-10 mass% CaO and the products of interaction of reprocessing charges of vanadium-containing converter slags intended for he formation of manganese and calcium pyrovanadates with additions of calcium oxide within 10-90 mass%. It is established that in the case of 1-6 mass% CaO content in manganese pyrovanadate solid interstitial solutions appear, while at 6-20 mass% CaO - solid substitution solutions form. The results of calculating elementary cell parameters as well as melting temperatures and pyrovanadate solid solution solubility depending on CaO content are presented. The best solubility of introduction solid solutions during vanadium extraction according to the lime technology is found

  18. Electrochemical oxidation of sulfites by DWCNTs, MWCNTs, higher fullerenes and manganese

    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.

  19. Metal Oxide Nanostructures in Food Applications: Quality Control and Packaging

    Vardan Galstyan

    2018-04-01

    Full Text Available Metal oxide materials have been applied in different fields due to their excellent functional properties. Metal oxides nanostructuration, preparation with the various morphologies, and their coupling with other structures enhance the unique properties of the materials and open new perspectives for their application in the food industry. Chemical gas sensors that are based on semiconducting metal oxide materials can detect the presence of toxins and volatile organic compounds that are produced in food products due to their spoilage and hazardous processes that may take place during the food aging and transportation. Metal oxide nanomaterials can be used in food processing, packaging, and the preservation industry as well. Moreover, the metal oxide-based nanocomposite structures can provide many advantageous features to the final food packaging material, such as antimicrobial activity, enzyme immobilization, oxygen scavenging, mechanical strength, increasing the stability and the shelf life of food, and securing the food against humidity, temperature, and other physiological factors. In this paper, we review the most recent achievements on the synthesis of metal oxide-based nanostructures and their applications in food quality monitoring and active and intelligent packaging.

  20. Zinc oxide nanostructures for electrochemical cortisol biosensing

    Vabbina, Phani Kiran; Kaushik, Ajeet; Tracy, Kathryn; Bhansali, Shekhar; Pala, Nezih

    2014-05-01

    In this paper, we report on fabrication of a label free, highly sensitive and selective electrochemical cortisol immunosensors using one dimensional (1D) ZnO nanorods (ZnO-NRs) and two dimensional nanoflakes (ZnO-NFs) as immobilizing matrix. The synthesized ZnO nanostructures (NSs) were characterized using scanning electron microscopy (SEM), selective area diffraction (SAED) and photoluminescence spectra (PL) which showed that both ZnO-NRs and ZnO-NFs are single crystalline and oriented in [0001] direction. Anti-cortisol antibody (Anti-Cab) are used as primary capture antibodies to detect cortisol using electrochemical impedance spectroscopy (EIS). The charge transfer resistance increases linearly with increase in cortisol concentration and exhibits a sensitivity of 3.078 KΩ. M-1 for ZnO-NRs and 540 Ω. M -1 for ZnO-NFs. The developed ZnO-NSs based immunosensor is capable of detecting cortisol at 1 pM. The observed sensing parameters are in physiological range. The developed sensors can be integrated with microfluidic system and miniaturized potentiostat to detect cortisol at point-of-care.

  1. Oxidative Precipitation of Manganese from Acid Mine Drainage by Potassium Permanganate

    Regeane M. Freitas

    2013-01-01

    Full Text Available Although oxidative precipitation by potassium permanganate is a widely recognised process for manganese removal, research dealing with highly contaminated acid mine drainage (AMD has yet to be performed. The present study investigated the efficiency of KMnO4 in removing manganese from AMD effluents. Samples of AMD that originated from inactive uranium mine in Brazil were chemically characterised and treated by KMnO4 at pH 3.0, 5.0, and 7.0. Analyses by Raman spectroscopy and geochemical modelling using PHREEQC code were employed to assess solid phases. Results indicated that the manganese was rapidly oxidised by KMnO4 in a process enhanced at higher pH. The greatest removal, that is, 99%, occurred at pH 7.0, when treated waters presented manganese levels as low as 1.0 mg/L, the limit established by the Brazilian legislation. Birnessite (MnO2, hausmannite (Mn3O4, and manganite (MnOOH were detected by Raman spectroscopy. These phases were consistently identified by the geochemical model, which also predicted phases containing iron, uranium, manganese, and aluminium during the correction of the pH as well as bixbyite (Mn2O3, nsutite (MnO2, pyrolusite (MnO2, and fluorite (CaF2 following the KMnO4 addition.

  2. Low temperature self-assembled growth of rutile TiO2/manganese oxide nanocrystalline films

    Sun, Zhenya; Zhou, Daokun; Du, Jianhua; Xie, Yuxing

    2017-10-01

    We report formation of rutile TiO2 nanocrystal at low temperature range in the presence of α-MnO2 which self-assembled onto sulfanyl radical activated silicon oxide substrate. SEM, HRTEM, XPS and Raman spectroscopy were used to study the morphology and oxidation state of synthesised crystals. The results showed that when the α-MnO2 was reduced to Mn3O4, it induced the formation of rutile instead of anatase phase in the TiCl4-HCl aqueous system. The finding will promote the understanding of phase transformation mechanism when manganese oxide and titanium oxide co-exist in soil and water environment.

  3. Water clustering on nanostructured iron oxide films

    Merte, Lindsay Richard; Bechstein, Ralf; Peng, G.

    2014-01-01

    , but it is not well-understood how these hydroxyl groups and their distribution on a surface affect the molecular-scale structure at the interface. Here we report a study of water clustering on a moire-structured iron oxide thin film with a controlled density of hydroxyl groups. While large amorphous monolayer...... islands form on the bare film, the hydroxylated iron oxide film acts as a hydrophilic nanotemplate, causing the formation of a regular array of ice-like hexameric nanoclusters. The formation of this ordered phase is localized at the nanometre scale; with increasing water coverage, ordered and amorphous...

  4. Manganese oxidation and bacterial diversity on different filter media coatings during the start-up of drinking water biofilters

    Breda, I. L.; Ramsay, L.; Roslev, P.

    2017-01-01

    Manganese removal is a typical concern in drinking water production. Biofiltration may be used when treating groundwater sources but the onset of manganese removal in virgin biofilters can vary considerably. The aim of this study was to investigate the effect of different filter media on manganese...... by manganese oxide, while 48, 57 and 72 days were required by virgin quartz, calcium carbonate and polystyrene, respectively. The bacterial community was investigated using DAPI staining, quantitative polymerase chain reaction (qPCR), 16S rRNA gene pyrosequencing, and bacterial enrichments. Bacterial abundance...

  5. Elucidation of the electrochromic mechanism of nanostructured iron oxides films

    Garcia-Lobato, M.A.; Martinez, Arturo I.; Castro-Roman, M. [Center for Research and Advanced Studies of the National Polytechnic Institute, Cinvestav Campus Saltillo, Carr. Saltillo-Monterrey Km. 13, Ramos Arizpe, Coah. 25900 (Mexico); Perry, Dale L. [Mail Stop 70A1150, Lawrence Berkeley National Laboratory, University of California, Berkeley, CA 94720 (United States); Zarate, R.A. [Departamento de Fisica, Facultad de Ciencias, Universidad Catolica del Norte, Casilla 1280, Antofagasta (Chile); Escobar-Alarcon, L. (Departamento de Fisica, Instituto Nacional de Investigaciones Nucleares, A.P. 18-1027, 11801 Mexico)

    2011-02-15

    Nanostructured hematite thin films were electrochemically cycled in an aqueous solution of LiOH. Through optical, structural, morphological, and magnetic measurements, the coloration mechanism of electrochromic iron oxide thin films was elucidated. The conditions for double or single electrochromic behavior are given in this work. During the electrochemical cycling, it was found that topotactic transformations of hexagonal crystal structures are favored; i.e. {alpha}-Fe{sub 2}O{sub 3} to Fe(OH){sub 2} and subsequently to {delta}-FeOOH. These topotactic redox reactions are responsible for color changes of iron oxide films. (author)

  6. Annealing-induced Fe oxide nanostructures on GaAs

    Lu, Y X; Ahmad, E; Xu, Y B; Thompson, S M

    2005-01-01

    We report the evolution of Fe oxide nanostructures on GaAs(100) upon pre- and post-growth annealing conditions. GaAs nanoscale pyramids were formed on the GaAs surface due to wet etching and thermal annealing. An 8.0-nm epitaxial Fe film was grown, oxidized, and annealed using a gradient temperature method. During the process the nanostripes were formed, and the evolution has been demonstrated using transmission and reflection high energy electron diffraction, and scanning electron microscopy...

  7. Biodegradation and corrosion behavior of manganese oxidizer Bacillus cereus ACE4 in diesel transporting pipeline

    Rajasekar, A.; Ganesh Babu, T.; Karutha Pandian, S.; Maruthamuthu, S.; Palaniswamy, N.; Rajendran, A.

    2007-01-01

    The degradation problem of petroleum products arises since hydrocarbon acts as an excellent food source for a wide variety of microorganisms. Microbial activity leads to unacceptable level of turbidity, corrosion of pipeline and souring of stored product. The present study emphasizes the role of Bacillus cereus ACE4 on degradation of diesel and its influence on corrosion of API 5LX steel. A demonstrating bacterial strain ACE4 was isolated from corrosion products and 16S rRNA gene sequence analysis showed that it has more than 99% similarity with B. cereus. The biodegradation and corrosion studies revealed that B. cereus degraded the aliphatic protons and aromatic protons in diesel and is capable of oxidizing ferrous/manganese into oxides. This is the first report that discloses the involvement of manganese oxidizer B. cereus ACE4 on biodegradation of diesel and its influence on corrosion in a tropical country pipeline

  8. A kinetic study of the enhancement of solution chemiluminescence of glyoxylic acid oxidation by manganese species.

    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.

  9. Stress response to cadmium and manganese in Paracentrotus lividus developing embryos is mediated by nitric oxide

    Migliaccio, Oriana; Castellano, Immacolata; Romano, Giovanna; Palumbo, Anna

    2014-01-01

    Highlights: • NO is produced in sea urchin embryos in response to cadmium and manganese. • Cadmium and manganese affect the expression of specific genes. • NO levels regulate directly or indirectly the expression of some metal-induced genes. • NO is proposed as a sensor of different stress agents in sea urchin embryos. - Abstract: Increasing concentrations of contaminants, often resulting from anthropogenic activities, have been reported to occur in the marine environment and affect marine organisms. Among these, the metal ions cadmium and manganese have been shown to induce developmental delay and abnormalities, mainly reflecting skeleton elongation perturbation, in the sea urchin Paracentrotus lividus, an established model for toxicological studies. Here, we provide evidence that the physiological messenger nitric oxide (NO), formed by L-arginine oxidation by NO synthase (NOS), mediates the stress response induced by cadmium and manganese in sea urchins. When NO levels were lowered by inhibiting NOS, the proportion of abnormal plutei increased. Quantitative expression of a panel of 19 genes involved in stress response, skeletogenesis, detoxification and multidrug efflux processes was followed at different developmental stages and under different conditions: metals alone, metals in the presence of NOS inhibitor, NO donor and NOS inhibitor alone. These data allowed the identification of different classes of genes whose metal-induced transcriptional expression was directly or indirectly mediated by NO. These results open new perspectives on the role of NO as a sensor of different stress agents in sea urchin developing embryos

  10. Stress response to cadmium and manganese in Paracentrotus lividus developing embryos is mediated by nitric oxide

    Migliaccio, Oriana; Castellano, Immacolata [Laboratory of Cellular and Developmental Biology, Stazione Zoologica Anton Dohrn, Villa Comunale, 80121 Naples (Italy); Romano, Giovanna [Laboratory of Functional and Evolutionary Ecology, Stazione Zoologica Anton Dohrn, Villa Comunale, 80121 Naples (Italy); Palumbo, Anna, E-mail: anna.palumbo@szn.it [Laboratory of Cellular and Developmental Biology, Stazione Zoologica Anton Dohrn, Villa Comunale, 80121 Naples (Italy)

    2014-11-15

    Highlights: • NO is produced in sea urchin embryos in response to cadmium and manganese. • Cadmium and manganese affect the expression of specific genes. • NO levels regulate directly or indirectly the expression of some metal-induced genes. • NO is proposed as a sensor of different stress agents in sea urchin embryos. - Abstract: Increasing concentrations of contaminants, often resulting from anthropogenic activities, have been reported to occur in the marine environment and affect marine organisms. Among these, the metal ions cadmium and manganese have been shown to induce developmental delay and abnormalities, mainly reflecting skeleton elongation perturbation, in the sea urchin Paracentrotus lividus, an established model for toxicological studies. Here, we provide evidence that the physiological messenger nitric oxide (NO), formed by L-arginine oxidation by NO synthase (NOS), mediates the stress response induced by cadmium and manganese in sea urchins. When NO levels were lowered by inhibiting NOS, the proportion of abnormal plutei increased. Quantitative expression of a panel of 19 genes involved in stress response, skeletogenesis, detoxification and multidrug efflux processes was followed at different developmental stages and under different conditions: metals alone, metals in the presence of NOS inhibitor, NO donor and NOS inhibitor alone. These data allowed the identification of different classes of genes whose metal-induced transcriptional expression was directly or indirectly mediated by NO. These results open new perspectives on the role of NO as a sensor of different stress agents in sea urchin developing embryos.

  11. Nanostructured Thermoelectric Oxides for Energy Harvesting Applications

    Abutaha, Anas I.

    2015-11-24

    As the world strives to adapt to the increasing demand for electrical power, sustainable energy sources are attracting significant interest. Around 60% of energy utilized in the world is wasted as heat. Different industrial processes, home heating, and exhausts in cars, all generate a huge amount of unused waste heat. With such a huge potential, there is also significant interest in discovering inexpensive technologies for power generation from waste heat. As a result, thermoelectric materials have become important for many renewable energy research programs. While significant advancements have been done in improving the thermoelectric properties of the conventional heavy-element based materials (such as Bi2Te3 and PbTe), high-temperature applications of thermoelectrics are still limited to one materials system, namely SiGe, since the traditional thermoelectric materials degrade and oxidize at high temperature. Therefore, oxide thermoelectrics emerge as a promising class of materials since they can operate athigher temperatures and in harsher environments compared to non-oxide thermoelectrics. Furthermore, oxides are abundant and friendly to the environment. Among oxides, crystalline SrTiO3 and ZnO are promising thermoelectric materials. The main objective of this work is therefore to pursue focused investigations of SrTiO3 and ZnO thin films and superlattices grown by pulsed laser deposition (PLD), with the goal of optimizing their thermoelectric properties by following different strategies. First, the effect of laser fluence on the thermoelectric properties of La doped epitaxial SrTiO3 films is discussed. Films grown at higher laser fluences exhibit better thermoelectric performance. Second, the role of crystal orientation in determining the thermoelectric properties of epitaxial Al doped ZnO (AZO) films is explained. Vertically aligned (c-axis) AZO films have superior thermoelectric properties compared to other films with different crystal orientations. Third

  12. Aging promotes todorokite formation from layered manganese oxide at near-surface conditions

    Cui, Haojie [Chinese Academy of Sciences, Xiamen (China). Key Lab. of Urban Environment and Health; Huazhong Agricultural Univ., Ministry of Agriculture, Wuhan (China). Key Lab. of Subtropical Agricultural Resources and Environment; Liu, Fan; Feng, Xionghan; Tan, Wenfeng [Huazhong Agricultural Univ., Ministry of Agriculture, Wuhan (China). Key Lab. of Subtropical Agricultural Resources and Environment; Wang, Ming Kuang [National Taiwan Univ., Taipei (China). Dept. of Agricultural Chemistry

    2010-12-15

    Todorokite is one common manganese oxide in soils and sediments and is commonly formed from layered Na-buserite. Aging processes can alter the physicochemical properties of freshly formed Na-buserite in natural environments. However, it is not clear whether and how aging affects the formation of todorokites. In the present paper, Na-buserite with aging treatment was employed to prepare todorokite at atmospheric pressure to investigate the effects of aging treatment of Na-buserite on the formation of todorokite. Four aged Na-buserite samples, which are produced through oxidation of Mn{sup 2+} in concentrated NaOH medium by O{sub 2} with aging for 3, 6, 9, and 12 months, were employed to investigate the effects of aging processes on the transformation from Na-buserite to todorokite by Mg{sup 2+}-templating reaction at atmospheric pressure. The manganese oxides were examined using X-ray diffraction (XRD), elemental analysis, determinations of the average manganese oxidation number, infrared spectroscopy (IR), and transmission electron microscopy (TEM). The XRD, IR, and elemental analyses indicate that aging treatment can alter the substructure of the freshly synthesized Na-buserite. During the aging process, some of the Mn(III) may migrate into the interlayer region or disproportionate to form Mn{sup 2+} and Mn{sup 4+} from the layer of Na-buserite and the concomitant formation of layer vacancies. The interlayer Mn{sup 3+} or Mn{sup 2+} occupied above or below the layer vacancy sites and become corner-sharing octahedral. XRD analyses and TEM clearly show that the transformation from Na-buserite to todorokite was promoted by aging treatments. The alterations of substructure of aged Na-buserites can promote the rearrangement of manganese to construct a tunnel structure during the transformation from layered manganese oxides to tunnel-structure todorokite at atmospheric pressure. The transformation from Na-buserite to todorokite was promoted by aging treatments at

  13. Conductive transition metal oxide nanostructured electrochromic material and optical switching devices constructed thereof

    Mattox, Tracy M.; Koo, Bonil; Garcia, Guillermo; Milliron, Delia J.; Trizio, Luca De; Dahlman, Clayton

    2017-10-10

    An electrochromic device includes a nanostructured transition metal oxide bronze layer that includes one or more transition metal oxide and one or more dopant, a solid state electrolyte, and a counter electrode. The nanostructured transition metal oxide bronze selectively modulates transmittance of near-infrared (NIR) spectrum and visible spectrum radiation as a function of an applied voltage to the device.

  14. Influence of the fuel in the nanostructure catalyzer oxides synthesis

    Zampiva, R.Y.S.; Panta, P.C.; Carlos, R.B.; Alves, A.K.; Bergmann, C.P.

    2012-01-01

    Among the techniques used in catalysts production, the solution combustion synthesis (SCS) has been increasingly applied due the possibility of producing, at low cost, highly pure and homogeneous nanostructured powders. The smaller the particle diameter, the greater the activity of the catalyst. In SCS, the size of the particles produced depends on the process variables. In order to formulate the optimal methodology for the preparation of nanostructured oxides for catalysis, it was studied the fuel-oxidant concentration ratio, and the use of glycine and polyethylene glycol with molecular weight 200 (PEG 200) as fuel in the SCS of Iron, Magnesium and Molybdenum based catalysts. The phase identification of the products was performed by x-ray diffraction (XRD). Particle size and surface area analysis were done to characterize the particles size and the samples morphology was obtained by scanning electron microscopy. Results indicated the formation of high purity nanomaterials obtained for low concentrations of fuel, and a wide variation in the nanostructure sizes depending on the concentration and type of fuel used. (author)

  15. The effect of acidity of electrolyte on the porosity and the nanostructure morphology of electrolytic manganese dioxide

    Adelkhani, H.

    2012-01-01

    The effects of acidity of electrolyte (pH) on the hysteresis behavior, the specific surface area, and nanostructure morphology of electrolytic manganese dioxides (EMDs) have been studied by using the Barrett-Joyner-Halenda (BJH) analysis, X-ray diffraction (XRD) and scanning electron microscopy (SEM) images analysis. EMD samples are electrodeposited at a variable pH (6 to 1) and many fixed pH (2, 3, 4, 5, and 6). Results indicate that pH play key roles in the characteristics of EMD. The samples obtained at low pH (2 and 3) show multi-branched morphology and represent a H4 hysteresis loop. At pH 4 and 5, a uniform and dense structure of MnO 2 is obtained without hysteresis behavior. The sample electrodeposited at pH 6 shows a regular reticulate, that its adsorption-desorption isotherm show hysteresis behavior. By electrodeposition at a variable pH, the sample shows a cauliflower-like and multi-branched form. From the viewpoint of classification of isotherm, pH strongly affects on Type of isotherm. The results show that γ-MnO 2 is as main-product of electrodeposition and α-MnO 2 and β-MnO 2 were obtained as side-product at low and high pH, respectively.

  16. The effect of acidity of electrolyte on the porosity and the nanostructure morphology of electrolytic manganese dioxide

    Adelkhani, H., E-mail: adelkhani@hotmail.com [Material Research School, NSTRI, P.O. Box: 14395-836, Tehran (Iran, Islamic Republic of)

    2012-06-15

    The effects of acidity of electrolyte (pH) on the hysteresis behavior, the specific surface area, and nanostructure morphology of electrolytic manganese dioxides (EMDs) have been studied by using the Barrett-Joyner-Halenda (BJH) analysis, X-ray diffraction (XRD) and scanning electron microscopy (SEM) images analysis. EMD samples are electrodeposited at a variable pH (6 to 1) and many fixed pH (2, 3, 4, 5, and 6). Results indicate that pH play key roles in the characteristics of EMD. The samples obtained at low pH (2 and 3) show multi-branched morphology and represent a H4 hysteresis loop. At pH 4 and 5, a uniform and dense structure of MnO{sub 2} is obtained without hysteresis behavior. The sample electrodeposited at pH 6 shows a regular reticulate, that its adsorption-desorption isotherm show hysteresis behavior. By electrodeposition at a variable pH, the sample shows a cauliflower-like and multi-branched form. From the viewpoint of classification of isotherm, pH strongly affects on Type of isotherm. The results show that {gamma}-MnO{sub 2} is as main-product of electrodeposition and {alpha}-MnO{sub 2} and {beta}-MnO{sub 2} were obtained as side-product at low and high pH, respectively.

  17. Oxide nanostructures through self-assembly

    Aggarwal, S.; Ogale, S. B.; Ganpule, C. S.; Shinde, S. R.; Novikov, V. A.; Monga, A. P.; Burr, M. R.; Ramesh, R.; Ballarotto, V.; Williams, E. D.

    2001-03-01

    A prominent theme in inorganic materials research is the creation of uniformly flat thin films and heterostructures over large wafers, which can subsequently be lithographically processed into functional devices. This letter proposes an approach that will lead to thin film topographies that are directly counter to the above-mentioned philosophy. Recent years have witnessed considerable research activity in the area of self-assembly of materials, stimulated by observations of self-organized behavior in biological systems. We have fabricated uniform arrays of nonplanar surface features by a spontaneous assembly process involving the oxidation of simple metals, especially under constrained conditions on a variety of substrates, including glass and Si. In this letter we demonstrate the pervasiveness of this process through examples involving the oxidation of Pd, Cu, Fe, and In. The feature sizes can be controlled through the grain size and thickness of the starting metal thin film. Finally, we demonstrate how such submicron scale arrays can serve as templates for the design and development of self-assembled, nanoelectronic devices.

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

    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

  19. Fluorescence studies of Rhodamine 6G functionalized silicon oxide nanostructures

    Baumgaertel, Thomas; Borczyskowski, Christian von; Graaf, Harald

    2010-01-01

    Selective anchoring of optically active molecules on nanostructured surfaces is a promising step towards the creation of nanoscale devices with new functionalities. Recently we have demonstrated the electrostatic attachment of charged fluorescent molecules on silicon oxide nanostructures prepared by atomic force microscopy (AFM) nanolithography via local anodic oxidation (LAO) of dodecyl-terminated silicon. In this paper we report on our findings from a more detailed optical investigation of the bound dye Rhodamine 6G. High sensitivity optical wide field microscopy as well as confocal laser microscopy have been used to characterize the Rhodamine fluorescence emission. A highly interesting question concerns the interaction between an emitter close to a silicon surface because mechanisms such as energy transfer and fluorescence quenching will occur which are still not fully understood. Since the oxide thickness can be varied during preparation continuously from 1 to ∼ 5 nm, it is possible to investigate the fluorescence of the bound dye in close proximity to the underlying silicon. Using confocal laser microscopy we were also able to obtain optical spectra from the bound molecules. Together with the results from an analysis of their photochemical bleaching behaviour, we conjecture that some of the Rhodamine 6G molecules on the structure are interacting with the oxide, causing a spectral shift and differences in their photochemical properties.

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

    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

  1. Electrochemical synthesis of birnessite-type layered manganese oxides for rechargeable lithium batteries

    Nakayama, Masaharu; Kanaya, Taku; Lee, Jong-Won; Popov, Branko N.

    Layered manganese dioxide (MnO 2) films intercalated with Li +, Na + or Mg 2+ ions were synthesized by a one-step electrochemical method. The electrodeposition was potentiostatically performed by applying an anodic potential of 1.0 V vs. Ag/AgCl in an aqueous MnSO 4 solution containing a perchlorate salt of the cation. The electrodeposited oxide films have a birnessite-type layered structure with alkali cations and water molecules between manganese oxide layers. The galvanostatic charge-discharge experiments performed in 1 M LiPF 6-DME/PC solution indicated that the Mg 2+-intercalated MnO 2 electrode exhibits an initial discharge capacity as large as 140 mAh g -1 and it shows a better capacity retention during cycling as compared with the Li +- or Na +-intercalated MnO 2 electrode.

  2. Gallium Oxide Nanostructures for High Temperature Sensors

    Chintalapalle, Ramana V. [Univ. of Texas, El Paso, TX (United States)

    2015-04-30

    Gallium oxide (Ga2O3) thin films were produced by sputter deposition by varying the substrate temperature (Ts) in a wide range (Ts=25-800 °C). The structural characteristics and electronic properties of Ga2O3 films were evaluated using X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray spectrometry (EDS), Rutherford backscattering spectrometry (RBS) and spectrophotometric measurements. The effect of growth temperature is significant on the chemistry, crystal structure and morphology of Ga2O3 films. XRD and SEM analyses indicate that the Ga2O3 films grown at lower temperatures were amorphous while those grown at Ts≥500 oC were nanocrystalline. RBS measurements indicate the well-maintained stoichiometry of Ga2O3 films at Ts=300-800 °C. The electronic structure determination indicated that the nanocrystalline Ga2O3films exhibit a band gap of ~5 eV. Tungsten (W) incorporated Ga2O3 films were produced by co-sputter deposition. W-concentration was varied by the applied sputtering-power. No secondary phase formation was observed in W-incorporated Ga2O3 films. W-induced effects were significant on the structure and electronic properties of Ga2O3 films. The band gap of Ga2O3 films without W-incorporation was ~5 eV. Oxygen sensor characteristics evaluated using optical and electrical methods indicate a faster response in W-doped Ga2O3 films compared to intrinsic Ga2O3 films. The results demonstrate the applicability of both intrinsic and W-doped Ga-oxide films for oxygen sensor application at temperatures ≥700 °C.

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

    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

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

    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.

  5. Microstructural characterization of the cycling behavior of electrodeposited manganese oxide supercapacitors using 3D electron tomography

    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.

  6. Characteristics and defluoridation performance of granular activated carbons coated with manganese oxides

    Ma Yue; Wang Shuguang; Fan Maohong; Gong Wenxin; Gao Baoyu

    2009-01-01

    Using a redox process, granular activated carbon (GAC) was coated with manganese oxides to enhance its ability to adsorb fluoride from an aqueous solution. Compared with plain GAC, the fluoride adsorption capacity of this new adsorbent was improved and at least three times greater than that of uncoated GAC. The surface characteristics of coated GAC were observed with scanning electron microscopy. The surface area of the new adsorbent was calculated using the Brunauer-Emmett-Teller method. X-ray diffraction revealed that manganese oxides are amorphous. X-ray photoelectron spectroscopy demonstrated that manganese existed primarily in the oxidation state +IV. Kinetic and equilibrium adsorption data showed that the adsorption process follows the pseudo-second order kinetic and Freundlich equation models. The sorption data also indicated that the removal of fluoride by adsorption is a highly complex process, involving both boundary layer diffusion and intra-particle diffusion. The pH value of solution influences fluoride removal, and the optimum equilibrium pH value of fluoride adsorption is 3.0.

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

    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.

  8. Oxidative cleavage of a phenolic diarylpropane lignin model dimer by manganese peroxidase from Phanerochaete chrysosporium

    Wariishi, Hiroyuki; Valli, K.; Gold, M.H.

    1989-01-01

    In the presence of Mn II and H 2 O 2 , homogeneous manganese peroxidase oxidized 1-(3,5-dimethoxy-4-hydroxyphenyl)-2-(4-methoxyphenyl)-1,3-dihydroxypropane (I) to yield 1-(3,5-dimethoxy-4-hydroxyphenyl)-2-(4-methoxyphenyl)-1-oxo-3-hydroxypropane (II), 2,6-dimethoxy-1,4-benzoquinone (III), 2,6-dimethoxy-1,4-dihydroxybenzene (IV), 1-(4-methoxyphenyl)-1-oxo-2-hydroxyethane (V), 1-(4-methoxyphenyl)-1,2-dihydroxyethane (VI), syringaldehyde (VIII), and 2-(4-methoxyphenyl)-3-hydroxypropanal (IX). Chemically prepared manganese(III) malonate catalyzed the same reactions. Oxidation of I in H 2 18 O under argon resulted in >80% incorporation of 18 O into the phenylglycol VI, the hydroquinone IV, and the quinone III. Oxidation of I in H 2 18 O under aerobic conditions resulted in 40% incorporation of 18 O into VI but no 18 O incorporation into V. Finally, oxidation of I under 18 O 2 resulted in 89% and 28% incorporation of 18 O into V and VI, respectively. These results are explained by mechanisms involving the one-electron oxidation of the substrate I by enzyme-generated Mn III to produce a phenoxy radical intermediate I'. Subsequent C α -C β bond cleavage of the radical intermediate yields syringaldehyde (VIII) and a C 6 -C 2 benzylic radical. Syringaldehyde is oxidized by Mn III in several steps to a cyclohexadiene cation intermediate I double-prime, which is attacked by water to yield the benzoquinone III. The C 6 -C 2 radical is scavenged by O 2 to form a peroxy radical that decomposes to V and VI. In these reactions, Mn III generated by manganese peroxidase catalyzes both formation of the substrate phenoxy radical and oxidation of carbon-centered radical intermediates, to yield reactive cations

  9. QSAR analysis for nano-sized layered manganese-calcium oxide in water oxidation: An application of chemometric methods in artificial photosynthesis.

    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.

  10. Nanostructured oxides for energy storage applications in batteries and supercapacitors

    Chandra, A.; Roberts, A. J.; Yee, E. L. H.; Slade, R. C. T.

    2009-01-01

    Nanostructured materials are extensively investigated for application in energy storage and power generation devices. This paper deals with the synthesis and characterization of nanomaterials based on oxides of vanadium and with their application as electrode materials for energy storage systems viz. supercapacitors. These nano-oxides have been synthesized using a hydrothermal route in the presence of templates: 1-hexadecylamine, Tweens and Brij types. Using templates during synthesis enables tailoring of the particle morphology and physical characteristics of synthesized powders. Broad X-ray diffraction peaks show the formation of nanoparticles, confirmed using scanning electron microscopy (SEM) and transmission electron microscopy (TEM) investigations. SEM studies show that a large range of nanostructures such as needles, fibers, particles, etc. can be synthesized. These particles have varying surface areas and electrical conductivity. Enhancement of surface area as much as seven times relative to surface areas of starting parent materials has been observed. These properties make such materials ideal candidates for application as electrode materials in super capacitors. Assembly and characterization of supercapacitors based on electrodes containing these active nano-oxides are discussed. Specific capacitance of >100 F g -1 has been observed. The specific capacitance decreases with cycling: causes of this phenomenon are presented. (authors)

  11. Biological water-oxidizing complex: a nano-sized manganese-calcium oxide in a protein environment.

    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.

  12. Zinc oxide nanostructured layers for gas sensing applications

    Caricato, A. P.; Cretí, A.; Luches, A.; Lomascolo, M.; Martino, M.; Rella, R.; Valerini, D.

    2011-03-01

    Various kinds of zinc oxide (ZnO) nanostructures, such as columns, pencils, hexagonal pyramids, hexagonal hierarchical structures, as well as smooth and rough films, were grown by pulsed laser deposition using KrF and ArF excimer lasers, without use of any catalyst. ZnO films were deposited at substrate temperatures from 500 to 700°C and oxygen background pressures of 1, 5, 50, and 100 Pa. Quite different morphologies of the deposited films were observed using scanning electron microscopy when different laser wavelengths (248 or 193 nm) were used to ablate the bulk ZnO target. Photoluminescence studies were performed at different temperatures (down to 7 K). The gas sensing properties of the different nanostructures were tested against low concentrations of NO2. The variation in the photoluminescence emission of the films when exposed to NO2 was used as transduction mechanism to reveal the presence of the gas. The nanostructured films with higher surface-to-volume ratio and higher total surface available for gas adsorption presented higher responses, detecting NO2 concentrations down to 3 ppm at room temperature.

  13. Crystal habit dependent quantum confined photoluminescence of zinc oxide nanostructures

    Arellano, Ian Harvey J.; Payawan, Leon Jr. M.; Sarmago, Roland V.

    2008-01-01

    Diverse zinc oxide crystal habits namely wire, rods, tubes, whiskers and tetrapods were synthesized via hydrothermal and carbothermal reduction routes. A vapor current induced regionalization in the carbothermal synthesis lead to the isolation of these crystal habits for characterization. The surface morphology of the nanostructures was analyzed via field emission scanning electron microscopy (FESEM). The morphology and crystallinity of the as-synthesized nanostructure architectural motifs were related to their photoluminescence (PL). The photoluminescence at 157 nm was taken using F2 excimer laser and a crystal habit dependent response was observed. X-ray diffraction (XRD) analyses were conducted to deduce the degree of crystallinity showing results consistent with the excitonic emission at the band edge and visible emission at the electron-hole recombination sites. The presence of minimal crystal defects which gave the green emission was supported by energy dispersive spectroscopy (EDS) data. Transmission spectroscopy for the tetrapods exhibited an interesting PL reduction associated with high-energy deep traps in the nanostructures. Furthermore, some intensity dependent characteristics were deduced indicating quantum confined properties of these nano structures. (author)

  14. Review of Fabrication Methods, Physical Properties, and Applications of Nanostructured Copper Oxides Formed via Electrochemical Oxidation

    Wojciech J. Stepniowski

    2018-05-01

    Full Text Available Typically, anodic oxidation of metals results in the formation of hexagonally arranged nanoporous or nanotubular oxide, with a specific oxidation state of the transition metal. Recently, the majority of transition metals have been anodized; however, the formation of copper oxides by electrochemical oxidation is yet unexplored and offers numerous, unique properties and applications. Nanowires formed by copper electrochemical oxidation are crystalline and composed of cuprous (CuO or cupric oxide (Cu2O, bringing varied physical and chemical properties to the nanostructured morphology and different band gaps: 1.44 and 2.22 eV, respectively. According to its Pourbaix (potential-pH diagram, the passivity of copper occurs at ambient and alkaline pH. In order to grow oxide nanostructures on copper, alkaline electrolytes like NaOH and KOH are used. To date, no systemic study has yet been reported on the influence of the operating conditions, such as the type of electrolyte, its temperature, and applied potential, on the morphology of the grown nanostructures. However, the numerous reports gathered in this paper will provide a certain view on the matter. After passivation, the formed nanostructures can be also post-treated. Post-treatments employ calcinations or chemical reactions, including the chemical reduction of the grown oxides. Nanostructures made of CuO or Cu2O have a broad range of potential applications. On one hand, with the use of surface morphology, the wetting contact angle is tuned. On the other hand, the chemical composition (pure Cu2O and high surface area make such materials attractive for renewable energy harvesting, including water splitting. While compared to other fabrication techniques, self-organized anodization is a facile, easy to scale-up, time-efficient approach, providing high-aspect ratio one-dimensional (1D nanostructures. Despite these advantages, there are still numerous challenges that have to be faced, including the

  15. Reduced graphene oxide wrapped Ag nanostructures for enhanced SERS activity

    Nair, Anju K.; Kala, M. S.; Thomas, Sabu; Kalarikkal, Nandakumar

    2018-04-01

    Graphene - metal nanoparticle hybrids have received great attention due to their unique electronic properties, large specific surface area, very high conductivity and more charge transfer. Thus, it is extremely advantages to develop a simple and efficient process to disperse metal nanostructures over the surface of graphene sheets. Herein, we report a hydrothermal assisted strategy for developing reduced graphene oxide /Ag nanomorphotypes (cube, wire) for surface enhanced Raman scattering (SERS) applications, considering the advantages of synergistic effect of graphene and plasmonic properties of Ag nanomorphotypes.

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

    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).

  17. Morphology–dependent electrochemical sensing properties of manganese dioxide–graphene oxide hybrid for guaiacol and vanillin

    Gan, Tian; Shi, Zhaoxia; Deng, Yaping; Sun, Junyong; Wang, Haibo

    2014-01-01

    Highlights: • MnO 2 with different morphologies were prepared via facile methods. • MnO 2 are loaded on GO via simply grinding which have high solubility and stability. • MnO 2 –GO exhibit high electrocatalytic activities depending on their shapes. • MnO 2 –GO is first used to the determination of guaiacol and vanillin simultaneously. - Abstract: Various morphologies of manganese dioxide (MnO 2 ) electrocatalysts, including nanoflowers, nanorods, nanotubes, nanoplates, nanowires and microspheres were prepared via facile hydrothermal synthesis and precipitation methods. By simply grinding with graphene oxide (GO), MnO 2 could be readily dissolved in water with high solubility and stability. The structures and electrochemical performances of these as–prepared MnO 2 –GO hybrids were fully characterized by various techniques, and the properties were found to be strongly dependent on morphology. As sensing materials for the simultaneous determination of guaiacol and vanillin for the first time, the nanoflowers–like MnO 2 , coupled with GO, exhibited relatively high sensitivity. The enhanced electrocatalytic activity was ascribed to the high purity, good crystallinity, and unique porous microstructure, which were favorable for transfer of electrons. These results may provide valuable insights for the development of nanostructured modified electrodes for next–generation high–performance electrochemical sensors

  18. Synthesis, characterization and biological studies of copper oxide nanostructures

    Jillani, Saquf; Jelani, Mohsan; Hassan, Najam Ul; Ahmad, Shahbaz; Hafeez, Muhammad

    2018-04-01

    The development of synthetic methods has been broadly accepted as an area of fundamental importance to the understanding and application of nanoscale materials. It allows the individual to modulate basic parameters such as morphology, particle size, size distributions, and composition. Several methods have been developed to synthesize CuO nanostructures with diverse morphologies, sizes, and dimensions using different chemical and physical based approaches. In this work, CuO nanostructures have been synthesized by aqueous precipitation method and simple chemical deposition method. The characterization of these products has been carried out by the x-ray Diffraction (XRD), Scanning Electron Microscope (SEM), Fourier Transform Infrared (FTIR) and UV–vis spectroscopy. Biological activity such as antibacterial nature of synthesized CuO is also explored. XRD peaks analysis revealed the monoclinic crystalline phase of copper oxide nanostructures. While the rod-like and particle-like morphologies have been observed in SEM results. FTIR spectra have confirmed the formation of CuO nanoparticles by exhibiting its characteristic peaks corresponding to 494 cm‑1 and 604 cm‑1. The energy band gap of the as-prepared CuO nanostructures determined from UV–vis spectra is found to be 2.18 eV and 2.0 eV for precipitation and chemically deposited samples respectively. The antibacterial activity results described that the synthesized CuO nanoparticles showed better activity against Staphylococcus aureus. The investigated results suggested the synthesis of highly stable CuO nanoparticles with significant antibacterial activities.

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

    Matthias Augustin

    2015-01-01

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

  20. Bio-inspired iron and manganese complexes derived from mixed N,O ligands for the oxidation of olefins

    Moelands, M.A.H.

    2014-01-01

    This Thesis describes the synthesis and structural analysis of bio-inspired iron and manganese complexes used for the catalytic oxidation of olefin substrates. The development of catalytic systems for oxidation chemistry that are based on first row transition metals and that apply a green oxidant

  1. Characterization of manganese oxide precipitates from Appalachian coal mine drainage treatment systems

    Tan Hui; Zhang Gengxin; Heaney, Peter J.; Webb, Samuel M.; Burgos, William D.

    2010-01-01

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

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

    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.

  3. Amorphous manganese-calcium oxides as a possible evolutionary origin for the CaMn₄ cluster in photosystem II.

    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.

  4. Controlling of morphology and electrocatalytic properties of cobalt oxide nanostructures prepared by potentiodynamic deposition method

    Hallaj, Rahman [Department of Chemistry, University of Kurdistan, P.O. Box 416, Sanandaj (Iran, Islamic Republic of); Akhtari, Keivan [Department of Chemistry, University of Kurdistan, P.O. Box 416, Sanandaj (Iran, Islamic Republic of); Research Center for Nanotechnology, University of Kurdistan, P.O.Box 416, Sanandaj (Iran, Islamic Republic of); Salimi, Abdollah, E-mail: absalimi@uok.ac.ir [Department of Chemistry, University of Kurdistan, P.O. Box 416, Sanandaj (Iran, Islamic Republic of); Research Center for Nanotechnology, University of Kurdistan, P.O.Box 416, Sanandaj (Iran, Islamic Republic of); Soltanian, Saied [Department of Physics, University of Kurdistan, P.O. Box 416, Sanandaj (Iran, Islamic Republic of)

    2013-07-01

    Electrodeposited cobalt oxide nanostructures were prepared by Repetitive Triangular Potential Scans (RTPS) as a simple, remarkably fast and scalable potentiodynamic method. Electrochemical deposition of cobalt oxide nanostructures onto GC electrode was performed from aqueous Co(NO{sub 3}){sub 2}, (pH 6) solution using cyclic voltammetry method. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) were used to characterize the morphology of fabricated nanostructures. The evaluation of electrochemical properties of deposited films was performed using cyclic voltametry (CV) and impedance spectroscopy (IS) techniques. The analysis of the experimental data clearly showed that the variations of potential scanning ranges during deposition process have drastic effects on the geometry, chemical structure and particle size of cobalt oxide nanoparticles. In addition, the electrochemical and electrocatalytic properties of prepared nanostructures can be controlled through applying different potential windows in electrodeposition process. The imaging and voltammetric studies suggested to the existence of at least three different shapes of cobalt-oxide nanostructures in various potential windows applied for electrodeposition. With enlarging the applied potential window, the spherical-like cobalt oxide nanoparticles with particles sizes about 30–50 nm changed to the grain-like structures (30 nm × 80 nm) and then to the worm-like cobalt oxide nanostructures with 30 nm diameter and 200–400 nm in length. Furthermore, the roughness of the prepared nanostructures increased with increasing positive potential window. The GC electrodes modified with cobalt oxide nanostructures shows excellent electrocatalytic activity toward H{sub 2}O{sub 2} and As (III) oxidation. The electrocatalytic activity of cobalt oxide nanostructures prepared at more positive potential window toward hydrogen peroxide oxidation was increased, while for As(III) oxidation the electrocatalytic

  5. Controlling of morphology and electrocatalytic properties of cobalt oxide nanostructures prepared by potentiodynamic deposition method

    Hallaj, Rahman; Akhtari, Keivan; Salimi, Abdollah; Soltanian, Saied

    2013-01-01

    Electrodeposited cobalt oxide nanostructures were prepared by Repetitive Triangular Potential Scans (RTPS) as a simple, remarkably fast and scalable potentiodynamic method. Electrochemical deposition of cobalt oxide nanostructures onto GC electrode was performed from aqueous Co(NO 3 ) 2 , (pH 6) solution using cyclic voltammetry method. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) were used to characterize the morphology of fabricated nanostructures. The evaluation of electrochemical properties of deposited films was performed using cyclic voltametry (CV) and impedance spectroscopy (IS) techniques. The analysis of the experimental data clearly showed that the variations of potential scanning ranges during deposition process have drastic effects on the geometry, chemical structure and particle size of cobalt oxide nanoparticles. In addition, the electrochemical and electrocatalytic properties of prepared nanostructures can be controlled through applying different potential windows in electrodeposition process. The imaging and voltammetric studies suggested to the existence of at least three different shapes of cobalt-oxide nanostructures in various potential windows applied for electrodeposition. With enlarging the applied potential window, the spherical-like cobalt oxide nanoparticles with particles sizes about 30–50 nm changed to the grain-like structures (30 nm × 80 nm) and then to the worm-like cobalt oxide nanostructures with 30 nm diameter and 200–400 nm in length. Furthermore, the roughness of the prepared nanostructures increased with increasing positive potential window. The GC electrodes modified with cobalt oxide nanostructures shows excellent electrocatalytic activity toward H 2 O 2 and As (III) oxidation. The electrocatalytic activity of cobalt oxide nanostructures prepared at more positive potential window toward hydrogen peroxide oxidation was increased, while for As(III) oxidation the electrocatalytic activity decreased

  6. Methods of making metal oxide nanostructures and methods of controlling morphology of same

    Wong, Stanislaus S; Hongjun, Zhou

    2012-11-27

    The present invention includes a method of producing a crystalline metal oxide nanostructure. The method comprises providing a metal salt solution and providing a basic solution; placing a porous membrane between the metal salt solution and the basic solution, wherein metal cations of the metal salt solution and hydroxide ions of the basic solution react, thereby producing a crystalline metal oxide nanostructure.

  7. Manganese-oxidizing photosynthesis before the rise of cyanobacteria

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

    2012-12-01

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

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

    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.

  9. Microwave irradiation controls the manganese oxidation states of nanostructured (Li[Li0.2Mn0.52Ni0.13Co0.13Al0.02]O2) layered cathode materials for high-performance lithium ion batteries

    Jafta, CJ

    2015-02-01

    Full Text Available A hybrid synthesis procedure, combining microwave irradiation and conventional annealing process, is described for the preparation of lithium-rich manganese-rich cathode materials, Li[Li0.2Mn0.54Ni0.13Co0.13]O2 (LMNC) and its aluminum...

  10. Electrodeposited highly-ordered manganese oxide nanowire arrays for supercapacitors

    Liu, Haifeng; Lu, Bingqiang; Wei, Shuiqiang; Bao, Mi; Wen, Yanxuan; Wang, Fan

    2012-07-01

    Large arrays of well-aligned Mn oxide nanowires were prepared by electrodeposition using anodic aluminum oxide templates. The sizes of nanowires were tuned by varying the electrotype solution involved and the MnO2 nanowires with 10 μm in length were obtained in a neutral KMnO4 bath for 1 h. MnO2 nanowire arrays grown on conductor substance save the tedious electrode-making process, and electrochemical characterization demonstrates that the MnO2 nanowire arrays electrode has good capacitive behavior. Due to the limited mass transportation in narrow spacing, the spacing effects between the neighbor nanowires have show great influence to the electrochemical performance.

  11. Nanostructured magnesium oxide biosensing platform for cholera detection

    Patel, Manoj K.; Azahar Ali, Md.; Agrawal, Ved V.; Ansari, Z. A.; Ansari, S. G.; Malhotra, B. D.

    2013-04-01

    We report fabrication of highly crystalline nanostructured magnesium oxide (NanoMgO, size >30 nm) film electrophoretically deposited onto indium-tin-oxide (ITO) glass substrate for Vibrio cholerae detection. The single stranded deoxyribonucleic acid (ssDNA) probe, consisting of 23 bases (O1 gene sequence) immobilized onto NanoMgO/ITO electrode surface, has been characterized using electrochemical, Fourier Transform-Infra Red, and UltraViolet-visible spectroscopic techniques. The hybridization studies of ssDNA/NanoMgO/ITO bioelectrode with fragmented target DNA conducted using differential pulse voltammetry reveal sensitivity as 16.80 nA/ng/cm2, response time of 3 s, linearity as 100-500 ng/μL, and stability of about 120 days.

  12. Role of manganese oxides in peptide synthesis: implication in chemical evolution

    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.

  13. Transformation from layered to tunnel structures: Synthesis, characterization, and applications of manganese oxide octahedral molecular sieves

    Xia, Guan-Guang

    Manganese oxide based octahedral molecular sieves (OMS) have been found to have a wide variety of applications as catalysts, absorbents, and battery materials due to their unique structures and physical and chemical properties. OMS materials are made up of manganese oxide octahedral building blocks sharing comers and edges to form tunnel structures. Manganese species in the framework of OMS materials are mixed valent with various ion-exchangeable cations residing in the tunnels playing important roles in charge balancing and special chemical activities. With different synthetic parameters such as the template used, temperature, pressure, and the pH of the synthetic media, layered birnessite materials were hydrothermally transformed into distinct tunnel structures with different tunnel sizes, including Mg-3x3 (OMS-1), NH4-2x2 (NH4-OMS-2), Na-2x4 (OMS-5), and other manganese oxides. Characterization of the OMS materials with a wide variety of instruments has revealed that most of them are nano-fibrous hollow crystals ith large surface areas, high ion-exchange capabilities, and relatively high thermal stabilities. The Na-2x4 tunnel structure sodium MnOx has been synthesized for the first time and studied in detail, including synthetic strategies, structural analyses, and other physical and chemical property analyses. As catalysts, the synthetic OMS materials show high catalytic activities and shape-selective properties. For example, the results of the competitive oxidation of cycloalkanes with tertiary butyl hydrogen peroxide (TBHP) over different tunnel sized ONIS materials have proven that the OMS materials with larger tunnels are more favorable for the oxidation of the biggest molecule, cyclooctane, than the smallest one, cyclohexane. Besides the tunnel size effects, tunnel cations in the OMS materials also have influences on their catalytic activities. The study of carbon monoxide cleanup for fuel cell applications demonstrates that Ag-OMS-2 (a hollandite

  14. Surface nanostructuring by ion-induced localized plasma expansion in zinc oxide

    El-Said, A. S., E-mail: elsaid@kfupm.edu.sa, E-mail: a.s.el-said@hzdr.de [Physics Department, King Fahd University of Petroleum and Minerals, Dhahran 31261 (Saudi Arabia); Institute of Ion Beam Physics and Materials Research, Helmholtz-Zentrum Dresden-Rossendorf (HZDR), 01328 Dresden (Germany); Physics Department, Faculty of Science, Mansoura University, 35516 Mansoura (Egypt); Moslem, W. M. [Department of Physics, Faculty of Science, Port Said University, Port Said 42521 (Egypt); Centre for Theoretical Physics, British University in Egypt (BUE), El-Shorouk City, Cairo (Egypt); Djebli, M. [Theoretical Physics Laboratory, Faculty of Physics USTHB, B.P. 32 Bab Ezzour, 16079 Algiers (Algeria)

    2014-06-09

    Creation of hillock-like nanostructures on the surface of zinc oxide single crystals by irradiation with slow highly charged ions is reported. At constant kinetic energy, the nanostructures were only observed after irradiation with ions of potential energies above a threshold between 19.1 keV and 23.3 keV. The size of the nanostructures increases as a function of potential energy. A plasma expansion approach is used to explain the nanostructures creation. The calculations showed that the surface nanostructures became taller with the increase of ionic temperature. The influence of charged cluster formation and the relevance of their polarity are discussed.

  15. Surface nanostructuring by ion-induced localized plasma expansion in zinc oxide

    El-Said, A. S.; Moslem, W. M.; Djebli, M.

    2014-01-01

    Creation of hillock-like nanostructures on the surface of zinc oxide single crystals by irradiation with slow highly charged ions is reported. At constant kinetic energy, the nanostructures were only observed after irradiation with ions of potential energies above a threshold between 19.1 keV and 23.3 keV. The size of the nanostructures increases as a function of potential energy. A plasma expansion approach is used to explain the nanostructures creation. The calculations showed that the surface nanostructures became taller with the increase of ionic temperature. The influence of charged cluster formation and the relevance of their polarity are discussed.

  16. Production of biogenic manganese oxides coupled with methane oxidation in a bioreactor for removing metals from wastewater.

    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.

  17. Catalytic oxidation of cyanides in an aqueous phase over individual and manganese-modified cobalt oxide systems

    Christoskova, St.; Stoyanova, M.

    2009-01-01

    The possibility for purification of wastewaters containing free cyanides by applying of a new method based on cyanides catalytic oxidation with air to CO 2 and N 2 at low temperature and atmospheric pressure was investigated. On this purpose, individual and modified with manganese Co-oxide systems as active phase of environmental catalysts were synthesized. The applied method of synthesis favours the preparation of oxide catalytic systems with high active oxygen content (total-O* and surface-O* s ) possessing high mobility, and the metal ions being in a high oxidation state and in an octahedral coordination-factors determining high activity in reactions of complete oxidation. The catalysts employed were characterized by powder X-ray diffraction, Infrared spectroscopy, and chemical analysis. The effect of pH of the medium and catalyst loading on the effectiveness of the cyanide oxidation process, expressed by the degree of conversion (α, %), by the rate constant (k, min -1 ), and COD was studied. The results obtained reveal that using catalysts investigated a high cyanide removal efficiency could be achieved even in strong alkaline medium. The higher activity of the manganese promoted catalytic sample could be explained on the basis of higher total active oxygen content and its higher mobility both depending on the conditions, under which the synthesis of catalyst is being carried out.

  18. Synthesis and characterization of monodispersed orthorhombic manganese oxide nanoparticles produced by Bacillus sp. cells simultaneous to its bioremediation

    Sinha, Arvind [Enzyme and Microbial Biochemistry Laboratory, Department of Chemistry, Indian Institute of Technology, Delhi, Hauz Khas, New Delhi 110 016 (India); Singh, Vidya Nand; Mehta, Bodh Raj [Thin Film Laboratory, Department of Physics, Indian Institute of Technology, Delhi Hauz Khas, New Delhi 110016 (India); Khare, Sunil Kumar, E-mail: skhare@rocketmail.com [Enzyme and Microbial Biochemistry Laboratory, Department of Chemistry, Indian Institute of Technology, Delhi, Hauz Khas, New Delhi 110 016 (India)

    2011-08-30

    Highlights: {yields} An efficient process wherein remediated manganese is synthesized into nanoparticles. {yields} A microbial process for manganese nanoparticle synthesis from metal waste streams. {yields} Nanoparticles characterized as monodispersed, spherical and 4.62 {+-} 0.14 nm sized MnO{sub 2}. -- Abstract: A heavy metal resistant strain of Bacillus sp. (MTCC10650) is reported. The strain exhibited the property of bioaccumulating manganese, simultaneous to its remediation. The nanoparticles thus formed were characterized and identified using energy dispersive X-ray analysis (EDAX), high resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), powder X-ray diffraction (PXRD) and atomic force microscopy (AFM). When the cells were challenged with manganese, the cells effectively synthesized nanoparticles of average size 4.62 {+-} 0.14 nm. These were mostly spherical and monodispersed. The ex situ enzymatically synthesized nanoparticles exhibited an absorbance maximum at 329 nm. These were more discrete, small and uniform, than the manganese oxide nanoparticles recovered after cell sonication. The use of Bacillus sp. cells seems promising and advantageous approach. Since, it serves dual purposes of (i) remediation and (ii) nanoparticle synthesis. Considering the increasing demand of developing environmental friendly and cost effective technologies for nanoparticle synthesis, these cells can be exploited for the remediation of manganese from the environment in conjunction with development of a greener process for the controlled synthesis of manganese oxide nanoparticles.

  19. Synthesis and characterization of monodispersed orthorhombic manganese oxide nanoparticles produced by Bacillus sp. cells simultaneous to its bioremediation

    Sinha, Arvind; Singh, Vidya Nand; Mehta, Bodh Raj; Khare, Sunil Kumar

    2011-01-01

    Highlights: → An efficient process wherein remediated manganese is synthesized into nanoparticles. → A microbial process for manganese nanoparticle synthesis from metal waste streams. → Nanoparticles characterized as monodispersed, spherical and 4.62 ± 0.14 nm sized MnO 2 . -- Abstract: A heavy metal resistant strain of Bacillus sp. (MTCC10650) is reported. The strain exhibited the property of bioaccumulating manganese, simultaneous to its remediation. The nanoparticles thus formed were characterized and identified using energy dispersive X-ray analysis (EDAX), high resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), powder X-ray diffraction (PXRD) and atomic force microscopy (AFM). When the cells were challenged with manganese, the cells effectively synthesized nanoparticles of average size 4.62 ± 0.14 nm. These were mostly spherical and monodispersed. The ex situ enzymatically synthesized nanoparticles exhibited an absorbance maximum at 329 nm. These were more discrete, small and uniform, than the manganese oxide nanoparticles recovered after cell sonication. The use of Bacillus sp. cells seems promising and advantageous approach. Since, it serves dual purposes of (i) remediation and (ii) nanoparticle synthesis. Considering the increasing demand of developing environmental friendly and cost effective technologies for nanoparticle synthesis, these cells can be exploited for the remediation of manganese from the environment in conjunction with development of a greener process for the controlled synthesis of manganese oxide nanoparticles.

  20. Recent advancements in the cobalt oxides, manganese oxides and their composite as an electrode material for supercapacitor: a review

    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.

  1. Efficient production of ultrapure manganese oxides via electrodeposition.

    Cheney, Marcos A; Joo, Sang Woo; Banerjee, Arghya; Min, Bong-Ki

    2012-08-01

    A new process for the production of electrolytic amorphous nanomanganese oxides (EAMD) with uniform size and morphology is described. EAMD are produced for the first time by cathodic deposition from a basic aqueous solution of potassium permanganate at a constant temperature of 16°C. The synthesized materials are characterized by XRD, SEM, TEM, and HRTEM. The materials produced at 5.0 V at constant temperature are amorphous with homogeneous size and morphology with an average particle size around 20 nm, which appears to be much lesser than the previously reported anodic EAMD. A potentiostatic electrodeposition with much lesser deposition rate (with respect to previously reported anodic depositions) is considered to be the reason behind the very low and homogenous particle size distribution due to the lesser agglomeration of our as-synthesized nanoparticles. Copyright © 2012 Elsevier Inc. All rights reserved.

  2. Characterization of manganese-gallium mixed oxide powders

    Sanchez Escribano, V.; Fernandez Lopez, E.; Sanchez Huidobro, P. [Universidad de Salamanca, Dept. de Quimica Inorganica (Spain); Panizza, M.; Resini, C.; Busca, G. [UNiversita di Genova, Dipt. di Ingegneria Chimica e di Processo, Genova (Italy); Resini, C. [Istituto Nazionale di Fisica della Materia, INFM (Spain); Gallardo- Amores, J.M. [Universidad Complutense, Dept. de Quimica Inorganica, Lab. Complutense de Altas Presiones, Madrid (Spain)

    2003-12-01

    Mn-Ga mixed oxides have been prepared by coprecipitation of the corresponding oxo-hydroxides as powders and have been characterized in relation to their structural and optical properties. The materials have been characterized by XRD, TG-DTA, skeletal IR and UV-visible-NIR spectroscopies. Large solubility of Mn in the diaspore type {alpha}-GaOOH oxo-hydroxide has been found. The spinel related structures of hausmannite Mn{sub 3}O{sub 4} and of {beta}-gallia present large reciprocal solubilities at least in a metastable form. At high temperature also bixbyite-type {alpha}-Mn{sub O3} solid solutions containing up to 20% at. Ga have been observed. (authors)

  3. Characterization of manganese?gallium mixed oxide powders

    Sánchez Escribano, Vicente; Fernández López, Enrique; Sánchez Huidobro, Paula; Panizza, Marta; Resini, Carlo; Gallardo-Amores, José M.; Busca, Guido

    2003-11-01

    MnGa mixed oxides have been prepared by coprecipitation of the corresponding oxo-hydroxides as powders and have been characterized in relation to their structural and optical properties. The materials have been characterized by XRD, TG-DTA, skeletal IR and UV-visible-NIR spectroscopies. Large solubility of Mn in the diaspore type α-GaOOH oxo-hydroxide has been found. The spinel related structures of hausmannite Mn 3O 4 and of β-gallia present large reciprocal solubilities at least in a metastable form. At high temperature also bixbyite-type α-Mn 2O 3 solid solutions containing up to 20% at. Ga have been observed.

  4. Guided self-assembly of nanostructured titanium oxide

    Wang Baoxiang; Rozynek, Zbigniew; Fossum, Jon Otto; Knudsen, Kenneth D; Yu Yingda

    2012-01-01

    A series of nanostructured titanium oxide particles were synthesized by a simple wet chemical method and characterized by means of small-angle x-ray scattering (SAXS)/wide-angle x-ray scattering (WAXS), atomic force microscope (AFM), scanning electron microscope (SEM), transmission electron microscope (TEM), thermal analysis, and rheometry. Tetrabutyl titanate (TBT) and ethylene glycol (EG) can be combined to form either TiO x nanowires or smooth nanorods, and the molar ratio of TBT:EG determines which of these is obtained. Therefore, TiO x nanorods with a highly rough surface can be obtained by hydrolysis of TBT with the addition of cetyl-trimethyl-ammonium bromide (CTAB) as surfactant in an EG solution. Furthermore, TiO x nanorods with two sharp ends can be obtained by hydrolysis of TBT with the addition of salt (LiCl) in an EG solution. The AFM results show that the TiO x nanorods with rough surfaces are formed by the self-assembly of TiO x nanospheres. The electrorheological (ER) effect was investigated using a suspension of titanium oxide nanowires or nanorods dispersed in silicone oil. Oil suspensions of titanium oxide nanowires or nanorods exhibit a dramatic reorganization when submitted to a strong DC electric field and the particles aggregate to form chain-like structures along the direction of applied electric field. Two-dimensional SAXS images from chains of anisotropically shaped particles exhibit a marked asymmetry in the SAXS patterns, reflecting the preferential self-assembly of the particles in the field. The suspension of rough TiO x nanorods shows stronger ER properties than that of the other nanostructured TiO x particles. We find that the particle surface roughness plays an important role in modification of the dielectric properties and in the enhancement of the ER effect. (paper)

  5. Guided self-assembly of nanostructured titanium oxide

    Wang, Baoxiang; Rozynek, Zbigniew; Fossum, Jon Otto; Knudsen, Kenneth D.; Yu, Yingda

    2012-02-01

    A series of nanostructured titanium oxide particles were synthesized by a simple wet chemical method and characterized by means of small-angle x-ray scattering (SAXS)/wide-angle x-ray scattering (WAXS), atomic force microscope (AFM), scanning electron microscope (SEM), transmission electron microscope (TEM), thermal analysis, and rheometry. Tetrabutyl titanate (TBT) and ethylene glycol (EG) can be combined to form either TiOx nanowires or smooth nanorods, and the molar ratio of TBT:EG determines which of these is obtained. Therefore, TiOx nanorods with a highly rough surface can be obtained by hydrolysis of TBT with the addition of cetyl-trimethyl-ammonium bromide (CTAB) as surfactant in an EG solution. Furthermore, TiOx nanorods with two sharp ends can be obtained by hydrolysis of TBT with the addition of salt (LiCl) in an EG solution. The AFM results show that the TiOx nanorods with rough surfaces are formed by the self-assembly of TiOx nanospheres. The electrorheological (ER) effect was investigated using a suspension of titanium oxide nanowires or nanorods dispersed in silicone oil. Oil suspensions of titanium oxide nanowires or nanorods exhibit a dramatic reorganization when submitted to a strong DC electric field and the particles aggregate to form chain-like structures along the direction of applied electric field. Two-dimensional SAXS images from chains of anisotropically shaped particles exhibit a marked asymmetry in the SAXS patterns, reflecting the preferential self-assembly of the particles in the field. The suspension of rough TiOx nanorods shows stronger ER properties than that of the other nanostructured TiOx particles. We find that the particle surface roughness plays an important role in modification of the dielectric properties and in the enhancement of the ER effect.

  6. Calcium manganese oxides as oxygen evolution catalysts: O2 formation pathways indicated by 18O-labelling studies.

    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.

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

    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

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

    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 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. Transformation kinetics and pathways of tetracycline antibiotics with manganese oxide

    Wanru, Chen [School of Civil and Environmental Engineering, Georgia Institute of Technology, Atlanta, GA 30332 (United States); Huang, Ching-Hua [School of Civil and Environmental Engineering, Georgia Institute of Technology, Atlanta, GA 30332 (United States)

    2011-05-15

    Tetracycline antibiotics including tetracycline (TTC), oxytetracycline (OTC) and chlorotetracycline (CTC) undergo rapid transformation to yield various products in the presence of MnO{sub 2} at mild conditions (pH 4-9 and 22 {sup o}C). Reaction rates follow the trend of CTC > TTC > OTC, and are affected by pH and complexation of TCs with Mg{sup 2+} or Ca{sup 2+}. Experimental results of TTC indicate that MnO{sub 2} promotes isomerization at the C ring to form iso-TTC and oxidizes the phenolic-diketone and tricarbonylamide groups, leading to insertion of up to 2 O most likely at the C9 and C2 positions. In contrast, reactions of OTC with MnO{sub 2} generate little iso-OTC, but occur mainly at the A ring's dimethylamine group to yield N-demethylated products. CTC yields the most complicated products upon reactions with MnO{sub 2}, encompassing transformation patterns observed with both TTC and OTC. The identified product structures suggest lower antibacterial activity than that of the parent tetracyclines. - Highlights: > Tetracyclines transform rapidly by MnO{sub 2} to yield complicated products. > Isomerized, (hydr)oxygenated and N-demethylated products are formed. > Transformation product structures may suggest lowered antibacterial activity. - The complex transformation pathways of three popular tetracycline antibiotics (tetracycline, oxytetracycline and chlorotetracycline) with MnO{sub 2} under environmental conditions are systematically evaluated and elucidated.

  10. Transformation kinetics and pathways of tetracycline antibiotics with manganese oxide

    Chen Wanru; Huang, Ching-Hua

    2011-01-01

    Tetracycline antibiotics including tetracycline (TTC), oxytetracycline (OTC) and chlorotetracycline (CTC) undergo rapid transformation to yield various products in the presence of MnO 2 at mild conditions (pH 4-9 and 22 o C). Reaction rates follow the trend of CTC > TTC > OTC, and are affected by pH and complexation of TCs with Mg 2+ or Ca 2+ . Experimental results of TTC indicate that MnO 2 promotes isomerization at the C ring to form iso-TTC and oxidizes the phenolic-diketone and tricarbonylamide groups, leading to insertion of up to 2 O most likely at the C9 and C2 positions. In contrast, reactions of OTC with MnO 2 generate little iso-OTC, but occur mainly at the A ring's dimethylamine group to yield N-demethylated products. CTC yields the most complicated products upon reactions with MnO 2 , encompassing transformation patterns observed with both TTC and OTC. The identified product structures suggest lower antibacterial activity than that of the parent tetracyclines. - Highlights: → Tetracyclines transform rapidly by MnO 2 to yield complicated products. → Isomerized, (hydr)oxygenated and N-demethylated products are formed. → Transformation product structures may suggest lowered antibacterial activity. - The complex transformation pathways of three popular tetracycline antibiotics (tetracycline, oxytetracycline and chlorotetracycline) with MnO 2 under environmental conditions are systematically evaluated and elucidated.

  11. Hierarchically Nanostructured Transition Metal Oxides for Lithium‐Ion Batteries

    Zheng, Mingbo; Tang, Hao; Li, Lulu; Hu, Qin; Zhang, Li; Xue, Huaiguo

    2018-01-01

    Abstract Lithium‐ion batteries (LIBs) have been widely used in the field of portable electric devices because of their high energy density and long cycling life. To further improve the performance of LIBs, it is of great importance to develop new electrode materials. Various transition metal oxides (TMOs) have been extensively investigated as electrode materials for LIBs. According to the reaction mechanism, there are mainly two kinds of TMOs, one is based on conversion reaction and the other is based on intercalation/deintercalation reaction. Recently, hierarchically nanostructured TMOs have become a hot research area in the field of LIBs. Hierarchical architecture can provide numerous accessible electroactive sites for redox reactions, shorten the diffusion distance of Li‐ion during the reaction, and accommodate volume expansion during cycling. With rapid research progress in this field, a timely account of this advanced technology is highly necessary. Here, the research progress on the synthesis methods, morphological characteristics, and electrochemical performances of hierarchically nanostructured TMOs for LIBs is summarized and discussed. Some relevant prospects are also proposed. PMID:29593962

  12. A novel nanostructure of cadmium oxide synthesized by mechanochemical method

    Tadjarodi, A., E-mail: tajarodi@iust.ac.ir [Research Laboratory of Inorganic Materials Synthesis, Department of Chemistry, Iran University of Science and Technology, 16846-13114 Tehran (Iran, Islamic Republic of); Imani, M. [Research Laboratory of Inorganic Materials Synthesis, Department of Chemistry, Iran University of Science and Technology, 16846-13114 Tehran (Iran, Islamic Republic of)

    2011-11-15

    Highlights: {yields} A novel nanostructure of CdO was synthesized by mechanochemical reaction followed by calcination. {yields} Mechanochemical method is a simple and low-cost to synthesize nanomaterials. {yields} The obtained precursor was characterized by FT-IR, NMR techniques and elemental analysis. {yields} SEM images showed cauliflower-like shape of sample with components average diameter of 68 nm. {yields} The rods and tubes bundles with single crystalline nature were revealed by ED pattern and TEM images. -- Abstract: Cauliflower-like cadmium oxide (CdO) nanostructure was synthesized by mechanochemical reaction followed calcination procedure. Cadmium acetate dihydrate and acetamide were used as reagents and the resulting precursor was calcinated at 450 {sup o}C for 2 h in air. The structures of the precursor and resultant product of the heating treatment were characterized using Fourier transform infrared (FT-IR) spectroscopy, nuclear magnetic resonance (NMR) spectroscopy and elemental analysis, X-ray powder diffraction (XRD), energy-dispersive X-ray spectroscopy analysis (EDX), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and electron diffraction pattern (ED). SEM and TEM images revealed the cauliflower-like morphology of the sample. This structure includes the bundles of rods and tubes in nanoscale, which combine with each other and form the resulting morphology with the average diameter, 68 nm of the components. ED pattern indicated the single crystal nature of the formed bundles.

  13. A novel nanostructure of cadmium oxide synthesized by mechanochemical method

    Tadjarodi, A.; Imani, M.

    2011-01-01

    Highlights: → A novel nanostructure of CdO was synthesized by mechanochemical reaction followed by calcination. → Mechanochemical method is a simple and low-cost to synthesize nanomaterials. → The obtained precursor was characterized by FT-IR, NMR techniques and elemental analysis. → SEM images showed cauliflower-like shape of sample with components average diameter of 68 nm. → The rods and tubes bundles with single crystalline nature were revealed by ED pattern and TEM images. -- Abstract: Cauliflower-like cadmium oxide (CdO) nanostructure was synthesized by mechanochemical reaction followed calcination procedure. Cadmium acetate dihydrate and acetamide were used as reagents and the resulting precursor was calcinated at 450 o C for 2 h in air. The structures of the precursor and resultant product of the heating treatment were characterized using Fourier transform infrared (FT-IR) spectroscopy, nuclear magnetic resonance (NMR) spectroscopy and elemental analysis, X-ray powder diffraction (XRD), energy-dispersive X-ray spectroscopy analysis (EDX), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and electron diffraction pattern (ED). SEM and TEM images revealed the cauliflower-like morphology of the sample. This structure includes the bundles of rods and tubes in nanoscale, which combine with each other and form the resulting morphology with the average diameter, 68 nm of the components. ED pattern indicated the single crystal nature of the formed bundles.

  14. Determination of the point-of-zero, charge of manganese oxides with different methods including an improved salt titration method

    Tan, W.F.; Lu, S.J.; Liu, F.; Feng, X.H.; He, J.Z.; Koopal, L.K.

    2008-01-01

    Manganese (Mn) oxides are important components in soils and sediments. Points-of-zero charge (PZC) of three synthetic Mn oxides (birnessite, cryptomelane, and todorokite) were determined by using three classical techniques (potentiometric titration or PT, rapid PT or R-PT, and salt titration or ST)

  15. Decolorization of methylene blue in layered manganese oxide suspension with H2O2

    Zhang Lili; Nie Yulun; Hu Chun; Hu Xuexiang

    2011-01-01

    Highlights: → Layered birnessite-type manganese oxides exhibited a well-crystallized octahedral layer (OL) structure with β-MnOOH, α-MnOOH and γ-Mn 3 O 4 . → The catalyst was highly effective for the decolorization and degradation of methylene blue in the presence of H 2 O 2 at neutral pH. → The 1 O 2 and O 2 · - were the main reactive oxygen species in the reaction. - Abstract: Layered birnessite-type manganese oxides (Na-OL-1) were prepared via a redox reaction involving MnO 4 - and Mn 2+ under markedly alkaline conditions. According to the XRD analysis, the resulting material exhibited a well-crystallized octahedral layer (OL) structure with several different phases, including β-MnOOH, α-MnOOH and γ-Mn 3 O 4 . The catalyst was highly effective for the decolorization and degradation of methylene blue (MB) in the presence of H 2 O 2 at neutral pH. The tested MB was completely decolorized in Na-OL-1 suspension by the fraction dosing of H 2 O 2 (556.5 mM at the beginning and then 183.8 mM at 40 min). Based on the studies of electron spin resonance and the effect of radical scavengers, the 1 O 2 and O 2 · - were the main reactive oxygen species (ROS) in the reaction. It was found that both oxygen and ROS were generated from the decomposition of H 2 O 2 in Na-OL-1 suspension, wherein the decomposition pathways were proposed. The generation of H 2 O 2 in Na-OL-1 suspension at air atmosphere indicated that the existence of multivalent manganese oxides greatly enhanced the interfacial electron transfer, leading to the high activity of Na-OL-1.

  16. Exchange interactions in a dinuclear manganese (II) complex with cyanopyridine-N-oxide bridging ligands

    Markosyan, A.S. [Faculty of Physics, M.V. Lomonosov Moscow State University, 119992 Moscow (Russian Federation); Department of Applied Physics, Stanford University (United States); Gaidukova, I.Yu.; Ruchkin, A.V. [Faculty of Physics, M.V. Lomonosov Moscow State University, 119992 Moscow (Russian Federation); Anokhin, A.O. [Institute of Metal Physics, Ural Division of the Russian, Ekaterinburg (Russian Federation); Irkhin, V.Yu., E-mail: valentin.irkhin@imp.uran.ru [Institute of Metal Physics, Ural Division of the Russian, Ekaterinburg (Russian Federation); Ryazanov, M.V.; Kuz’mina, N.P. [Faculty of Chemistry, M.V. Lomonosov Moscow State University, 119992 Moscow (Russian Federation); Nikiforov, V.N. [Faculty of Physics, M.V. Lomonosov Moscow State University, 119992 Moscow (Russian Federation)

    2014-01-01

    The magnetic properties of dinuclear manganese(II) complex [Mn(hfa){sub 2}cpo]{sub 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){sub 2}(cpo)]{sub 2} is simulated numerically by an extrapolation to spin S=5/2. The Mn–Mn exchange integral is evaluated.

  17. Improved capacity retention in rechargeable 4 V lithium/lithium manganese oxide (spinel) cells.

    Gummow, RJ

    1994-04-01

    Full Text Available manganese-ion oxidation state marginally above 3.5. 1. Introduction Over the past decade, the spine1 LiMnzOd has been studied extensively as an electrode for rechargeable lithium cells [l-7]. When O

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

    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.

  19. Amino acid-assisted synthesis of zinc oxide nanostructures

    Singh, Baljinder; Moudgil, Lovika; Singh, Gurinder; Kaura, Aman

    2018-05-01

    In this manuscript we have used experimental approach that can provide a fundamental knowledge about the role played by biomolecules in designing the shape of nanostructure (NS) at a microscopic level. The three different amino acids (AAs) - Arginine (Arg), Aspartic acid (Asp) and Histidine (His) coated Zinc oxide (ZnO) NSs to explain the growth mechanism of nanoparticles of different shapes. Based on the experimental methodology we propose that AA-ZnO (Asp and Arg) nanomaterials could form of rod like configuration and His-ZnO NPs could form tablet like configuration. The synthesized samples are characterized using transmission electron microscopy (TEM) and X-ray diffraction (XRD). Results reveal that AAs are responsible for formation of different NSs

  20. Zinc oxide nanostructures: new properties for advances applications

    Lupan, Oleg; Chow, Lee; Pauporte, Thierry

    2011-01-01

    Zinc oxide is a material which exhibits a variety of new properties at nanometer dimensions. Various synthesis techniques have been carried out to provide growth of nanowires, nanorods, nanorings, nanosprings, and nanobelts of ZnO under various conditions. These nanostructures show that ZnO possesses probably the richest family of nanoarchitectures among all materials, including their structures and properties. Such nanoarchitectures are potential building blocks for novel applications in optoelectronics, sensors, photovoltaic and nano-biomedical sciences. This work presents a review of various nano architectures of ZnO grown by the electrochemical, hydrothermal and solid-vapor phase techniques and their properties. The possible applications of ZnO nanowires as sensors, nano-DSSC, photodetectors and nano-LEDs will be presented.

  1. Stable Water Oxidation in Acid Using Manganese-Modified TiO2 Protective Coatings.

    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.

  2. Study of interaction and adsorption of aromatic amines by manganese oxides and their role in chemical evolution

    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.

  3. A general strategy toward the rational synthesis of metal tungstate nanostructures using plasma electrolytic oxidation method

    Jiang, Yanan; Liu, Baodan; Zhai, Zhaofeng; Liu, Xiaoyuan; Yang, Bing; Liu, Lusheng; Jiang, Xin

    2015-01-01

    Graphical abstract: A general strategy for the rational synthesis of tungstate nanostructure has been developed based on plasma electrolytic oxidation (PEO) technology (up). Using this method, ZnWO 4 and NiWO 4 nanostructures with controllable morphologies and superior crystallinity can be easily obtained (down), showing obvious advantage in comparison with conventional hydrothermal and sol–gel methods. - Highlights: • Plasma electrolyte oxidation (PEO) method has been used for the rational synthesis of tungstate nanostructures. • ZnWO 4 nanoplates have strong mechanical adhesion with porous TiO 2 film substrate. • The morphology and dimensional size of ZnWO 4 nanostructures can be selectively tailored by controlling the annealing temperature and growth time. • The PEO method can be widely applied to the growth of various metal oxides. - Abstract: A new method based on conventional plasma electrolytic oxidation (PEO) technology has been developed for the rational synthesis of metal tungstate nanostructures. Using this method, ZnWO 4 and NiWO 4 nanostructures with controllable morphologies (nanorods, nanosheets and microsheets) and superior crystallinity have been synthesized. It has been found that the morphology diversity of ZnWO 4 nanostructures can be selectively tailored through tuning the electrolyte concentration and annealing temperatures, showing obvious advantages in comparison to traditional hydrothermal and sol–gel methods. Precise microscopy analyses on the cross section of the PEO coating and ZnWO 4 nanostructures confirmed that the precursors initially precipitated in the PEO coating and its surface during plasma discharge process are responsible for the nucleation and subsequent growth of metal tungstate nanostructures by thermal annealing. The method developed in this work represents a general strategy toward the rational synthesis of metal oxide nanostructures and the formation mechanism of metal tungstate nanostructures fabricated by

  4. A general strategy toward the rational synthesis of metal tungstate nanostructures using plasma electrolytic oxidation method

    Jiang, Yanan; Liu, Baodan, E-mail: baodanliu@imr.ac.cn; Zhai, Zhaofeng; Liu, Xiaoyuan; Yang, Bing; Liu, Lusheng; Jiang, Xin, E-mail: xjiang@imr.ac.cn

    2015-11-30

    Graphical abstract: A general strategy for the rational synthesis of tungstate nanostructure has been developed based on plasma electrolytic oxidation (PEO) technology (up). Using this method, ZnWO{sub 4} and NiWO{sub 4} nanostructures with controllable morphologies and superior crystallinity can be easily obtained (down), showing obvious advantage in comparison with conventional hydrothermal and sol–gel methods. - Highlights: • Plasma electrolyte oxidation (PEO) method has been used for the rational synthesis of tungstate nanostructures. • ZnWO{sub 4} nanoplates have strong mechanical adhesion with porous TiO{sub 2} film substrate. • The morphology and dimensional size of ZnWO{sub 4} nanostructures can be selectively tailored by controlling the annealing temperature and growth time. • The PEO method can be widely applied to the growth of various metal oxides. - Abstract: A new method based on conventional plasma electrolytic oxidation (PEO) technology has been developed for the rational synthesis of metal tungstate nanostructures. Using this method, ZnWO{sub 4} and NiWO{sub 4} nanostructures with controllable morphologies (nanorods, nanosheets and microsheets) and superior crystallinity have been synthesized. It has been found that the morphology diversity of ZnWO{sub 4} nanostructures can be selectively tailored through tuning the electrolyte concentration and annealing temperatures, showing obvious advantages in comparison to traditional hydrothermal and sol–gel methods. Precise microscopy analyses on the cross section of the PEO coating and ZnWO{sub 4} nanostructures confirmed that the precursors initially precipitated in the PEO coating and its surface during plasma discharge process are responsible for the nucleation and subsequent growth of metal tungstate nanostructures by thermal annealing. The method developed in this work represents a general strategy toward the rational synthesis of metal oxide nanostructures and the formation mechanism of

  5. Manganese oxide electrode with excellent electrochemical performance for sodium ion batteries by pre-intercalation of K and Na ions.

    Feng, Mengya; Du, Qinghua; Su, Li; Zhang, Guowei; Wang, Guiling; Ma, Zhipeng; Gao, Weimin; Qin, Xiujuan; Shao, Guangjie

    2017-05-22

    Materials with a layered structure have attracted tremendous attention because of their unique properties. The ultrathin nanosheet structure can result in extremely rapid intercalation/de-intercalation of Na ions in the charge-discharge progress. Herein, we report a manganese oxide with pre-intercalated K and Na ions and having flower-like ultrathin layered structure, which was synthesized by a facile but efficient hydrothermal method under mild condition. The pre-intercalation of Na and K ions facilitates the access of electrolyte ions and shortens the ion diffusion pathways. The layered manganese oxide shows ultrahigh specific capacity when it is used as cathode material for sodium-ion batteries. It also exhibits excellent stability and reversibility. It was found that the amount of intercalated Na ions is approximately 71% of the total charge. The prominent electrochemical performance of the manganese oxide demonstrates the importance of design and synthesis of pre-intercalated ultrathin layered materials.

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

    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.

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

    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).

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

    Salter-Blanc, Alexandra J.; Lyon, Molly A.; Science University, Portland, OR; Ness, Stuart C.; Science University, Portland, OR; Tratnyek, Paul G.; Science University, Portland, OR

    2016-01-01

    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 [Hammett σ constants (σ − ), pK a s 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).

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

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

    Gallegos, María V., E-mail: plapimu@yahoo.com.ar [Pla.Pi.Mu-Planta Piloto Multipropósito, (CICPBA-UNLP) Cno. Centenario y 505, M.B. Gonnet, Buenos Aires (Argentina); Falco, Lorena R., E-mail: mlfalco@quimica.unlp.edu.ar [Pla.Pi.Mu-Planta Piloto Multipropósito, (CICPBA-UNLP) Cno. Centenario y 505, M.B. Gonnet, Buenos Aires (Argentina); Peluso, Miguel A., E-mail: apelu@quimica.unlp.edu.ar [Centro de Investigación y Desarrollo en Ciencias Aplicadas, “Dr. J. Ronco” CINDECA (CONICET CCT La Plata), 47 N°257, La Plata, Buenos Aires (Argentina); Sambeth, Jorge E., E-mail: sambeth@quimica.unlp.edu.ar [Centro de Investigación y Desarrollo en Ciencias Aplicadas, “Dr. J. Ronco” CINDECA (CONICET CCT La Plata), 47 N°257, La Plata, Buenos Aires (Argentina); Thomas, Horacio J. [Pla.Pi.Mu-Planta Piloto Multipropósito, (CICPBA-UNLP) Cno. Centenario y 505, M.B. Gonnet, Buenos Aires (Argentina)

    2013-06-15

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

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

    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.

  12. Oxygen reduction reaction catalysts of manganese oxide decorated by silver nanoparticles for aluminum-air batteries

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

    2016-01-01

    In this paper, the hybrid catalysts of manganese oxide decorated by silver nanoparticles (Ag-MnO x ) are fully investigated and show the excellent oxygen reduction reaction (ORR) activity. The Ag-MnO 2 is synthesized by a facile strategy of the electroless plating of silver on the manganese oxide. The catalysts are characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). Then, the ORR activities of the catalysts are systematically investigated by the rotating disk electrode (RDE) and aluminum-air battery technologies. The Ag nanoparticles with the diameters at about 10 nm are anchored on the surface of α-MnO 2 and a strong interaction between Ag and MnO 2 components in the hybrid catalyst are confirmed. The electrochemical tests show that the activity and stability of the 50%Ag-MnO 2 composite catalyst (the mass ratio of Ag/MnO 2 is 1:1) toward ORR are greatly enhanced comparing with single Ag or MnO 2 catalyst. Moreover, the peak power density of the aluminum-air battery with 50%Ag-MnO 2 can reach 204 mW cm −2 .

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

    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).

  14. Coating manganese oxide onto graphite electrodes by immersion for electrochemical capacitors

    Lin, C.-C.; Chen, H.-W.

    2009-01-01

    In this study, manganese oxide was coated on a graphite electrode by immersion. Durations for immersion were varied to control the amount of manganese oxide coated onto the electrode surface. Maximum capacitance of 556 mF cm -2 was obtained in 0.5 M LiCl and with better/superior conditions (immersion time = 80 min and potential scan rate = 10 mV s -1 ). In addition, cyclic voltammograms of the prepared electrode at different potential scan rates exhibited the approximately rectangular and symmetric current-potential characteristics of a capacitor. Furthermore, the chronopotentiometry (CP) charge-discharge curves of the electrode prepared at 80 min of immersion time with a constant current of 1 mA were symmetric and similar isosceles triangles, which demonstrate its high electrochemical reversibility and good stability. Finally, under scanning electron microscope (SEM), the surface of the electrode prepared at 80 min of immersion time and after 1500 cycles of potential cycling revealed that numerously three-dimensional network of macropores appeared on large spherical grains

  15. One-dimensional manganese-cobalt oxide nanofibres as bi-functional cathode catalysts for rechargeable metal-air batteries

    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 nanof...

  16. Effects of synthetic parameters on structure and electrochemical performance of spinel lithium manganese oxide by citric acid-assisted sol-gel method

    Yi Tingfeng; Dai Changsong; Gao Kun; Hu Xinguo

    2006-01-01

    The spinel lithium manganese oxide cathode materials were prepared by citric acid-assisted sol-gel method at 623-1073 K in air. The effects of pH value, raw material, synthesis temperature and time on structure and electrochemical performance of spinel lithium manganese oxide are investigated by X-ray diffraction (XRD), scanning electronic microscope (SEM) and cyclic voltammetry (CV). XRD data results strongly suggest that the synthesis temperature is the dominating factors of the formation of spinel phase, and spinel lithium manganese oxide powder with various crystallites size can be obtained by controlling the sintering time. CV shows that spinel lithium manganese oxide powder formed about 973 K presents the best electrochemical performance with well separated two peaks and the highest peak current. Charge-discharge test indicates that spinel lithium manganese oxide powders calcined at higher temperatures have high discharge capacity and capacity loss, and sintered at lower temperatures has low discharge capacity and high capacity retention

  17. Effects of synthetic parameters on structure and electrochemical performance of spinel lithium manganese oxide by citric acid-assisted sol-gel method

    Yi Tingfeng [Department of Applied Chemistry, Harbin Institute of Technology, Harbin 150001 (China)]. E-mail: tfyihit@hit.edu.cn; Dai Changsong [Department of Applied Chemistry, Harbin Institute of Technology, Harbin 150001 (China); Gao Kun [Department of Applied Chemistry, Harbin Institute of Technology, Harbin 150001 (China); Hu Xinguo [Department of Applied Chemistry, Harbin Institute of Technology, Harbin 150001 (China)

    2006-11-30

    The spinel lithium manganese oxide cathode materials were prepared by citric acid-assisted sol-gel method at 623-1073 K in air. The effects of pH value, raw material, synthesis temperature and time on structure and electrochemical performance of spinel lithium manganese oxide are investigated by X-ray diffraction (XRD), scanning electronic microscope (SEM) and cyclic voltammetry (CV). XRD data results strongly suggest that the synthesis temperature is the dominating factors of the formation of spinel phase, and spinel lithium manganese oxide powder with various crystallites size can be obtained by controlling the sintering time. CV shows that spinel lithium manganese oxide powder formed about 973 K presents the best electrochemical performance with well separated two peaks and the highest peak current. Charge-discharge test indicates that spinel lithium manganese oxide powders calcined at higher temperatures have high discharge capacity and capacity loss, and sintered at lower temperatures has low discharge capacity and high capacity retention.

  18. Hybrid manganese oxide films for supercapacitor application prepared by sol-gel technique

    Chen, Chin-Yi; Wang, Sheng-Chang; Tien, Yue-Han; Tsai, Wen-Ta; Lin, Chung-Kwei

    2009-01-01

    Hybrid films were prepared by adding various concentrations of meso-carbon microbeads (MCMB) during sol-gel processing of manganese oxide films. The heat-treated films were characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD). In addition, electrochemical performance of the MCMB-added Mn-oxide hybrid coatings was evaluated by cyclic voltammetry (CV) and compared with its unadded counterpart. Experimental results showed that Mn-oxide films exhibited a mixture of Mn 2 O 3 and Mn 3 O 4 phases. The higher the heat-treatment temperature, the more Mn 2 O 3 can be observed. The specific capacitance of the unadded Mn-oxide electrodes is 209 F/g. Because the MCMB particles provide more interfacial surface area for electrochemical reactions, a significant improvement can be noticed by adding MCMB in Mn-oxide coatings. The 300 o C heat-treated hybrid Mn-oxide coating with a Mn/MCMB ratio of 10/1 exhibits the highest value of 350 F/g, showing a ∼ 170% increase in specific capacitance.

  19. Multilayered films of cobalt oxyhydroxide nanowires/manganese oxide nanosheets for electrochemical capacitor

    Zheng, Huajun [State Key Laboratory Breeding Base of Green Chemistry Synthesis Technology, Zhejiang University of Technology, Hangzhou 310014 (China); ARC Centre of Excellence for Functional Nanomaterials, School of Chemical Engineering and AIBN, The University of Queensland, St Lucia, Brisbane, QLD 4072 (Australia); Tang, Fengqiu; Mukherji, Aniruddh; Yan, Xiaoxia; Wang, Lianzhou (Max) Lu, Gao Qing [ARC Centre of Excellence for Functional Nanomaterials, School of Chemical Engineering and AIBN, The University of Queensland, St Lucia, Brisbane, QLD 4072 (Australia); Lim, Melvin [Division of Environmental and Water Resources Engineering, School of Civil and Environmental Engineering, Nanyang Technological University, 639798 (Singapore)

    2010-01-15

    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{sup -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. (author)

  20. Electrochemical synthesis of magnetic nanostructures using anodic aluminum oxide templates

    Gong, Jie

    In this dissertation, template electrodeposition was employed to fabricate high quality magnetic nanostructures suited for the reliable investigation of novel spintronics phenomena such as CIMS, BMR, and CPP-GMR. Several critical aspects/steps relating to the synthesis process were investigated in this work. In order to obtain high quality magnetic nanostructures, free-standing and Si-supported anodic aluminum oxide templates with closely controlled pore diameters, lengths, as well as constriction sizes, were synthesized by anodization, followed by appropriate post-processing. The pore opening size on the barrier layer can be controlled down to 5 nm by ion beam etching. After optimization of the compositional, structural, and magnetic properties of homogeneous FeCoNiCu layers electrodeposited under different conditions, the pulsed deposition process of FeCoNI/Cu multilayers on n-Si was studied. The influence of Cu deposition potential and Fe2+ concentration on microstructure, chemical and electrochemical properties, magnetic properties, and hence magnetotransport properties were assessed. The dissolution of the FM layer during potential transition was minimized in order to control interface sharpness. Combined with the systematic sublayer thickness and FM layer composition optimization, unprecedented GMR sensitivity of 0.11%/Oe at 5-15 Oe was obtained. Growth of multilayer nanowires was performed, and contact to a single wire was attempted using an electrochemical technique. We succeeded in addressing a small number of nanowires and measured a CPP-GMR of 17%. Template electrodeposition thus provides a promising way to repeatably fabricate prototypes for spin dependent transport studies.

  1. Surface electronic and structural properties of nanostructured titanium oxide grown by pulsed laser deposition

    Fusi, M.; Maccallini, E.; Caruso, T.; Casari, C. S.; Bassi, A. Li; Bottani, C. E.; Rudolf, P.; Prince, K. C.; Agostino, R. G.

    Titanium oxide nanostructured thin films synthesized by pulsed laser deposition (PLD) were here characterized with a multi-technique approach to investigate the relation between surface electronic, structural and morphological properties. Depending on the growth parameters, these films present

  2. Hydroxylation of benzene to phenol over magnetic recyclable nanostructured CuFe mixed-oxide catalyst

    Makgwane, PR

    2015-03-01

    Full Text Available A highly active and magnetically recyclable nanostructured copper–iron oxide (CuFe) catalyst has been synthesized for hydroxylation of benzene to phenol under mild reaction conditions. The obtained catalytic results were correlated with the catalyst...

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

    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.

  4. Oxidation of triclosan by permanganate (Mn(VII)): importance of ligands and in situ formed manganese oxides.

    Jiang, Jin; Pang, Su-Yan; Ma, Jun

    2009-11-01

    Experiments were conducted to examine permanganate (Mn(VII); KMnO(4)) oxidation of the widely used biocide triclosan (one phenolic derivative) in aqueous solution at pH values of 5-9. Under slightly acidic conditions, the reactions displayed autocatalysis, suggesting the catalytic role of in situ formed MnO(2). This was further supported by the promoting effects of the addition of preformed MnO(2) colloids on Mn(VII) oxidations of triclosan and two other selected phenolics (i.e., phenol and 2,4-dichlorophenol), as well as p-nitrophenol which otherwise showed negligible reactivity toward Mn(VII) and MnO(2) colloids, respectively. Surprisingly, phosphate buffer significantly enhanced Mn(VII) oxidation of triclosan, as well as phenol and 2,4-dichlorophenol over a wide pH range. Further, several other selected ligands (i.e., pyrophosphate, EDTA, and humic acid) also exerted oxidation enhancement, supporting a scenario where highly active aqueous manganese intermediates (Mn(INT)(aq)) formed in situ upon Mn(VII) reduction might be stabilized to a certain extent in the presence of ligands and subsequently involved in further oxidation of target phenolics, whereas without stabilizing agents Mn(INT)(aq) autodecomposes or disproportionates spontaneously. The effectiveness of Mn(VII) for the oxidative removal of triclosan in natural water and wastewater was confirmed. Their background matrices were also found to accelerate Mn(VII) oxidation of phenolics.

  5. A multicopper oxidase is essential for manganese oxidation and laccase-like activity in Pedomicrobium sp. ACM 3067.

    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.

  6. Synthesis of Pt–Pd Bimetallic Porous Nanostructures as Electrocatalysts for the Methanol Oxidation Reaction

    Yong Yang

    2018-03-01

    Full Text Available Pt-based bimetallic nanostructures have attracted a great deal of attention due to their unique nanostructures and excellent catalytic properties. In this study, we prepared porous Pt–Pd nanoparticles using an efficient, one-pot co-reduction process without using any templates or toxic reactants. In this process, Pt–Pd nanoparticles with different nanostructures were obtained by adjusting the temperature and ratio of the two precursors; and their catalytic properties for the oxidation of methanol were studied. The porous Pt–Pd nanostructures showed better electrocatalytic activity for the oxidation of methanol with a higher current density (0.67 mA/cm2, compared with the commercial Pt/C catalyst (0.31 mA/cm2. This method provides one easy pathway to economically prepare different alloy nanostructures for various applications.

  7. Catalytic activity of bimetallic AuPd alloys supported MgO and MnO2 nanostructures and their role in selective aerobic oxidation of alcohols

    Hamed Alshammari

    2017-10-01

    Full Text Available The use of metal oxides as supports for gold and palladium (Au-Pd nano alloys constitutes new horizons to improve catalysts materials for very important reactions. From the literatures, Pd-based bimetallic nanostructures have great properties and active catalytic performance. In this study, nanostructures of magnesium oxide (MgO and manganese dioxide (MnO₂ were synthesised and utilized as supports for Au-Pd nanoparticle catalysts. Gold and palladium were deposited on these supports using sol-immobilisation method. The MgO and MnO2 supported Au-Pd catalysts were evaluated for the oxidation of benzyl alcohol and 1-octanol, respectively. These catalysts were found to be more selective, active and reusable than the corresponding monometallic Au and Pd catalysts. The effect of base supports on the disproportionation reaction during the oxidation process was investigated. The results show that MgO stopped the disproportionation reaction for both aromatic and aliphatic alcohols while MnO₂ stopped it in the case of benzyl alcohol only. The outcomes of this work shed light on the selective aerobic oxidation of alcohols using bimetallic Au-Pd nanoalloys and pave the way to a complete investigation of more basic metal oxides for various aliphatic alcohols.

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

    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

  9. Subchronic, Low-Level Intraperitoneal Injections of Manganese (IV) Oxide and Manganese (II) Chloride Affect Rat Brain Neurochemistry

    Nielsen, Brian S.; Larsen, Erik Huusfeldt; Ladefoged, Ole

    2017-01-01

    Manganese (Mn) is neurotoxic and can induce manganism, a Parkinson-like disease categorized as being a serious central nervous system irreversible neurodegenerative disease. An increased risk of developing symptoms of Parkinson disease has been linked to work-related exposure, for example......Cl2)/kg bw/day for 7 d/wk for 8 or 12 weeks. This dosing regimen adds relevant new knowledge about Mn neurotoxicity as a consequence of low-dose subchronic Mn dosing. Manganese concentrations increased in the striatum, the rest of the brain, and in plasma, and regional brain neurotransmitter...... with MnCl2. Plasma prolactin concentration was not significantly affected due to a potentially reduced dopaminergic inhibition of the prolactin release from the anterior hypophysis. No effects on the striatal α-synuclein and synaptophysin protein levels were detected....

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

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

    1990-07-01

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

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

    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.

  12. The Adsorption of Cd(II) on Manganese Oxide Investigated by Batch and Modeling Techniques.

    Huang, Xiaoming; Chen, Tianhu; Zou, Xuehua; Zhu, Mulan; Chen, Dong; Pan, Min

    2017-09-28

    Manganese (Mn) oxide is a ubiquitous metal oxide in sub-environments. The adsorption of Cd(II) on Mn oxide as function of adsorption time, pH, ionic strength, temperature, and initial Cd(II) concentration was investigated by batch techniques. The adsorption kinetics showed that the adsorption of Cd(II) on Mn oxide can be satisfactorily simulated by pseudo-second-order kinetic model with high correlation coefficients (R² > 0.999). The adsorption of Cd(II) on Mn oxide significantly decreased with increasing ionic strength at pH adsorption was independent of ionic strength at pH > 6.0, which indicated that outer-sphere and inner-sphere surface complexation dominated the adsorption of Cd(II) on Mn oxide at pH 6.0, respectively. The maximum adsorption capacity of Mn oxide for Cd(II) calculated from Langmuir model was 104.17 mg/g at pH 6.0 and 298 K. The thermodynamic parameters showed that the adsorption of Cd(II) on Mn oxide was an endothermic and spontaneous process. According to the results of surface complexation modeling, the adsorption of Cd(II) on Mn oxide can be satisfactorily simulated by ion exchange sites (X₂Cd) at low pH and inner-sphere surface complexation sites (SOCd⁺ and (SO)₂CdOH - species) at high pH conditions. The finding presented herein plays an important role in understanding the fate and transport of heavy metals at the water-mineral interface.

  13. The Adsorption of Cd(II on Manganese Oxide Investigated by Batch and Modeling Techniques

    Xiaoming Huang

    2017-09-01

    Full Text Available Manganese (Mn oxide is a ubiquitous metal oxide in sub-environments. The adsorption of Cd(II on Mn oxide as function of adsorption time, pH, ionic strength, temperature, and initial Cd(II concentration was investigated by batch techniques. The adsorption kinetics showed that the adsorption of Cd(II on Mn oxide can be satisfactorily simulated by pseudo-second-order kinetic model with high correlation coefficients (R2 > 0.999. The adsorption of Cd(II on Mn oxide significantly decreased with increasing ionic strength at pH < 5.0, whereas Cd(II adsorption was independent of ionic strength at pH > 6.0, which indicated that outer-sphere and inner-sphere surface complexation dominated the adsorption of Cd(II on Mn oxide at pH < 5.0 and pH > 6.0, respectively. The maximum adsorption capacity of Mn oxide for Cd(II calculated from Langmuir model was 104.17 mg/g at pH 6.0 and 298 K. The thermodynamic parameters showed that the adsorption of Cd(II on Mn oxide was an endothermic and spontaneous process. According to the results of surface complexation modeling, the adsorption of Cd(II on Mn oxide can be satisfactorily simulated by ion exchange sites (X2Cd at low pH and inner-sphere surface complexation sites (SOCd+ and (SO2CdOH− species at high pH conditions. The finding presented herein plays an important role in understanding the fate and transport of heavy metals at the water–mineral interface.

  14. The Adsorption of Cd(II) on Manganese Oxide Investigated by Batch and Modeling Techniques

    Huang, Xiaoming; Chen, Tianhu; Zou, Xuehua; Zhu, Mulan; Chen, Dong

    2017-01-01

    Manganese (Mn) oxide is a ubiquitous metal oxide in sub-environments. The adsorption of Cd(II) on Mn oxide as function of adsorption time, pH, ionic strength, temperature, and initial Cd(II) concentration was investigated by batch techniques. The adsorption kinetics showed that the adsorption of Cd(II) on Mn oxide can be satisfactorily simulated by pseudo-second-order kinetic model with high correlation coefficients (R2 > 0.999). The adsorption of Cd(II) on Mn oxide significantly decreased with increasing ionic strength at pH adsorption was independent of ionic strength at pH > 6.0, which indicated that outer-sphere and inner-sphere surface complexation dominated the adsorption of Cd(II) on Mn oxide at pH 6.0, respectively. The maximum adsorption capacity of Mn oxide for Cd(II) calculated from Langmuir model was 104.17 mg/g at pH 6.0 and 298 K. The thermodynamic parameters showed that the adsorption of Cd(II) on Mn oxide was an endothermic and spontaneous process. According to the results of surface complexation modeling, the adsorption of Cd(II) on Mn oxide can be satisfactorily simulated by ion exchange sites (X2Cd) at low pH and inner-sphere surface complexation sites (SOCd+ and (SO)2CdOH− species) at high pH conditions. The finding presented herein plays an important role in understanding the fate and transport of heavy metals at the water–mineral interface. PMID:28956849

  15. Preparation of anionic clay–birnessite manganese oxide composites by interlayer oxidation of oxalate ions by permanganate

    Arulraj, James; Rajamathi, Michael

    2013-01-01

    Oxalate intercalated anionic clay-like nickel zinc hydroxysalt was obtained starting from nickel zinc hydroxyacetate, Ni 3 Zn 2 (OH) 8 (OAc) 2 ·2H 2 O, by anion exchange. The intercalated oxalate species was reacted with potassium permanganate in such a way that the layered manganese oxide formed was within the interlayer region of the anionic clay resulting in a layered composite in which the negative charges on the birnessite type manganese oxide layers compensate the positive charges on the anionic clay layers. Birnessite to anionic clay ratio could be varied by varying the reaction time or the amount of potassium permanganate used. - Graphical abstract: Nickel zinc hydroxyoxalate was reacted with potassium permanganate to get nickel zinc hydroxide birnessite composites in which the positive charges on the hydroxide layers are neutralized by the negative charges on birnessite layers. Highlights: ► Anionic and cationic layered solid composites prepared. ► Ni–Zn hydroxyoxalate reacted with KMnO 4 to deposit MnO 2 in the interlayer. ► Birnessite layers coexist with anionic clay layers in the composites. ► Birnessite/anionic clay ratio controlled by amount of KMnO 4 used and reaction time

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

    Arulraj, James [Materials Research Group, Department of Chemistry, St. Joseph' s College, 36 Langford Road, Bangalore 560 027 (India); Rajamathi, Michael, E-mail: mikerajamathi@rediffmail.com [Materials Research Group, Department of Chemistry, St. Joseph' s College, 36 Langford Road, Bangalore 560 027 (India)

    2013-02-15

    Oxalate intercalated anionic clay-like nickel zinc hydroxysalt was obtained starting from nickel zinc hydroxyacetate, Ni{sub 3}Zn{sub 2}(OH){sub 8}(OAc){sub 2}{center_dot}2H{sub 2}O, by anion exchange. The intercalated oxalate species was reacted with potassium permanganate in such a way that the layered manganese oxide formed was within the interlayer region of the anionic clay resulting in a layered composite in which the negative charges on the birnessite type manganese oxide layers compensate the positive charges on the anionic clay layers. Birnessite to anionic clay ratio could be varied by varying the reaction time or the amount of potassium permanganate used. - Graphical abstract: Nickel zinc hydroxyoxalate was reacted with potassium permanganate to get nickel zinc hydroxide birnessite composites in which the positive charges on the hydroxide layers are neutralized by the negative charges on birnessite layers. Highlights: Black-Right-Pointing-Pointer Anionic and cationic layered solid composites prepared. Black-Right-Pointing-Pointer Ni-Zn hydroxyoxalate reacted with KMnO{sub 4} to deposit MnO{sub 2} in the interlayer. Black-Right-Pointing-Pointer Birnessite layers coexist with anionic clay layers in the composites. Black-Right-Pointing-Pointer Birnessite/anionic clay ratio controlled by amount of KMnO{sub 4} used and reaction time.

  17. On the Response of Nascent Soot Nanostructure and Oxidative Reactivity to Photoflash Exposure

    Wei Wang

    2017-07-01

    Full Text Available Soot particles are a kind of major pollutant from fuel combustion. To enrich the understanding of soot, this work focuses on investigating detailed influences of instantaneous external irradiation (conventional photoflash exposure on nanostructure as well as oxidation reactivity of nascent soot particles. By detailed soot characterizations flash can reduce the mass of soot and soot nanostructure can be reconstructed substantially without burning. After flash, the degree of soot crystallization increases while the soot reactive rate decreases and the activation energy increases. In addition, nanostructure and oxidative reactivity of soot in air and Ar after flash are different due to their different thermal conductivities.

  18. Using Iron-Manganese Co-Oxide Filter Film to Remove Ammonium from Surface Water.

    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 - .

  19. Recent Advancements in the Cobalt Oxides, Manganese Oxides, and Their Composite As an Electrode Material for Supercapacitor: A Review

    Santosh J. Uke

    2017-08-01

    Full Text Available Recently, our modern society demands the portable electronic devices such as mobile phones, laptops, smart watches, etc. Such devices demand light weight, flexible, and low-cost energy storage systems. Among different energy storage systems, supercapacitor has been considered as one of the most potential energy storage systems. This has several significant merits such as high power density, light weight, eco-friendly, etc. The electrode material is the important part of the supercapacitor. Recent studies have shown that there are many new advancement in electrode materials for supercapacitors. In this review, we focused on the recent advancements in the cobalt oxides, manganese oxides, and their composites as an electrode material for supercapacitor.

  20. Heterogeneous catalytic ozonation of ciprofloxacin in water with carbon nanotube supported manganese oxides as catalyst

    Sui, Minghao, E-mail: suiminghao.sui@gmail.com [State Key Laboratory of Pollution Control and Resource Reuse, School of Environmental Science and Engineering, Tongji University, 1239 Siping Road, Shanghai 200092 (China); Xing, Sichu; Sheng, Li; Huang, Shuhang; Guo, Hongguang [State Key Laboratory of Pollution Control and Resource Reuse, School of Environmental Science and Engineering, Tongji University, 1239 Siping Road, Shanghai 200092 (China)

    2012-08-15

    Highlights: Black-Right-Pointing-Pointer Ciprofloxacin in water was degraded by heterogeneous catalytic ozonation. Black-Right-Pointing-Pointer MnOx were supported on MWCNTs to serve as catalyst for ozonation. Black-Right-Pointing-Pointer MnOx/MWCNT exhibited highly catalytic activity on ozonation of ciprofloxacin in water. Black-Right-Pointing-Pointer MnOx/MWCNT resulted in effective antibacterial activity inhibition on ciprofloxacin. Black-Right-Pointing-Pointer MnOx/MWCNT promoted the generation of hydroxyl radicals. - Abstract: Carbon nanotube-supported manganese oxides (MnOx/MWCNT) were used as catalysts to assist ozone in degrading ciprofloxacin in water. Manganese oxides were successfully loaded on multi-walled carbon nanotube surfaces by simply impregnating the carbon nanotube with permanganate solution. The catalytic activities of MnOx/MWCNT in ciprofloxacin ozonation, including degradation, mineralization effectiveness, and antibacterial activity change, were investigated. The presence of MnOx/MWCNT significantly elevated the degradation and mineralization efficiency of ozone on ciprofloxacin. The microbiological assay with a reference Escherichia coli strain indicated that ozonation with MnOx/MWCNT results in more effective antibacterial activity inhibition of ciprofloxacin than that in ozonation alone. The effects of catalyst dose, initial ciprofloxacin concentration, and initial pH conditions on ciprofloxacin ozonation with MnOx/MWCNT were surveyed. Electron spin resonance trapping was applied to assess the role of MnOx/MWCNT in generating hydroxyl radicals (HO{center_dot}) during ozonation. Stronger 5,5-dimethyl-1-pyrroline-N-oxide-OH signals were observed in the ozonation with MnOx/MWCNT compared with those in ozonation alone, indicating that MnOx/MWCNT promoted the generation of hydroxyl radicals. The degradation of ciprofloxacin was studied in drinking water and wastewater process samples to gauge the potential effects of water background matrix on

  1. Understanding the role of manganese dioxide in the oxidation of phenolic compounds by aqueous permanganate.

    Jiang, Jin; Gao, Yuan; Pang, Su-Yan; Lu, Xue-Ting; Zhou, Yang; Ma, Jun; Wang, Qiang

    2015-01-06

    Recent studies have shown that manganese dioxide (MnO2) can significantly accelerate the oxidation kinetics of phenolic compounds such as triclosan and chlorophenols by potassium permanganate (Mn(VII)) in slightly acidic solutions. However, the role of MnO2 (i.e., as an oxidant vs catalyst) is still unclear. In this work, it was demonstrated that Mn(VII) oxidized triclosan (i.e., trichloro-2-phenoxyphenol) and its analogue 2-phenoxyphenol, mainly generating ether bond cleavage products (i.e., 2,4-dichlorophenol and phenol, respectively), while MnO2 reacted with them producing appreciable dimers as well as hydroxylated and quinone-like products. Using these two phenoxyphenols as mechanistic probes, it was interestingly found that MnO2 formed in situ or prepared ex situ greatly accelerated the kinetics but negligibly affected the pathways of their oxidation by Mn(VII) at acidic pH 5. The yields (R) of indicative products 2,4-dichlorophenol and phenol from their respective probes (i.e., molar ratios of product formed to probe lost) under various experimental conditions were quantified. Comparable R values were obtained during the treatment by Mn(VII) in the absence vs presence of MnO2. Meanwhile, it was confirmed that MnO2 could accelerate the kinetics of Mn(VII) oxidation of refractory nitrophenols (i.e., 2-nitrophenol and 4-nitrophenol), which otherwise showed negligible reactivity toward Mn(VII) and MnO2 individually, and the effect of MnO2 was strongly dependent upon its concentration as well as solution pH. These results clearly rule out the role of MnO2 as a mild co-oxidant and suggest a potential catalytic effect on Mn(VII) oxidation of phenolic compounds regardless of their susceptibility to oxidation by MnO2.

  2. Treatment of synthetic urban runoff using manganese oxide-coated sand in the presence of magnetic field

    Maryam Foroughi

    2013-01-01

    Conclusion: Manganese oxide-coated sand filter in the presence of magnetic field improve the quality of urban runoff significantly. Authors believe that this approach is simple, economical and efficient as in comparison to other existing methods. This could be a promising treatment technology that can enhance quality of urban runoff and industrial wastewaters.

  3. Coprecipitation mechanisms and products in manganese oxidation in the presence of cadmium

    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

  4. Relationship between anti-oxidant capacity and manganese accumulation in the soft tissues of two freshwater molluscs: Unio pictorum mancus (Lamellibranchia, Unionidae and Viviparus ater (Gastropoda, Prosobranchia

    Oscar RAVERA

    2005-08-01

    Full Text Available Manganese is an element of great importance in the life cycle of plants and animals. For example, it plays an essential role as an activator of various enzymatic systems such as isoenzymes of superoxide dismutase. Freshwater Unionidae concentrate relatively large amounts of manganese in their tissues, but little is known about the physiological role of this metal. The aim of this research is to acquire a better knowledge of the role of manganese in molluscs which accumulate large amounts of this metal and in those with low manganese concentrations. As manganese is one of the metals present in the superoxide molecule, the possible relationship between manganese concentration in the soft tissues of molluscs and the antioxidant capacity of the metal can usefully be tested. To this end two species of molluscs were analysed: Unio pictorum mancus (Lamellibranchia, Unionidae, which is very rich in manganese, and Viviparus ater (Gastropoda, Prosobranchia which has a low manganese content. The adults of both species were analysed for manganese concentration by ICP, and for antioxidant capacity as RAC (Relative Antioxidant Capacity by a superoxide dismutase method. The results clearly demonstrate the active role played by manganese against free radicals and consequently the important role of the metal in protecting Unio against oxidative stress. The low concentration of manganese in Viviparus may be the result of the effective excretion of this metal, as was found for ruthenium.

  5. Effect of cationic/anionic organic surfactants on evaporation induced self assembled tin oxide nanostructured films

    Khun Khun, Kamalpreet; Mahajan, Aman; Bedi, R.K.

    2011-01-01

    Tin oxide nanostructures with well defined morphologies have been obtained through an evaporation induced self assembly process. The technique has been employed using an ultrasonic nebulizer for production of aersol and its subsequent deposition onto a heated glass substrate. The precursor used for aersol production was modified by introducing cationic and anionic surfactants namely cetyl trimethyl ammonium bromide and sodium dodecyl sulphate respectively. The effect of surfactants on the structural, electrical and optical properties of self assembled tin oxide nanostructures were investigated by using X-ray diffraction, field emission scanning electroscope microscopy, two probe technique and photoluminiscence studies. The results reveal that high concentration of surfactants in the precursor solution leads to reduction in crystallite size with significant changes in the morphology of tin oxide nanostructures. Photoluminiscence studies of the nanostructures show emissions in the visible region which exhibit marked changes in the intensities upon variation of surfactants in the precursor solutions.

  6. Effect of cationic/anionic organic surfactants on evaporation induced self assembled tin oxide nanostructured films

    Khun Khun, Kamalpreet [Material Science Laboratory, Department of Physics, Guru Nanak Dev University, Amritsar 143005 (India); Mahajan, Aman, E-mail: dramanmahajan@yahoo.co.in [Material Science Laboratory, Department of Physics, Guru Nanak Dev University, Amritsar 143005 (India); Bedi, R.K. [Material Science Laboratory, Department of Physics, Guru Nanak Dev University, Amritsar 143005 (India)

    2011-01-15

    Tin oxide nanostructures with well defined morphologies have been obtained through an evaporation induced self assembly process. The technique has been employed using an ultrasonic nebulizer for production of aersol and its subsequent deposition onto a heated glass substrate. The precursor used for aersol production was modified by introducing cationic and anionic surfactants namely cetyl trimethyl ammonium bromide and sodium dodecyl sulphate respectively. The effect of surfactants on the structural, electrical and optical properties of self assembled tin oxide nanostructures were investigated by using X-ray diffraction, field emission scanning electroscope microscopy, two probe technique and photoluminiscence studies. The results reveal that high concentration of surfactants in the precursor solution leads to reduction in crystallite size with significant changes in the morphology of tin oxide nanostructures. Photoluminiscence studies of the nanostructures show emissions in the visible region which exhibit marked changes in the intensities upon variation of surfactants in the precursor solutions.

  7. Sea-urchin-like iron oxide nanostructures for water treatment

    Lee, Hyun Uk; Lee, Soon Chang; Lee, Young-Chul; Vrtnik, Stane; Kim, Changsoo; Lee, SangGap; Lee, Young Boo; Nam, Bora; Lee, Jae Won; Park, So Young; Lee, Sang Moon; Lee, Jouhahn

    2013-01-01

    Highlights: • The u-MFN were synthesized via a ultrasound irradiation and/or calcinations process. • The u-MFN exhibited excellent adsorption capacities. • The u-MFN also displayed excellent adsorption of organic polluent after recycling. • The u-MFN has the potential to be used as an efficient adsorbent material. -- Abstract: To obtain adsorbents with high capacities for removing heavy metals and organic pollutants capable of quick magnetic separation, we fabricated unique sea-urchin-like magnetic iron oxide (mixed γ-Fe 2 O 3 /Fe 3 O 4 phase) nanostructures (called u-MFN) with large surface areas (94.1 m 2 g −1 ) and strong magnetic properties (57.9 emu g −1 ) using a simple growth process and investigated their potential applications in water treatment. The u-MFN had excellent removal capabilities for the heavy metals As(V) (39.6 mg g −1 ) and Cr(VI) (35.0 mg g −1 ) and the organic pollutant Congo red (109.2 mg g −1 ). The u-MFN also displays excellent adsorption of Congo red after recycling. Because of its high adsorption capacity, fast adsorption rate, and quick magnetic separation from treated water, the u-MFN developed in the present study is expected to be an efficient magnetic adsorbent for heavy metals and organic pollutants in aqueous solutions

  8. Bio-templated synthesis of lithium manganese oxide microtubes and their application in Li+ recovery

    Yu, Qianqian; Sasaki, Keiko; Hirajima, Tsuyoshi

    2013-01-01

    Highlights: • Biogenic birnessite was used to synthesize microtube-type Li + ion sieve. • The biomineral facilitates LMO formation at a lower temperature. • HMO-MT with high Li + uptake capacity was obtained. • Temperature effects on properties of HMO-MTs were studied. -- Abstract: Microbial transformations, a primary pathway for the Mn oxides formation in nature, provide potential for material-oriented researchers to fabricate new materials. Using Mn oxidizing fungus Paraconiothyrium sp. WL-2 as a bio-oxidizer as well as a bio-template, a special lithium ion sieve with microtube morphology was prepared through a solid-state transformation. Varying the calcination temperature from 300 to 700 °C was found to influence sample properties and consequently, the adsorption of Li + . Lithium manganese oxide microtube (LMO-MTs) calcined at different temperatures as well as their delithiated products (HMO-MTs) were characterized by X-ray diffraction (XRD), X-ray absorption fine structure (XAFS) spectroscopy, scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Calcination temperatures affect not only the content but also the crystal structure of LMO spinel, which is important in Li + adsorption. The optimized sample was obtained after calcination at 500 °C for 4 h, which shows higher Li + adsorption capacity than particulate materials

  9. Bio-templated synthesis of lithium manganese oxide microtubes and their application in Li+ recovery.

    Yu, Qianqian; Sasaki, Keiko; Hirajima, Tsuyoshi

    2013-11-15

    Microbial transformations, a primary pathway for the Mn oxides formation in nature, provide potential for material-oriented researchers to fabricate new materials. Using Mn oxidizing fungus Paraconiothyrium sp. WL-2 as a bio-oxidizer as well as a bio-template, a special lithium ion sieve with microtube morphology was prepared through a solid-state transformation. Varying the calcination temperature from 300 to 700 °C was found to influence sample properties and consequently, the adsorption of Li(+). Lithium manganese oxide microtube (LMO-MTs) calcined at different temperatures as well as their delithiated products (HMO-MTs) were characterized by X-ray diffraction (XRD), X-ray absorption fine structure (XAFS) spectroscopy, scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Calcination temperatures affect not only the content but also the crystal structure of LMO spinel, which is important in Li(+) adsorption. The optimized sample was obtained after calcination at 500 °C for 4h, which shows higher Li(+) adsorption capacity than particulate materials. Copyright © 2013 Elsevier B.V. All rights reserved.

  10. Mesoporous iron–manganese oxides for sulphur mustard and soman degradation

    Štengl, Václav, E-mail: stengl@iic.cas.cz [Department of Solid State Chemistry, Institute of Inorganic Chemistry AS CR, v.v.i., 250 68 Řež (Czech Republic); J.E. Purkyně University in Ústí nad Labem, Faculty of Environment, 400 96 Ústí nad Labem (Czech Republic); Grygar, Tomáš Matys [Department of Solid State Chemistry, Institute of Inorganic Chemistry AS CR, v.v.i., 250 68 Řež (Czech Republic); J.E. Purkyně University in Ústí nad Labem, Faculty of Environment, 400 96 Ústí nad Labem (Czech Republic); Bludská, Jana [Department of Solid State Chemistry, Institute of Inorganic Chemistry AS CR, v.v.i., 250 68 Řež (Czech Republic); Opluštil, František; Němec, Tomáš [Military Technical Institute of Protection Brno, Veslařská 230, 628 00 Brno (Czech Republic)

    2012-12-15

    Graphical abstract: Display Omitted Highlights: ► New nanodispersive materials based on Fe and Mn oxides for degradations of warfare agents. ► The best activities for the degradation of sulphur mustard (97.9% in 64 min) and soman (97.9% in 64 min). ► One pot synthesis with friendly transformed to industrial conditions. -- Abstract: Substituted iron(III)–manganese(III, IV) oxides, ammonio-jarosite and birnessite, were prepared by a homogeneous hydrolysis of potassium permanganate and iron(III) sulphate with 2-chloroacetamide and urea, respectively. Synthesised oxides were characterised using Brunauer–Emmett–Teller (BET) surface area and Barrett–Joiner–Halenda porosity (BJH), X-ray diffraction (XRD), infrared spectroscopy (IR), Raman spectroscopy and scanning electron microscopy (SEM). The oxides were taken for an experimental evaluation of their reactivity against sulphur mustard (HD) and soman (GD). When ammonio-jarosite formation is suppressed by adding urea to the reaction mixture, the reaction products are mixtures of goethite, schwertmannite and ferrihydrite, and their degradation activity against soman considerably increases. The best activities for the degradation of sulphur mustard (97.9% in 64 min) and soman (97.9% in 64 min) were observed for FeMn{sub 7}5 with 32.6 wt.% Fe (36.8 wt.% Mn) and FeMn{sub 3}7U with 60.8 wt.% Fe (10.1 wt.% Mn) samples, respectively.

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

    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.

  12. Borate electrolyte additives for high voltage lithium nickel manganese oxide electrode: A comparative study

    Chen, Zhiting; Wang, Cun; Xing, Lidan; Wang, Xianshu; Tu, Wenqiang; Zhu, Yunmin; Li, Weishan

    2017-01-01

    Highlights: •TMB and TEB effective improve the cyclic stability of LNMO at high voltage. •The performance of LNMO with TMB-containing electrolyte is superior to that of TEB. •LNMO shows catalytic effect on the oxidation reaction of TEB. •The film generated in TMB shows better ability on suppressing LNMO shedding than TEB. -- Abstract: Trimethyl borate (TMB) and triethyl borate (TEB) are used as film-forming electrolyte additives for high voltage Lithium nickel manganese oxide (LNMO) cathode. DFT calculation and initial charge curve of LNMO reveal that the oxidation activity of TEB is higher than that of TMB. Addition of 2% TMB and 2% TEB effectively improve the capacity retention of high voltage LNMO from 23.4% to 85.3% and 72.6% after 600 cycles, respectively. The film generated in TMB-containing electrolyte shows better ability on suppressing the LNMO shedding in comparison with that of TEB, resulting in higher capacity retention of LNMO in TMB-containing electrolyte at high voltage. The superior performance of LNMO with TMB-containing electrolyte should be ascribed to its less intense film-forming reaction which generates a denser protective surface film on LNMO surface. However, why LNMO shows catalyzation effect on TEB oxidation but not on TMB is unclear, which needs further intensive investigation.

  13. Mesoporous iron–manganese oxides for sulphur mustard and soman degradation

    Štengl, Václav; Grygar, Tomáš Matys; Bludská, Jana; Opluštil, František; Němec, Tomáš

    2012-01-01

    Graphical abstract: Display Omitted Highlights: ► New nanodispersive materials based on Fe and Mn oxides for degradations of warfare agents. ► The best activities for the degradation of sulphur mustard (97.9% in 64 min) and soman (97.9% in 64 min). ► One pot synthesis with friendly transformed to industrial conditions. -- Abstract: Substituted iron(III)–manganese(III, IV) oxides, ammonio-jarosite and birnessite, were prepared by a homogeneous hydrolysis of potassium permanganate and iron(III) sulphate with 2-chloroacetamide and urea, respectively. Synthesised oxides were characterised using Brunauer–Emmett–Teller (BET) surface area and Barrett–Joiner–Halenda porosity (BJH), X-ray diffraction (XRD), infrared spectroscopy (IR), Raman spectroscopy and scanning electron microscopy (SEM). The oxides were taken for an experimental evaluation of their reactivity against sulphur mustard (HD) and soman (GD). When ammonio-jarosite formation is suppressed by adding urea to the reaction mixture, the reaction products are mixtures of goethite, schwertmannite and ferrihydrite, and their degradation activity against soman considerably increases. The best activities for the degradation of sulphur mustard (97.9% in 64 min) and soman (97.9% in 64 min) were observed for FeMn 7 5 with 32.6 wt.% Fe (36.8 wt.% Mn) and FeMn 3 7U with 60.8 wt.% Fe (10.1 wt.% Mn) samples, respectively.

  14. Intraparticle diffusion coefficient of lithium on granulated adsorbent of manganese oxide in seawater

    Miyai, Yoshitaka; Kanoh, Hirofumi; Feng, Qi; Ooi, Kenta

    1995-01-01

    Five kinds of manganese-oxide adsorbent granulated with different particle sizes were prepared using polyvinyl chloride (PVC) as a binder. Rates of lithium adsorption on the adsorbents were measured in lithium-enriched seawater ([Li]=3.1 mg·dm -3 ) by a batch method. The intraparticle diffusivities (D p 's) of lithium were evaluated in terms of the model of pore diffusion with a Freundrich-type adsorption isotherm. The D p values were about 2 x 10 -6 cm·s -1 and slightly dependent on particle size. The D p values were also evaluated using column adsorption data. The calculated values (about 4 x 10 -6 cm·s -1 ) agreed comparatively well with those derived from the batch adsorption data. The agreement suggests that the intraparticle diffusion is a rate-determining step in column adsorption at space velocity above 200 h -1 . (author)

  15. Preparation and Characterization of a PEDOT-Manganese Oxide Composite, and Its Application to Electrochemical Sensing

    Arena, A.

    2016-01-01

    Stable and transparent aqueous dispersions of a hybrid organic-inorganic composite, are prepared by electrochemically doping Manganese Oxide into Polyethylendioxythiophene (PEDOT). Films deposited from the PEDOT-MnOx dispersions, are characterized by means of electrical and optical measurements, and by means of Atomic Force Microscopy (AFM) investigations. The PEDOT-MnOx composite is then used to modify one of the gold electrodes of a simple electrochemical cell, in which Nafion is used as a solid electrolyte. The cell is characterized using time domain electrical measurements. It is found that distinguishable redox peaks arise in the current-voltage loops of the cell, as nanomolar amounts of either acetic acid and ammonia, are added to the deionized water into which the cell is immersed. The intensity of such current peaks, is linearly related to the concentration of the analytes, in the nanomolar range of concentrations. (paper)

  16. Manganese oxide octahedral molecular sieves as insertion electrodes for rechargeable Mg batteries

    Rasul, Shahid; Suzuki, Shinya; Yamaguchi, Shu; Miyayama, Masaru

    2013-01-01

    Magnesium has been inserted electrochemically into manganese oxide octahedral molecular sieves (OMS-5 MnO2) at room temperature. Discharge/charge profiles show that a large amount of Mg, i.e., 0.37 Mg/Mn can be inserted electrochemically using 1 M Mg(ClO4)2/AN electrolyte when OMS-5 is prepared in presence of acetylene black. X-ray diffraction analysis and discharge/charge profiles verify that a solid state solution reaction takes place upon Mg insertion into the host lattice with concurrent reduction of Mn4+ to Mn2+. However, upon each reduction of Mn by Mg insertion and resultant dissolution into electrolyte, decrease in the active compound occurs consequently. A low intrinsic electronic conductivity of OMS-5 was suggested to play a vital role in Mg insertion into the host. © 2013 Elsevier Ltd.

  17. Hydrous manganese oxide-polyacrylonitrile (HMO-PAN) composite for the treatment of radioactive laundry wastewater

    Sanghwa Oh; Won Sik Shin; Sang-June Choi

    2015-01-01

    Hydrous manganese oxide-polyacrylonitrile (HMO-PAN) composite was applied for the removal of Co 2+ , Sr 2+ and Cs + from radioactive laundry wastewater. Single- and multi-solute competitive sorptions onto HMO-PAN were investigated. The maximum sorption capacity was in the order of Co 2+ (0.573) > Cs + (0.551) > Sr 2+ (0.310 mmol g -1 ). Sorption of the metals occurred via physical adsorption due to weak van der Waals force and ion exchange with Mn 2+ in HMO-PAN. Sorption behaviors were not related to the types of the surfactants. Among the tested surfactants, SDBS and SOBS remarkably increased the distribution coefficient of Co 2+ and Sr 2+ , respectively. (author)

  18. Manganese oxide octahedral molecular sieves as insertion electrodes for rechargeable Mg batteries

    Rasul, Shahid

    2013-11-01

    Magnesium has been inserted electrochemically into manganese oxide octahedral molecular sieves (OMS-5 MnO2) at room temperature. Discharge/charge profiles show that a large amount of Mg, i.e., 0.37 Mg/Mn can be inserted electrochemically using 1 M Mg(ClO4)2/AN electrolyte when OMS-5 is prepared in presence of acetylene black. X-ray diffraction analysis and discharge/charge profiles verify that a solid state solution reaction takes place upon Mg insertion into the host lattice with concurrent reduction of Mn4+ to Mn2+. However, upon each reduction of Mn by Mg insertion and resultant dissolution into electrolyte, decrease in the active compound occurs consequently. A low intrinsic electronic conductivity of OMS-5 was suggested to play a vital role in Mg insertion into the host. © 2013 Elsevier Ltd.

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

    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.

  20. Effect of support on the catalytic activity of manganese oxide catalyts for toluene combustion

    Pozan, Gulin Selda

    2012-01-01

    Highlights: ► α-Al 2 O 3 , obtained from Bohmite, as a support for enhancing of the activity. ► The support material for catalytic oxidation. ► The manganese state and oxygen species effect on the catalytic combustion reaction. - Abstract: The aim of this work was to study combustion of toluene (1000 ppm) over MnO 2 modified with different supports. α-Al 2 O 3 and γ-Al 2 O 3 obtained from Boehmite, γ-Al 2 O 3 (commercial), SiO 2 , TiO 2 and ZrO 2 were used as commercial support materials. In view of potential interest of this process, the influence of support material on the catalytic performance was discussed. The deposition of 9.5MnO 2 was performed by impregnation over support. The catalysts were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), temperature programmed reduction and oxidation (TPR/TPO) and thermogravimetric analysis (TGA). The catalytic tests were carried out at atmospheric pressure in a fixed-bed flow reactor. 9.5MnO 2 /α-Al 2 O 3 (B) (synthesized from Boehmite) catalyst exhibits the highest catalytic activity, over which the toluene conversion was up to 90% at a temperature of 289 °C. Considering all the characterization and reaction data reported in this study, it was concluded that the manganese state and oxygen species played an important role in the catalytic activity.

  1. Iron and manganese in oxide minerals and in glasses: preliminary consideration of Eh buffering potential at Yucca Mountain, Nevada

    Caporuscio, F.A.; Vaniman, D.T.

    1985-04-01

    The tuffs of Yucca Mountain at the Nevada Test Site are currently under investigation as a possible deep burial site for high-level radioactive waste disposal. One of the main concerns is the effect of oxidizing groundwater on the transport of radionuclides. Rock components that may affect the oxygen content of groundwater include Fe-Ti oxides, Mn oxides, and glasses that contain ferrous iron. Some phenocryst Fe-Ti oxides at Yucca Mountain are in reduced states, whereas groundmass Fe-Ti oxides have been oxidized to hematite, rutile, and pseudobrookite (Fe 3+ -bearing phases) exclusively. Estimates of Fe 2+ -bearing oxides indicate that less than 0.33 vol% phenocrysts is available to act as solid buffering agents of Eh. Of this percentage, significant amounts of Fe-Ti oxides are isolated from effective interaction with groundwater because they occur in densely welded, devitrified tuffs that have low interstitial permeability. Manganese oxides occur primarily along fractures in the ash-flow tuffs. Because the Mn oxides are concentrated along the same pathways (fractures) where transport has occurred in the past, these small volume percentages could act as buffers. However, the oxidation states of actual Mn-oxide phases are high (Mn 4+ ), and these minerals have virtually no potential for reducing groundwater Eh. Manganese oxides may even act as oxidizing agents. However, regardless of their poor capabilities as reducing agents, the Mn oxides could be important as sorbents of heavy metals at Yucca Mountain. The lack of accessible, pristine Fe-Ti oxides and the generally high oxidation states of Mn oxides seem to rule out these oxides as Eh buffers of the Yucca Mountain groundwater system. Reduction of ferrous iron within glassy tuffs may have some effect on Eh, but further study is needed. At present it is prudent to assume that minerals and glasses have little or no capacity for reducing oxygen-rich groundwater at Yucca Mountain. 25 refs., 3 figs., 12 tabs

  2. A Review on Anodic Aluminum Oxide Methods for Fabrication of Nanostructures for Organic Solar Cells

    Goszczak, Arkadiusz Jaroslaw; Cielecki, Pawel Piotr

    2018-01-01

    Implementation of nanostructures into the organic solar cell (OSC) architecture has great influence on the device performance. Nanostructuring the active layer increases the interfacial area between donor and acceptor, which enhances the probability of exciton dissociation. Introduction of nanost......Implementation of nanostructures into the organic solar cell (OSC) architecture has great influence on the device performance. Nanostructuring the active layer increases the interfacial area between donor and acceptor, which enhances the probability of exciton dissociation. Introduction......, low fabrication cost and easy control over its nano-scale morphology, make AAO patterning methods an intriguing candidate for nanopatterning. Hence, in this work, we present a review on the fabrication techniques and on nanostructures from Anodic Aluminum Oxide (AAO) for OSC applications...

  3. Manganese scavenging and oxidative stress response mediated by type VI secretion system in Burkholderia thailandensis.

    Si, Meiru; Zhao, Chao; Burkinshaw, Brianne; Zhang, Bing; Wei, Dawei; Wang, Yao; Dong, Tao G; Shen, Xihui

    2017-03-14

    Type VI secretion system (T6SS) is a versatile protein export machinery widely distributed in Gram-negative bacteria. Known to translocate protein substrates to eukaryotic and prokaryotic target cells to cause cellular damage, the T6SS has been primarily recognized as a contact-dependent bacterial weapon for microbe-host and microbial interspecies competition. Here we report contact-independent functions of the T6SS for metal acquisition, bacteria competition, and resistance to oxidative stress. We demonstrate that the T6SS-4 in Burkholderia thailandensis is critical for survival under oxidative stress and is regulated by OxyR, a conserved oxidative stress regulator. The T6SS-4 is important for intracellular accumulation of manganese (Mn 2+ ) under oxidative stress. Next, we identified a T6SS-4-dependent Mn 2+ -binding effector TseM, and its interacting partner MnoT, a Mn 2+ -specific TonB-dependent outer membrane transporter. Similar to the T6SS-4 genes, expression of mnoT is regulated by OxyR and is induced under oxidative stress and low Mn 2+ conditions. Both TseM and MnoT are required for efficient uptake of Mn 2+ across the outer membrane under Mn 2+ -limited and -oxidative stress conditions. The TseM-MnoT-mediated active Mn 2+ transport system is also involved in contact-independent bacteria-bacteria competition and bacterial virulence. This finding provides a perspective for understanding the mechanisms of metal ion uptake and the roles of T6SS in bacteria-bacteria competition.

  4. Study of the phase composition of nanostructures produced by the local anodic oxidation of titanium films

    Avilov, V. I.; Ageev, O. A.; Konoplev, B. G.; Smirnov, V. A.; Solodovnik, M. S.; Tsukanova, O. G.

    2016-01-01

    The results of experimental studies of the phase composition of oxide nanostructures formed by the local anodic oxidation of a titanium thin film are reported. The data of the phase analysis of titanium-oxide nanostructures are obtained by X-ray photoelectron spectroscopy in the ion profiling mode of measurements. It is established that the surface of titanium-oxide nanostructures 4.5 ± 0.2 nm in height possesses a binding energy of core levels characteristic of TiO_2 (458.4 eV). By analyzing the titanium-oxide nanostructures in depth by X-ray photoelectron spectroscopy, the formation of phases with binding energies of core levels characteristic of Ti_2O_3 (456.6 eV) and TiO (454.8 eV) is established. The results can be used in developing the technological processes of the formation of a future electronic-component base for nanoelectronics on the basis of titanium-oxide nanostructures and probe nanotechnologies.

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

    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.

  6. Manganese mediated oxidation of progesterone in alkaline medium: Mechanism study and quantitative determination

    Shamsipur, Mojtaba; Pashabadi, Afshin; Taherpour, Avat; Bahrami, Kiumars; Sharghi, Hashem

    2017-01-01

    Highlights: • This is first report on oxidation of progesterone in alkaline medium using a new manganese (III) Schiff base complex. • Utilizing QM and MM, we modelled and interpreted the observed electrochemical behavior of complex on carbon and gold materials as platform. • The long term stability of proposed sensor is improved relative to previously reported immunosensors for P4. • A detailed mechanism was developed for the oxidation of P4. • The proposed sensor was applied to quantify P4 in cow’s milk. - Abstract: We report here a non-immunosensing approach for the electrocatalytic oxidation of progesterone (P4) in alkaline medium using a salen-type manganese Schiff base complex (Mn(III)-SB) as a suitable electrocatalyst. We explored the role of carbon surface at glassy carbon electrode (GCE) and gold surface at glassy carbon/gold nanoparticles modified electrode (GCE/AuNPs) on immobilization of the Mn(III)-SB complex using cyclic voltammetry (CV) and density functional theory (DFT) calculations. The GCE/Mn(III)-SB displayed a pair of small redox peaks attributed to Mn(II) ⇄ Mn(III) with a small peak-to-peak separation (ΔE p ), while GCE/AuNP/Mn(III)-SB displayed redox peaks with larger densities, but with a wider ΔE p . A combined molecular mechanics (MM) and quantum mechanics (QM) study were carried out to investigate the variation of surface configuration and energy barrier, when the Mn(III)-SB immobilization was modeled on GCE and GCE/Au surface. Cyclic voltammetry and hydrodynamic amperometry were used for the quantitative determination of P4. A limit of detection (LOD) of 11.4 nM was obtained using amperometry. The sensor retained 91% of its original response after 3 months, which is improved compared to previously reported P4 immunosensors. For the first time, a detailed mechanism for oxidation of P4 in alkaline medium was suggested. The proposed sensor was utilized to determine progesterone in milk samples.

  7. Nanostructure sensitization of transition metal oxides for visible-light photocatalysis

    Hongjun Chen

    2014-05-01

    Full Text Available To better utilize the sunlight for efficient solar energy conversion, the research on visible-light active photocatalysts has recently attracted a lot of interest. The photosensitization of transition metal oxides is a promising approach for achieving effective visible-light photocatalysis. This review article primarily discusses the recent progress in the realm of a variety of nanostructured photosensitizers such as quantum dots, plasmonic metal nanostructures, and carbon nanostructures for coupling with wide-bandgap transition metal oxides to design better visible-light active photocatalysts. The underlying mechanisms of the composite photocatalysts, e.g., the light-induced charge separation and the subsequent visible-light photocatalytic reaction processes in environmental remediation and solar fuel generation fields, are also introduced. A brief outlook on the nanostructure photosensitization is also given.

  8. Sea-urchin-like iron oxide nanostructures for water treatment

    Lee, Hyun Uk, E-mail: leeho@kbsi.re.kr [Division of Materials Science, Korea Basic Science Institute, Daejeon 305-333 (Korea, Republic of); Lee, Soon Chang [Department of Fine Chemical Engineering and Applied Chemistry, Chungnam National University, Daejeon 305-764 (Korea, Republic of); Lee, Young-Chul [Department of Biological Engineering, College of Engineering, Inha University, Incheon 402-751 (Korea, Republic of); Vrtnik, Stane; Kim, Changsoo; Lee, SangGap [Division of Materials Science, Korea Basic Science Institute, Daejeon 305-333 (Korea, Republic of); Lee, Young Boo; Nam, Bora [Jeonju Center, Korea Basic Science Institute, Jeonju 561-756 (Korea, Republic of); Lee, Jae Won [Department of Energy Engineering, Dankook University, Cheonan 330-714 (Korea, Republic of); Park, So Young; Lee, Sang Moon [Division of Materials Science, Korea Basic Science Institute, Daejeon 305-333 (Korea, Republic of); Lee, Jouhahn, E-mail: jouhahn@kbsi.re.kr [Division of Materials Science, Korea Basic Science Institute, Daejeon 305-333 (Korea, Republic of)

    2013-11-15

    Highlights: • The u-MFN were synthesized via a ultrasound irradiation and/or calcinations process. • The u-MFN exhibited excellent adsorption capacities. • The u-MFN also displayed excellent adsorption of organic polluent after recycling. • The u-MFN has the potential to be used as an efficient adsorbent material. -- Abstract: To obtain adsorbents with high capacities for removing heavy metals and organic pollutants capable of quick magnetic separation, we fabricated unique sea-urchin-like magnetic iron oxide (mixed γ-Fe{sub 2}O{sub 3}/Fe{sub 3}O{sub 4} phase) nanostructures (called u-MFN) with large surface areas (94.1 m{sup 2} g{sup −1}) and strong magnetic properties (57.9 emu g{sup −1}) using a simple growth process and investigated their potential applications in water treatment. The u-MFN had excellent removal capabilities for the heavy metals As(V) (39.6 mg g{sup −1}) and Cr(VI) (35.0 mg g{sup −1}) and the organic pollutant Congo red (109.2 mg g{sup −1}). The u-MFN also displays excellent adsorption of Congo red after recycling. Because of its high adsorption capacity, fast adsorption rate, and quick magnetic separation from treated water, the u-MFN developed in the present study is expected to be an efficient magnetic adsorbent for heavy metals and organic pollutants in aqueous solutions.

  9. Oxidation of nonylphenol and octylphenol by manganese dioxide: Kinetics and pathways

    Lu, Zhijiang; Gan, Jay

    2013-01-01

    Due to their potent estrogenicity and ubiquitous occurrence, non-ionic surfactant metabolites nonylphenol (NP) and octylphenol (OP) are of significant concern. Abiotic chemical oxidation by naturally abundant metal oxides may be an important route of their environmental attenuation, but is poorly understood. We investigated the reaction kinetics and pathways of NP and OP with MnO 2 . At pH 5.5 and 100 mg/L δ-MnO 2 , 92, 84 and 76% of 4-n-NP, 4-tert-OP and technical nonylphenol (tNP) was transformed in 90 min, respectively. A further experiment using a Mn-containing soil and Mn-removed soil confirmed that soil MnO 2 caused NP removal. Multiple reaction products, including hydroquinone, hydroxylated products, dimers and trimers were identified through fragmentation analysis by GC–MS/MS and UPLC–MS/MS, allowing the construction of tentative pathways. This study suggested that abiotic oxidation by MnO 2 may contribute to the dissipation of tNP, 4-n-NP, 4-tert-OP and their analogues in the natural environment. Highlights: •The oxidation of nonylphenol and octylphenol by manganese dioxide was efficient and pH dependent. •The importance of soil MnO 2 was further confirmed by experiment using Mn-containing soil. •The reaction in environment is substantially slower than with synthetic MnO 2 . •The oxidation was inhibited by metal ions and enhanced by humic acids. •Reaction pathway is proposed based on reaction intermediates identified. -- Naturally occurring MnO 2 may contribute significantly to the attenuation of nonylphenol and octylphenol in soil, water and sediment

  10. Heterogeneous Reaction of SO2 on Manganese Oxides: the Effect of Crystal Structure and Relative Humidity.

    Yang, Weiwei; Zhang, Jianghao; Ma, Qingxin; Zhao, Yan; Liu, Yongchun; He, Hong

    2017-07-03

    Manganese oxides from anthropogenic sources can promote the formation of sulfate through catalytic oxidation of SO 2 . In this study, the kinetics of SO 2 reactions on MnO 2 with different morphologies (α, β, γ and δ) was investigated using flow tube reactor and in situ Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS). Under dry conditions, the reactivity towards SO 2 uptake was highest on δ-MnO 2 but lowest on β-MnO 2 , with a geometric uptake coefficient (γ obs ) of (2.42 ± 0.13) ×10 -2 and a corrected uptake coefficient (γ c ) of (1.48 ± 0.21) ×10 -6 for the former while γ obs of (3.35 ± 0.43) ×10 -3 and γ c of (7.46 ± 2.97) ×10 -7 for the latter. Under wet conditions, the presence of water altered the chemical form of sulfate and was in favor for the heterogeneous oxidation of SO 2 . The maximum sulfate formation rate was reached at 25% RH and 45% for δ-MnO 2 and γ-MnO 2 , respectively, possibly due to their different crystal structures. The results suggest that morphologies and RH are important factors influencing the heterogeneous reaction of SO 2 on mineral aerosols, and that aqueous oxidation process involving transition metals of Mn might be a potential important pathway for SO 2 oxidation in the atmosphere.

  11. A Versatile Route for the Synthesis of Nickel Oxide Nanostructures Without Organics at Low Temperature

    Shah MA

    2008-01-01

    Full Text Available AbstractNickel oxide nanoparticles and nanoflowers have been synthesized by a soft reaction of nickel powder and water without organics at 100 °C. The mechanism for the formation of nanostructures is briefly described in accordance with decomposition of metal with water giving out hydrogen. The structure, morphology, and the crystalline phase of resulting nanostructures have been characterized by various techniques. Compared with other methods, the present method is simple, fast, economical, template-free, and without organics. In addition, the approach is nontoxic without producing hazardous waste and could be expanded to provide a general and convenient strategy for the synthesis of nanostructures to other functional nanomaterials.

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

    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.

  13. The oxidation of acid azo dye AY 36 by a manganese oxide containing mine waste

    Clarke, Catherine E.; Kielar, Filip; Johnson, Karen L.

    2013-01-01

    Highlights: ► This study looks at the oxidative breakdown of the amine containing dye acid yellow 36 by a Mn oxide containing mine waste. ► The oxidation proceeds by successive one electron transfers between the dye molecule and the Mn oxide minerals. ► The initial decolorization of the dye is rapid, but does not involve the cleavage of the azo bond. -- Abstract: The oxidative breakdown of acid azo dye acid yellow 36 (AY 36) by a Mn oxide containing mine tailings is demonstrated. The oxidation reaction is pH dependent with the rate of decolorization increasing with decreasing pH. The oxidation reaction mechanism is initiated at the amino moiety and proceeds via successive, one electron transfers from the dye to the Mn oxide minerals. The reaction pathway involves the formation of a number of colorless intermediate products, some of which hydrolyze in a Mn oxide-independent step. Decolorization of the dye is rapid and is observed before the cleavage of the azo-bond, which is a slower process. The terminal oxidation products were observed to be p-benzoquinone and 3-hydroxybenzenesulfonate. The reaction order of the initial decolorization was determined to be pseudo fractional order with respect to pH and pseudo first order with respect to dye concentration and Mn tailings’ surface area

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

    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.

  15. Promotion effect of manganese oxide on the electrocatalytic activity of Pt/C for methanol oxidation in acid medium

    Abdel Hameed, R.M.; Fetohi, Amani E.; Amin, R.S.; El-Khatib, K.M.

    2015-01-01

    Graphical abstract: Physical and electrochemical properties of Pt/C, Pt–MnO_2/C-1 and Pt–MnO_2/C-2 electrocatalysts. - Highlights: • Adding MnO_2 to Pt/C improved the dispersion of Pt nanoparticles. • The existence of MnO_2 improved the kinetics of methanol oxidation reaction. • R_c_t value of Pt–MnO_2/C was about 10 times as low as that at Pt/C. • The removal of CO_a_d_s poisoning species was facilitated at Pt–MnO_2/C. - Abstract: The modification of Pt/C by incorporating metal oxides for electrocatalytic oxidation of methanol has gained major attention because of the efficiency loss during the course of long-time operation. This work describes the preparation of Pt–MnO_2/C electrocatalysts through a chemical route using ethylene glycol or a mixture of ethylene glycol and sodium borohydride as a reducing agent. The crystallite structure and particle size of synthesized electrocatalysts are determined using X-ray diffraction (XRD) and transmission electron microscopy (TEM). The addition of MnO_2 improves the dispersion of Pt nanoparticles. The electrocatalytic activity of Pt–MnO_2/C towards methanol oxidation in H_2SO_4 solution is investigated using cyclic voltammetry and electrochemical impedance spectroscopy. The onset potential value of methanol oxidation peak is negatively shifted by 169 mV when MnO_2 is introduced to Pt/C. Moreover, the charge transfer resistance value at Pt–MnO_2/C is about 10 times as low as that at Pt/C. Chronoamperometry and chronopotentiometry show that CO tolerance is greatly improved at Pt–MnO_2/C. The increased electrocatalytic activity and enhanced ability to clean platinum surface elect manganese oxide as a suitable promoter for the anode performance in direct methanol fuel cells (DMFCs).

  16. In situ synthesis of manganese oxides on polyester fiber for formaldehyde decomposition at room temperature

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

    2015-12-01

    Removal of low-level formaldehyde (HCHO) is of great interest for indoor air quality improvement. Supported materials especially those with low air pressure drop are of necessity for air purification. Manganese oxides (MnOx) was in situ deposited on the surface of fibers of a non-woven fabric made of polyethylene terephthalate (PET). As-synthesized MnOx/PET were characterized by SEM, XRD, TEM, ATR-FTIR and XPS analysis. The growth of MnOx layer on PET is thought to start with partial hydrolysis of PET, followed by surface oxidation by KMnO4 and then surface-deposition of MnOx particles from the bulk phase. The MnOx particles assembled with nanosheets were uniformly coated on the PET fibers. MnOx/PET showed good activity for HCHO decomposition at room temperature which followed the Mars-van Krevelen mechanism. The removal of HCHO was kept over 94% after 10 h continuous reaction under the conditions of inlet HCHO concentration ∼0.6 mg/m3, space velocity ∼17,000 h-1 and relative humidity∼50%. This research provides a facile method to deposit active MnOx onto polymers with low air resistance, and composite MnOx/PET material is promising for indoor air purification.

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

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

    2015-11-01

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

  18. Thermodynamic analysis of a combined-cycle solar thermal power plant with manganese oxide-based thermochemical energy storage

    Lei Qi

    2017-01-01

    Full Text Available 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.

  19. Thermodynamic analysis of a combined-cycle solar thermal power plant with manganese oxide-based thermochemical energy storage

    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.

  20. Hierarchical oxide-based composite nanostructures for energy, environmental, and sensing applications

    Gao, Pu-Xian; Shimpi, Paresh; Cai, Wenjie; Gao, Haiyong; Jian, Dunliang; Wrobel, Gregory

    2011-02-01

    Self-assembled composite nanostructures integrate various basic nano-elements such as nanoparticles, nanofilms and nanowires toward realizing multifunctional characteristics, which promises an important route with potentially high reward for the fast evolving nanoscience and nanotechnology. A broad array of hierarchical metal oxide based nanostructures have been designed and fabricated in our research group, involving semiconductor metal oxides, ternary functional oxides such as perovskites and spinels and quaternary dielectric hydroxyl metal oxides with diverse applications in efficient energy harvesting/saving/utilization, environmental protection/control, chemical sensing and thus impacting major grand challenges in the area of materials and nanotechnology. Two of our latest research activities have been highlighted specifically in semiconductor oxide alloy nanowires and metal oxide/perovskite composite nanowires, which could impact the application sectors in ultraviolet/blue lighting, visible solar absorption, vehicle and industry emission control, chemical sensing and control for vehicle combustors and power plants.

  1. Benzyl Alcohol-Mediated Versatile Method to Fabricate Nonstoichiometric Metal Oxide Nanostructures.

    Qamar, Mohammad; Adam, Alaaldin; Azad, Abdul-Majeed; Kim, Yong-Wah

    2017-11-22

    Nanostructured metal oxides with cationic or anionic deficiency find applications in a wide range of technological areas including the energy sector and environment. However, a facile route to prepare such materials in bulk with acceptable reproducibility is still lacking; many synthesis techniques are still only bench-top and cannot be easily scaled-up. Here, we report that the benzyl alcohol (BA)-mediated method is capable of producing a host of nanostructured metal oxides (MO x , where M = Ti, Zn, Ce, Sn, In, Ga, or Fe) with inherent nonstoichiometry. It employs multifunctional BA as a solvent, a reducing agent, and a structure-directing agent. Depending on the oxidation states of metal, elemental or nonstoichiometric oxide forms are obtained. Augmented photoelectrochemical oxidation of water under visible light by some of these nonstoichiometric oxides highlights the versatility of the BA-mediated synthesis protocol.

  2. Rapid synthesis of tin oxide nanostructures by microwave-assisted thermal oxidation for sensor applications

    Phadungdhitidhada, S.; Ruankham, P.; Gardchareon, A.; Wongratanaphisan, D.; Choopun, S.

    2017-09-01

    In the present work nanostructures of tin oxides were synthesized by a microwave-assisted thermal oxidation. Tin precursor powder was loaded into a cylindrical quartz tube and further radiated in a microwave oven. The as-synthesized products were characterized by scanning electron microscope, transmission electron microscope, and x-ray diffractometer. The results showed that two different morphologies of SnO2 microwires (MWs) and nanoparticles (NPs) were obtained in one minute of microwave radiation under atmospheric ambient. A few tens of the SnO2 MWs with the length of 10-50 µm were found. Some parts of the MWs were decorated with the SnO2 NPs. However, most of the products were SnO2 NPs with the diameter ranging from 30-200 nm. Preparation under loosely closed system lead to mixed phase SnO-SnO2 NPs with diameter of 30-200 nm. The single-phase of SnO2 could be obtained by mixing the Sn precursor powders with CuO2. The products were mostly found to be SnO2 nanowires (NWs) and MWs. The diameter of SnO2 NWs was less than 50 nm. The SnO2 NPs, MWs, and NWs were in the cassiterite rutile structure phase. The SnO NPs was in the tetragonal structure phase. The growth direction of the SnO2 NWs was observed in (1 1 0) and (2 2 1) direction. The ethanol sensor performance of these tin oxide nanostructures showed that the SnO-SnO2 NPs exhibited extremely high sensitivity. Invited talk at 5th Thailand International Nanotechnology Conference (Nano Thailand-2016), 27-29 November 2016, Nakhon Ratchasima, Thailand.

  3. Synthesis of cadmium oxide doped ZnO nanostructures using electrochemical deposition

    Singh, Trilok; Pandya, D.K.; Singh, R.

    2011-01-01

    Research highlights: → Ternary ZnCdO alloy semiconductor nanostructures were grown using electrochemical deposition. → X-ray diffraction measurements showed that the nanostructures were of wurtzite structure and possessed a compressive stress along the c-axis direction. → The cut-off wavelength shifted from blue to red on account of the Cd incorporation in the ZnO and the average transmittance decreased by ∼31%. → The bandgap tuning for 4-16 at% Cd in the initial solution was achieved in the range of 3.08-3.32 eV (up to 0.24 eV). - Abstract: Ternary ZnCdO alloy semiconductor nanostructures were grown using electrochemical deposition. Crystalline nanostructures/nanorods with cadmium concentration ranging from 4 to 16 at% in the initial solution were electrodeposited on tin doped indium oxide (ITO) conducting glass substrates at a constant cathodic potential -0.9 V and subsequently annealed in air at 300 deg. C. X-ray diffraction measurements showed that the nanostructures were of wurtzite structure and possessed a compressive stress along the c-axis direction. The elemental composition of nanostructures was confirmed by energy dispersive spectroscopy (EDS). ZnO nanostructures were found to be highly transparent and had an average transmittance of 85% in the visible range of the spectrum. After the incorporation of Cd content into ZnO the average transmittance decreased and the bandgap tuning was also achieved.

  4. Improvement in grade of minerals using simultaneous Bio-oxidation of invisible gold concentrate and deep-sea manganese crust

    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

  5. Durability of carbon-supported manganese oxide nanoparticles for the oxygen reduction reaction (ORR) in alkaline medium

    Roche, I.; Chainet, E.; Chatenet, M.; Vondrák, Jiří

    2008-01-01

    Roč. 38, č. 9 (2008), s. 1195-1201 ISSN 0021-891X R&D Projects: GA AV ČR KJB4813302; GA ČR GA104/02/0731 Grant - others:CNRS(FR) 18105 Institutional research plan: CEZ:AV0Z40320502 Keywords : oxygen reduction reaction * rotating ring-disc electrode * carbon-supported manganese oxide Subject RIV: CA - Inorganic Chemistry Impact factor: 1.540, year: 2008

  6. Nanostructured tungsten trioxide thin films synthesized for photoelectrocatalytic water oxidation: a review.

    Zhu, Tao; Chong, Meng Nan; Chan, Eng Seng

    2014-11-01

    The recent developments of nanostructured WO3 thin films synthesized through the electrochemical route of electrochemical anodization and cathodic electrodeposition for the application in photoelectrochemical (PEC) water splitting are reviewed. The key fundamental reaction mechanisms of electrochemical anodization and cathodic electrodeposition methods for synthesizing nanostructured WO3 thin films are explained. In addition, the effects of metal oxide precursors, electrode substrates, applied potentials and current densities, and annealing temperatures on size, composition, and thickness of the electrochemically synthesized nanostructured WO3 thin films are elucidated in detail. Finally, a summary is given for the general evaluation practices used to calculate the energy conversion efficiency of nanostructured WO3 thin films and a recommendation is provided to standardize the presentation of research results in the field to allow for easy comparison of reported PEC efficiencies in the near future. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  7. Fabrication of orderly nanostructured PLGA scaffolds using anodic aluminum oxide templates.

    Wang, Gou-Jen; Lin, Yan-Cheng; Li, Ching-Wen; Hsueh, Cheng-Chih; Hsu, Shan-Hui; Hung, Huey-Shan

    2009-08-01

    In this research, two simple fabrication methods to fabricate orderly nanostructured PLGA scaffolds using anodic aluminum oxide (AAO) template were conducted. In the vacuum air-extraction approach, the PLGA solution was cast on an AAO template first. The vacuum air-extraction process was then applied to suck the semi-congealed PLGA into the nanopores of the AAO template to form a bamboo sprouts array of PLGA. The surface roughness of the nanostructured scaffolds, ranging from 20 nm to 76 nm, can be controlled by the sucking time of the vacuum air-extraction process. In the replica molding approach, the PLGA solution was cast on the orderly scraggy barrier-layer surface of an AAO membrane to fabricate a PLGA scaffold of concave nanostructure. Cell culture experiments using the bovine endothelial cells (BEC) demonstrated that the nanostructured PLGA membrane can increase the cell growing rate, especially for the bamboo sprouts array scaffolds with smaller surface roughness.

  8. Biotic manganese oxidation coupled with methane oxidation using a continuous-flow bioreactor system under marine conditions.

    Kato, Shingo; Miyazaki, Masayuki; Kikuchi, Sakiko; Kashiwabara, Teruhiko; Saito, Yumi; Tasumi, Eiji; Suzuki, Katsuhiko; Takai, Ken; Cao, Linh Thi Thuy; Ohashi, Akiyoshi; Imachi, Hiroyuki

    2017-10-01

    Biogenic manganese oxides (BioMnOx) can be applied for the effective removal and recovery of trace metals from wastewater because of their high adsorption capacity. Although a freshwater continuous-flow system for a nitrifier-based Mn-oxidizing microbial community for producing BioMnOx has been developed so far, a seawater continuous-flow bioreactor system for BioMnOx production has not been established. Here, we report BioMnOx production by a methanotroph-based microbial community by using a continuous-flow bioreactor system. The bioreactor system was operated using a deep-sea sediment sample as the inoculum with methane as the energy source for over 2 years. The BioMnOx production became evident after 370 days of reactor operation. The maximum Mn oxidation rate was 11.4 mg L -1 day -1 . An X-ray diffraction analysis showed that the accumulated BioMnOx was birnessite. 16S rRNA gene-based clone analyses indicated that methanotrophic bacterial members were relatively abundant in the system; however, none of the known Mn-oxidizing bacteria were detected. A continuous-flow bioreactor system coupled with nitrification was also run in parallel for 636 days, but no BioMnOx production was observed in this bioreactor system. The comparative experiments indicated that the methanotroph-based microbial community, rather than the nitrifier-based community, was effective for BioMnOx production under the marine environmental conditions.

  9. Electrical characterization of a laminar manganese oxide type birnessite; Caracterizacion electrica de un oxido de manganeso laminar tipo birnesita

    Arias, N. P.; Becerra, M. E.; Giraldo, O., E-mail: ohgiraldoo@unal.edu.co [Universidad Nacional de Colombia, Sede Manizales, Facultad de Ciencias Exactas y Naturales, Laboratorio de Materiales Nanoestructurados y Funcionales, Carrera 27 No. 64-60, 170004 Manizales (Colombia)

    2015-07-01

    This paper records the characterization of a manganese oxide synthesized by solid state routes which is analogous to natural mineral called birnessite. The analysis of X-ray diffraction and average oxidation state of manganese show that the material has a lamellar structure containing manganese in oxidation states (+4) and (+3). The results of electron microscopy along with surface area and pore size measurements reveal the presence of micro and meso pores in the material. Impedance spectroscopy suggests that high frequency electrical conduction occurs in the volume and on the border of the aggregates; in contrast, ionic conductivity at low frequencies was associated with potassium ions located in the interlaminar region. Ac conductivity values at low frequencies were 1.599 x 10{sup -6} Ω{sup -1} cm{sup -1} and 6.416 x 10{sup -5} Ω{sup -1} cm{sup -1} at high frequencies. These values are associated with an increased probability of electron jumping as frequency increases. These findings contribute to the understanding of electrical conduction processes and provides important information about its potential applications. As a result, this research will prove relevant in the field of batteries, super capacitors and heterogeneous catalysis, among others. (Author)

  10. Mechanisms of Bond Cleavage during Manganese Oxide and UV Degradation of Glyphosate: Results from Phosphate Oxygen Isotopes and Molecular Simulations.

    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.

  11. Mutation in HFE gene decreases manganese accumulation and oxidative stress in the brain after olfactory manganese exposure.

    Ye, Qi; Kim, Jonghan

    2016-06-01

    Increased accumulation of manganese (Mn) in the brain is significantly associated with neurobehavioral deficits and impaired brain function. Airborne Mn has a high systemic bioavailability and can be directly taken up into the brain, making it highly neurotoxic. While Mn transport is in part mediated by several iron transporters, the expression of these transporters is altered by the iron regulatory gene, HFE. Mutations in the HFE gene are the major cause of the iron overload disorder, hereditary hemochromatosis, one of the prevalent genetic diseases in humans. However, whether or not HFE mutation modifies Mn-induced neurotoxicity has not been evaluated. Therefore, our goal was to define the role of HFE mutation in Mn deposition in the brain and the resultant neurotoxic effects after olfactory Mn exposure. Mice carrying the H67D HFE mutation, which is homologous to the H63D mutation in humans, and their control, wild-type mice, were intranasally instilled with MnCl2 with different doses (0, 0.2, 1.0 and 5.0 mg kg(-1)) daily for 3 days. Mn levels in the blood, liver and brain were determined using inductively-coupled plasma mass spectrometry (ICP-MS). H67D mutant mice showed significantly lower Mn levels in the blood, liver, and most brain regions, especially in the striatum, while mice fed an iron-overload diet did not. Moreover, mRNA expression of ferroportin, an essential exporter of iron and Mn, was up-regulated in the striatum. In addition, the levels of isoprostane, a marker of lipid peroxidation, were increased in the striatum after Mn exposure in wild-type mice, but were unchanged in H67D mice. Together, our results suggest that the H67D mutation provides decreased susceptibility to Mn accumulation in the brain and neurotoxicity induced by inhaled Mn.

  12. Nanostructured carbon-metal oxide composite electrodes for supercapacitors: a review

    Zhi, Mingjia; Xiang, Chengcheng; Li, Jiangtian; Li, Ming; Wu, Nianqiang

    2012-12-01

    This paper presents a review of the research progress in the carbon-metal oxide composites for supercapacitor electrodes. In the past decade, various carbon-metal oxide composite electrodes have been developed by integrating metal oxides into different carbon nanostructures including zero-dimensional carbon nanoparticles, one-dimensional nanostructures (carbon nanotubes and carbon nanofibers), two-dimensional nanosheets (graphene and reduced graphene oxides) as well as three-dimensional porous carbon nano-architectures. This paper has described the constituent, the structure and the properties of the carbon-metal oxide composites. An emphasis is placed on the synergistic effects of the composite on the performance of supercapacitors in terms of specific capacitance, energy density, power density, rate capability and cyclic stability. This paper has also discussed the physico-chemical processes such as charge transport, ion diffusion and redox reactions involved in supercapacitors.

  13. Nanostructured carbon-metal oxide composite electrodes for supercapacitors: a review.

    Zhi, Mingjia; Xiang, Chengcheng; Li, Jiangtian; Li, Ming; Wu, Nianqiang

    2013-01-07

    This paper presents a review of the research progress in the carbon-metal oxide composites for supercapacitor electrodes. In the past decade, various carbon-metal oxide composite electrodes have been developed by integrating metal oxides into different carbon nanostructures including zero-dimensional carbon nanoparticles, one-dimensional nanostructures (carbon nanotubes and carbon nanofibers), two-dimensional nanosheets (graphene and reduced graphene oxides) as well as three-dimensional porous carbon nano-architectures. This paper has described the constituent, the structure and the properties of the carbon-metal oxide composites. An emphasis is placed on the synergistic effects of the composite on the performance of supercapacitors in terms of specific capacitance, energy density, power density, rate capability and cyclic stability. This paper has also discussed the physico-chemical processes such as charge transport, ion diffusion and redox reactions involved in supercapacitors.

  14. Synthesis and electrochemical behavior of nanostructured cauliflower-shape Co-Ni/Co-Ni oxides composites

    Gupta, Vinay; Kawaguchi, Toshikazu; Miura, Norio

    2009-01-01

    Nanostructured Co-Ni/Co-Ni oxides were electrochemically deposited onto stainless steel electrode by electrochemical method and characterized for their structural and supercapacitive properties. The SEM images indicated that the obtained Co-Ni/Co-Ni oxides had cauliflower-type nanostructure. The X-ray diffraction pattern showed the formation of Co 3 O 4 , NiO, Co and Ni. The EDX elemental mapping images indicated that Ni, Co and O are distributed uniformly. The deposited Co-Ni/Co-Ni oxides showed good supercapacitive characteristics with a specific capacitance of 331 F/g at 1 mA/cm 2 current density in 1 M KOH electrolyte. A mechanism of the formation of cauliflower-shape Co-Ni/Co-Ni oxides was proposed. A variety of promising applications in the fields such as energy storage devices and sensors can be envisioned from Co-Ni/Co-Ni oxides

  15. Engineering firecracker-like beta-manganese dioxides@spinel nickel cobaltates nanostructures for high-performance supercapacitors

    Kuang, Min; Wen, Zhong Quan; Guo, Xiao Long; Zhang, Sheng Mao; Zhang, Yu Xin

    2014-12-01

    An effective and rational strategy is developed for large-scale growth of firecracker-like Ni-substituted Co3O4 (NiCo2O4) nanosheets on β-MnO2 nanowires (NWs) with robust adhesion as high-performance electrode for electrochemical capacitors. The NiCo2O4-MnO2 nanostructures display much higher specific capacitance (343 F g-1 at current density of 0.5 A g-1), better rate capability (75.3% capacitance retention from 0.5 A g-1 to 8 A g-1) and excellent cycle stability (5% capacitance loss after 3000 cycles) than Co3O4-MnO2 nanostructures. Moreover, an asymmetric supercapacitor based on NiCo2O4-MnO2 NWs as the positive electrode and activated graphenes (AG) as the negative electrode achieves an energy density of 9.4 Wh kg-1 and a maximum power density of 2.5 kW kg-1. These attractive findings suggest this novel core-shell nanostructure promising for electrochemical applications as an efficient supercapacitive electrode.

  16. A Generalizable Top-Down Nanostructuring Method of Bulk Oxides: Sequential Oxygen-Nitrogen Exchange Reaction.

    Lee, Lanlee; Kang, Byungwuk; Han, Suyoung; Kim, Hee-Eun; Lee, Moo Dong; Bang, Jin Ho

    2018-05-27

    A thermal reaction route that induces grain fracture instead of grain growth is devised and developed as a top-down approach to prepare nanostructured oxides from bulk solids. This novel synthesis approach, referred to as the sequential oxygen-nitrogen exchange (SONE) reaction, exploits the reversible anion exchange between oxygen and nitrogen in oxides that is driven by a simple two-step thermal treatment in ammonia and air. Internal stress developed by significant structural rearrangement via the formation of (oxy)nitride and the creation of oxygen vacancies and their subsequent combination into nanopores transforms bulk solid oxides into nanostructured oxides. The SONE reaction can be applicable to most transition metal oxides, and when utilized in a lithium-ion battery, the produced nanostructured materials are superior to their bulk counterparts and even comparable to those produced by conventional bottom-up approaches. Given its simplicity and scalability, this synthesis method could open a new avenue to the development of high-performance nanostructured electrode materials that can meet the industrial demand of cost-effectiveness for mass production. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

    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.

  18. Synthesis of manganese oxides and antimony silicates and their applications to take up Thorium-234

    Al-Attar, L.; Budeir, Y.

    2009-07-01

    Birnessite, a layered manganese oxide, antimonysilicate and their corresponding cation-exchange derivatives were tested for their ability to take up thorium using a batch-type method. Sorption experiments were performed in different concentrations of acid, and sodium, potassium and calcium nitrate solutions in order to evaluate the influence of cations likely to be present in waste effluents. The results were expressed in terms of distribution coefficients. Linear regressions of the logarithmic plots enabled the elucidation of exchange mechanisms. Variation in the magnitude and mechanism of thorium sorption on the exchangers was ascribed to structural differences and the exchange properties of the materials, as well as the aqueous chemistry of the actinide element. The work expanded to included investigation of thorium solution' pH in controlling the sorption process. In nitric acid solutions, H-antimonysilicate proved to be the best sorbent. The hydrated layer structure of birnessite allows for facile mobility of the interlayer cations with fast kinetics and little structural rearrangement, making it of great importance for intercalation and ion exchange uses in salt conditions. Potassium had the most, and calcium the least, effect on thorium selectivity by birnessites, when they are present as macro components. Conversely, calcium ions did greatly inhibit the sorption behaviour of the actinide on Ca-doped antimonysilicate. Studying the effect of thorium solution' pH reflected the microcrystal modifications of birnessites occurred during experiments. (authors)

  19. Effect of support on the catalytic activity of manganese oxide catalyts for toluene combustion.

    Pozan, Gulin Selda

    2012-06-30

    The aim of this work was to study combustion of toluene (1000ppm) over MnO(2) modified with different supports. α-Al(2)O(3) and γ-Al(2)O(3) obtained from Boehmite, γ-Al(2)O(3) (commercial), SiO(2), TiO(2) and ZrO(2) were used as commercial support materials. In view of potential interest of this process, the influence of support material on the catalytic performance was discussed. The deposition of 9.5MnO(2) was performed by impregnation over support. The catalysts were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), temperature programmed reduction and oxidation (TPR/TPO) and thermogravimetric analysis (TGA). The catalytic tests were carried out at atmospheric pressure in a fixed-bed flow reactor. 9.5MnO(2)/α-Al(2)O(3)(B) (synthesized from Boehmite) catalyst exhibits the highest catalytic activity, over which the toluene conversion was up to 90% at a temperature of 289°C. Considering all the characterization and reaction data reported in this study, it was concluded that the manganese state and oxygen species played an important role in the catalytic activity. Copyright © 2012 Elsevier B.V. All rights reserved.

  20. Nanocomposites of manganese oxides and carbon nanotubes for aqueous supercapacitor stacks

    Zhang Shengwen; Peng Chuang; Ng, Kok C. [Department of Chemical and Environmental Engineering, Faculty of Engineering, University of Nottingham, University Park, Nottingham NG7 2RD (United Kingdom); Chen, George Z., E-mail: george.chen@nottingham.ac.u [Department of Chemical and Environmental Engineering, Faculty of Engineering, University of Nottingham, University Park, Nottingham NG7 2RD (United Kingdom)

    2010-10-30

    Symmetrical supercapacitors and their serially connected two-cell stacks via a bipolar electrode were constructed with nanocomposites of manganese oxides and carbon nanotubes (MnO{sub x}/CNTs) as the electrode materials. Nanocomposites with different contents of MnO{sub x} were synthesised through the redox reaction between KMnO{sub 4} and CNTs in aqueous solutions. The nanocomposites were characterised by scanning and transmission electron microscopy, BET nitrogen adsorption and X-ray diffraction before being examined in a three-electrode cell with a novel trenched graphite disc electrode by electrochemical means, including cyclic voltammetry, galvanostatic charging-discharging, and electrochemical impedance spectroscopy. The nanocomposites demonstrated capacitive behaviour in the potential range of 0-0.85 V (vs Ag/AgCl) in aqueous KCl electrolytes with less than 9% capacitance decrease after 9000 charging-discharging cycles. Symmetrical supercapacitors of identical positive and negative MnO{sub x}/CNTs electrodes showed capacitive performance in good agreement with the individual electrodes (e.g. 0.90 V, 0.53 F, 1.3 cm{sup 2}). The bipolarly connected two-cell stacks of the symmetrical cells exhibited characteristics in accordance with expectation, including a doubled stack voltage and reduced internal resistance per cell.

  1. Quantum Femtosecond Magnetism: Phase Transition in Step with Light in a Strongly Correlated Manganese Oxide

    Wang, Jigang

    2014-03-01

    Research of non-equilibrium phase transitions of strongly correlated electrons is built around addressing an outstanding challenge: how to achieve ultrafast manipulation of competing magnetic/electronic phases and reveal thermodynamically hidden orders at highly non-thermal, femtosecond timescales? Recently we reveal a new paradigm called quantum femtosecond magnetism-photoinduced femtosecond magnetic phase transitions driven by quantum spin flip fluctuations correlated with laser-excited inter-atomic coherent bonding. We demonstrate an antiferromagnetic (AFM) to ferromagnetic (FM) switching during about 100 fs laser pulses in a colossal magneto-resistive manganese oxide. Our results show a huge photoinduced femtosecond spin generation, measured by magnetic circular dichroism, with photo-excitation threshold behavior absent in the picosecond dynamics. This reveals an initial quantum coherent regime of magnetism, while the optical polarization/coherence still interacts with the spins to initiate local FM correlations that compete with the surrounding AFM matrix. Our results thus provide a framework that explores quantum non-equilibrium kinetics to drive phase transitions between exotic ground states in strongly correlated elecrons, and raise fundamental questions regarding some accepted rules, such as free energy and adiabatic potential surface. This work is in collaboration with Tianqi Li, Aaron Patz, Leonidas Mouchliadis, Jiaqiang Yan, Thomas A. Lograsso, Ilias E. Perakis. This work was supported by the National Science Foundation (contract no. DMR-1055352). Material synthesis at the Ames Laboratory was supported by the US Department of Energy-Basic Energy Sciences (contract no. DE-AC02-7CH11358).

  2. Large coercivity and unconventional exchange coupling in manganese-oxide-coated manganese—gallium nanoparticles

    Feng Jun-Ning; Liu Wei; Geng Dian-Yu; Ma Song; Yu Tao; Zhao Xiao-Tian; Dai Zhi-Ming; Zhao Xin-Guo; Zhang Zhi-Dong

    2014-01-01

    The microstructures and magnetic properties of nanoparticles, each composed of an antiferromagnetic (AFM) manganese-oxide shell and a ferromagnetic-like core of manganese—gallium (MnGa) compounds, are studied. The core-shell structure is confirmed by transmission electron microscope (TEM). The ferromagnetic-like core contains three kinds of MnGa binary compounds, i.e., ferrimagnetic (FI) D0 22 -type Mn 3 Ga, ferromagnetic (FM) Mn 8 Ga 5 , and AFM D0 19 -type Mn 3 Ga, of which the first two correspond respectively to a hard magnetic phase and to a soft one. Decoupling effect between these two phases is found at low temperature, which weakens gradually with increasing temperature and disappears above 200 K. The exchange bias (EB) effect is observed simultaneously, which is caused by the exchange coupling between the AFM shell and FM-like core. A large coercivity of 6.96 kOe (1 Oe = 79.5775 A·m −1 ) and a maximum EB value of 0.45 kOe are achieved at 300 K and 200 K respectively. (special topic — international conference on nanoscience and technology, china 2013)

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

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

    2011-01-01

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

  4. Catalytic ozonation of fenofibric acid over alumina-supported manganese oxide

    Rosal, Roberto, E-mail: roberto.rosal@uah.es [Departamento de Quimica Analitica e Ingenieria Quimica, Universidad de Alcala, E-28771 Alcala de Henares (Spain); Gonzalo, Maria S.; Rodriguez, Antonio; Garcia-Calvo, Eloy [Departamento de Quimica Analitica e Ingenieria Quimica, Universidad de Alcala, E-28771 Alcala de Henares (Spain)

    2010-11-15

    The catalytic ozonation of fenofibric acid was studied using activated alumina and alumina-supported manganese oxide in a semicontinuous reactor. The rate constants at 20 deg. C for the non-catalytic reaction of fenofibric acid with ozone and hydroxyl radicals were 3.43 {+-} 0.20 M{sup -1} s{sup -1} and (6.55 {+-} 0.33) x 10{sup 9} M{sup -1} s{sup -1}, respectively. The kinetic constant for the catalytic reaction between fenofibric acid and hydroxyl radicals did not differ significantly from that of homogeneous ozonation, either using Al{sub 2}O{sub 3} or MnO{sub x}/Al{sub 2}O{sub 3}. The results showed a considerable increase in the generation of hydroxyl radicals due to the use of catalysts even in the case of catalytic runs performed using a real wastewater matrix. Both catalysts promoted the decomposition of ozone in homogeneous phase, but the higher production of hydroxyl radicals corresponded to the catalyst with more activity in terms of ozone decomposition. We did not find evidence of the catalysts having any effect on rate constants, which suggests that the reaction may not involve the adsorption of organics on catalyst surface.

  5. Heavy metals and manganese oxides in the genesee watershed, New York state: effects of geology and land use

    Whitney, P.R.

    1981-01-01

    Manganese oxide coatings on gravels from 255 sites on tributary streams in the Genesee River Watershed were analyzed for Mn, Fe, Zn, Cd, Co, Ni, Pb, and Cu. The results were compared with data on bedrock geology, surficial geology and land use, using factor analysis and stepwise multiple regression. All metals except Pb show strong positive correlation with Mn. This association results from the well-known tendency of Mn oxide precipitates to adsorb and incorporate dissolved trace metals. Pb may be present in a separate phase on the gravel surfaces; alternatively Pb abundance may be so strongly influenced by environmental factors that the effect of varying abundance of the carrier phase becomes relatively unimportant. When the effects of varying Mn abundance are allowed for, Pb and to a lesser extent Zn and Cu abundances are seen to be related to commercial, industrial and residential land use. In addition to this pollution effect, all the trace metals, Cd and Ni most strongly, tend to be more abundant in oxide coatings from streams in the forested uplands in the southern part of the area. This probably reflects increased geochemical mobility of the metals in the more acid soils and groundwater of the southern region. A strong Zn anomaly is present in streams draining areas underlain by the Lockport Formation. Oxide coatings in these streams contain up to 5% Zn, originating from disseminated sphalerite in the Lockport and secondary Zn concentrations in the overlying muck soils. The same group of metals, plus calcium and loss on ignition, were determined in the silt and clay (minus 230 mesh) fraction of stream sediments from 129 of the same sites, using a hot nitric acid leach. The amounts of manganese in the sediments are low (average 1020 ppm) and manganese oxides are, at most, of relatively minor significance in the trace-metal geochemistry of these sediments. The bulk of the trace metals in sediment appears to be associated with iron oxides, clays and organic

  6. Spinel-structured surface layers for facile Li ion transport and improved chemical stability of lithium manganese oxide spinel

    Lee, Hae Ri [Center for Energy Convergence Research, Korea Institute of Science Technology, Hwarang-ro 14-gil 5, Seongbuk-gu, Seoul 136-791 (Korea, Republic of); Department of Chemical and Biological Engineering, Korea University, 145, Anam-ro, Seongbuk-gu, Seoul 136-701 (Korea, Republic of); Seo, Hyo Ree; Lee, Boeun; Cho, Byung Won [Center for Energy Convergence Research, Korea Institute of Science Technology, Hwarang-ro 14-gil 5, Seongbuk-gu, Seoul 136-791 (Korea, Republic of); Lee, Kwan-Young [Department of Chemical and Biological Engineering, Korea University, 145, Anam-ro, Seongbuk-gu, Seoul 136-701 (Korea, Republic of); Oh, Si Hyoung, E-mail: sho74@kist.re.kr [Center for Energy Convergence Research, Korea Institute of Science Technology, Hwarang-ro 14-gil 5, Seongbuk-gu, Seoul 136-791 (Korea, Republic of)

    2017-01-15

    Graphical abstract: Strategically-designed spinel-structured nano-scale surface layer, LiM{sub x}Mn{sup IV}{sub 1−x}O{sub 4}, featuring a high Li{sup +} ion conductivity and a good chemical stability was applied on Al-doped LiMn{sub 2}O{sub 4} spinel for the drastic improvement of the electrochemical performance at the elevated temperature as a promising cathode material for lithium rechargeable batteries. - Highlights: • Spinel-structured surface layer with a high Li-ion conductivity and a good chemical stability was prepared. • Simple wet process was developed to apply nano-scale surface layer on aluminum doped lithium manganese oxide spinel. • The properties of nano-scale surface layer were characterized by analytical tools including GITT, HR-TEM and XAS. • Materials with surface coating layer exhibit an excellent electrochemical performance at the elevated temperature. - Abstract: Li-ion conducting spinel-structured oxide layer with a manganese oxidation state close to being tetravalent was prepared on aluminum-doped lithium manganese oxide spinel for improving the electrochemical performances at the elevated temperatures. This nanoscale surface layer provides a good ionic conduction path for lithium ion transport to the core and also serves as an excellent chemical barrier for protecting the high-capacity core material from manganese dissolution into the electrolyte. In this work, a simple wet process was employed to prepare thin LiAlMnO{sub 4} and LiMg{sub 0.5}Mn{sub 1.5}O{sub 4} layers on the surface of LiAl{sub 0.1}Mn{sub 1.9}O{sub 4}. X-ray absorption studies revealed an oxidation state close to tetravalent manganese on the surface layer of coated materials. Materials with these surface coating layers exhibited excellent capacity retentions superior to the bare material, without undermining the lithium ion transport characteristics and the high rate performances.

  7. In situ synthesis of manganese oxides on polyester fiber for formaldehyde decomposition at room temperature

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

    2015-01-01

    Graphical abstract: - Highlights: • The MnO x particles assembled with nanosheets were uniformly coated on PET fibers. • The growth process of MnO x layer on PET is clearly clarified. • MnO x /PET showed good activity for HCHO decomposition at room temperature. • MnO x /PET material is promising for indoor air purification due to its light, flexible and low air-resistant properties. - Abstract: Removal of low-level formaldehyde (HCHO) is of great interest for indoor air quality improvement. Supported materials especially those with low air pressure drop are of necessity for air purification. Manganese oxides (MnO x ) was in situ deposited on the surface of fibers of a non-woven fabric made of polyethylene terephthalate (PET). As-synthesized MnO x /PET were characterized by SEM, XRD, TEM, ATR-FTIR and XPS analysis. The growth of MnO x layer on PET is thought to start with partial hydrolysis of PET, followed by surface oxidation by KMnO 4 and then surface-deposition of MnO x particles from the bulk phase. The MnO x particles assembled with nanosheets were uniformly coated on the PET fibers. MnO x /PET showed good activity for HCHO decomposition at room temperature which followed the Mars–van Krevelen mechanism. The removal of HCHO was kept over 94% after 10 h continuous reaction under the conditions of inlet HCHO concentration ∼0.6 mg/m 3 , space velocity ∼17,000 h −1 and relative humidity∼50%. This research provides a facile method to deposit active MnO x onto polymers with low air resistance, and composite MnO x /PET material is promising for indoor air purification.

  8. In situ synthesis of manganese oxides on polyester fiber for formaldehyde decomposition at room temperature

    Wang, Jinlong [State Key Joint Laboratory of Environment Simulation and Pollution Control, School of Environment, Tsinghua University, Beijing 100084 (China); Collaborative Innovation Center for Regional Environmental Quality (China); Yunus, Rizwangul [State Key Joint Laboratory of Environment Simulation and Pollution Control, School of Environment, Tsinghua University, Beijing 100084 (China); Xinjiang Zhongtai Chemical Company, Xinjiang 831511 (China); Li, Jinge; Li, Peilin [State Key Joint Laboratory of Environment Simulation and Pollution Control, School of Environment, Tsinghua University, Beijing 100084 (China); Zhang, Pengyi, E-mail: zpy@tsinghua.edu.cn [State Key Joint Laboratory of Environment Simulation and Pollution Control, School of Environment, Tsinghua University, Beijing 100084 (China); Collaborative Innovation Center for Regional Environmental Quality (China); Kim, Jeonghyun [State Key Joint Laboratory of Environment Simulation and Pollution Control, School of Environment, Tsinghua University, Beijing 100084 (China); Collaborative Innovation Center for Regional Environmental Quality (China)

    2015-12-01

    Graphical abstract: - Highlights: • The MnO{sub x} particles assembled with nanosheets were uniformly coated on PET fibers. • The growth process of MnO{sub x} layer on PET is clearly clarified. • MnO{sub x}/PET showed good activity for HCHO decomposition at room temperature. • MnO{sub x}/PET material is promising for indoor air purification due to its light, flexible and low air-resistant properties. - Abstract: Removal of low-level formaldehyde (HCHO) is of great interest for indoor air quality improvement. Supported materials especially those with low air pressure drop are of necessity for air purification. Manganese oxides (MnO{sub x}) was in situ deposited on the surface of fibers of a non-woven fabric made of polyethylene terephthalate (PET). As-synthesized MnO{sub x}/PET were characterized by SEM, XRD, TEM, ATR-FTIR and XPS analysis. The growth of MnO{sub x} layer on PET is thought to start with partial hydrolysis of PET, followed by surface oxidation by KMnO{sub 4} and then surface-deposition of MnO{sub x} particles from the bulk phase. The MnO{sub x} particles assembled with nanosheets were uniformly coated on the PET fibers. MnO{sub x}/PET showed good activity for HCHO decomposition at room temperature which followed the Mars–van Krevelen mechanism. The removal of HCHO was kept over 94% after 10 h continuous reaction under the conditions of inlet HCHO concentration ∼0.6 mg/m{sup 3}, space velocity ∼17,000 h{sup −1} and relative humidity∼50%. This research provides a facile method to deposit active MnO{sub x} onto polymers with low air resistance, and composite MnO{sub x}/PET material is promising for indoor air purification.

  9. Well-ordered organic–inorganic hybrid layered manganese oxide nanocomposites with excellent decolorization performance

    Zhou, Junli; Yu, Lin; Sun, Ming; Ye, Fei; Lan, Bang; Diao, Guiqiang; He, Jun

    2013-01-01

    Well-ordered organic–inorganic hybrid layered manganese oxide nanocomposites (CTAB-Al-MO) with excellent decolorization performance were prepared through a two-step process. Specifically, the MnO 2 nanosheets were self-assembled in the presence of CTAB, and subsequently pillared with Keggin ions. The obtained CTAB-Al-MO with the basal spacing of 1.59 nm could be stable at 300 °C for 2 h and also possesses high total pore volumes (0.41 cm³ g −1 ) and high specific BET surface area (161 m 2 g −1 ), which is nine times larger than that of the pristine (19 m 2 g −1 ). Possible formation process for the highly thermal stable CTAB-Al-MO is proposed here. The decolorization experiments of methyl orange showed that the obtained CTAB-Al-MO exhibit excellent performance in wastewater treatment and the decolorization rate could reach 95% within 5 min. - Graphical Abstract: Well-ordered organic–inorganic hybrid LMO nanocomposites (CTAB-Al-MO) with excellent decolorization performance were prepared through a two-step process. Specifically, the MnO 2 nanosheets were self-assembled by CTAB, and subsequently pillared with Keggin ions. Highlights: ► A two-step synthesis method was used to prepare the CTAB-Al-MO. ► The CTAB-Al-MO has the large basal spacing and high specific BET surface area. ► The thermal stability of the well-ordered CTAB-Al-MO could obviously improve. ► The CTAB-Al-MO exhibits excellent oxidation and absorption ability to remove organic pollutants.

  10. Promotion effect of manganese oxide on the electrocatalytic activity of Pt/C for methanol oxidation in acid medium

    Abdel Hameed, R.M., E-mail: randa311eg@yahoo.com [Chemistry Department, Faculty of Science, Cairo University, Giza (Egypt); Fetohi, Amani E.; Amin, R.S.; El-Khatib, K.M. [Chemical Engineering Department, National Research Center, Dokki, Giza (Egypt)

    2015-12-30

    Graphical abstract: Physical and electrochemical properties of Pt/C, Pt–MnO{sub 2}/C-1 and Pt–MnO{sub 2}/C-2 electrocatalysts. - Highlights: • Adding MnO{sub 2} to Pt/C improved the dispersion of Pt nanoparticles. • The existence of MnO{sub 2} improved the kinetics of methanol oxidation reaction. • R{sub ct} value of Pt–MnO{sub 2}/C was about 10 times as low as that at Pt/C. • The removal of CO{sub ads} poisoning species was facilitated at Pt–MnO{sub 2}/C. - Abstract: The modification of Pt/C by incorporating metal oxides for electrocatalytic oxidation of methanol has gained major attention because of the efficiency loss during the course of long-time operation. This work describes the preparation of Pt–MnO{sub 2}/C electrocatalysts through a chemical route using ethylene glycol or a mixture of ethylene glycol and sodium borohydride as a reducing agent. The crystallite structure and particle size of synthesized electrocatalysts are determined using X-ray diffraction (XRD) and transmission electron microscopy (TEM). The addition of MnO{sub 2} improves the dispersion of Pt nanoparticles. The electrocatalytic activity of Pt–MnO{sub 2}/C towards methanol oxidation in H{sub 2}SO{sub 4} solution is investigated using cyclic voltammetry and electrochemical impedance spectroscopy. The onset potential value of methanol oxidation peak is negatively shifted by 169 mV when MnO{sub 2} is introduced to Pt/C. Moreover, the charge transfer resistance value at Pt–MnO{sub 2}/C is about 10 times as low as that at Pt/C. Chronoamperometry and chronopotentiometry show that CO tolerance is greatly improved at Pt–MnO{sub 2}/C. The increased electrocatalytic activity and enhanced ability to clean platinum surface elect manganese oxide as a suitable promoter for the anode performance in direct methanol fuel cells (DMFCs).

  11. Biological versus mineralogical chromium reduction: potential for reoxidation by manganese oxide.

    Butler, Elizabeth C; Chen, Lixia; Hansel, Colleen M; Krumholz, Lee R; Elwood Madden, Andrew S; Lan, Ying

    2015-11-01

    Hexavalent chromium (Cr(vi), present predominantly as CrO4(2-) in water at neutral pH) is a common ground water pollutant, and reductive immobilization is a frequent remediation alternative. The Cr(iii) that forms upon microbial or abiotic reduction often co-precipitates with naturally present or added iron (Fe), and the stability of the resulting Fe-Cr precipitate is a function of its mineral properties. In this study, Fe-Cr solids were formed by microbial Cr(vi) reduction using Desulfovibrio vulgaris strain RCH1 in the presence of the Fe-bearing minerals hematite, aluminum substituted goethite (Al-goethite), and nontronite (NAu-2, Clay Minerals Society), or by abiotic Cr(vi) reduction by dithionite reduced NAu-2 or iron sulfide (FeS). The properties of the resulting Fe-Cr solids and their behavior upon exposure to the oxidant manganese (Mn) oxide (birnessite) differed significantly. In microcosms containing strain RCH1 and hematite or Al-goethite, there was significant initial loss of Cr(vi) in a pattern consistent with adsorption, and significant Cr(vi) was found in the resulting solids. The solid formed when Cr(vi) was reduced by FeS contained a high proportion of Cr(iii) and was poorly crystalline. In microcosms with strain RCH1 and hematite, Cr precipitates appeared to be concentrated in organic biofilms. Reaction between birnessite and the abiotically formed Cr(iii) solids led to production of significant dissolved Cr(vi) compared to the no-birnessite controls. This pattern was not observed in the solids generated by microbial Cr(vi) reduction, possibly due to re-reduction of any Cr(vi) generated upon oxidation by birnessite by active bacteria or microbial enzymes. The results of this study suggest that Fe-Cr precipitates formed in groundwater remediation may remain stable only in the presence of active anaerobic microbial reduction. If exposed to environmentally common Mn oxides such as birnessite in the absence of microbial activity, there is the potential

  12. Surface engineering of one-dimensional tin oxide nanostructures for chemical sensors

    Ma, Yuanyuan; Qu, Yongquan; Zhou, Wei

    2013-01-01

    Nanostructured materials are promising candidates for chemical sensors due to their fascinating physicochemical properties. Among various candidates, tin oxide (SnO 2 ) has been widely explored in gas sensing elements due to its excellent chemical stability, low cost, ease of fabrication and remarkable reproducibility. We are presenting an overview on recent investigations on 1-dimensional (1D) SnO 2 nanostructures for chemical sensing. In particular, we focus on the performance of devices based on surface engineered SnO 2 nanostructures, and on aspects of morphology, size, and functionality. The synthesis and sensing mechanism of highly selective, sensitive and stable 1D nanostructures for use in chemical sensing are discussed first. This is followed by a discussion of the relationship between the surface properties of the SnO 2 layer and the sensor performance from a thermodynamic point of view. Then, the opportunities and recent progress of chemical sensors fabricated from 1D SnO 2 heterogeneous nanostructures are discussed. Finally, we summarize current challenges in terms of improving the performance of chemical (gas) sensors using such nanostructures and suggest potential applications. (author)

  13. Chemical degradation of trimethyl phosphate as surrogate for organo-phosporus pesticides on nanostructured metal oxides

    Štengl, Václav; Henych, Jiří; Matys Grygar, Tomáš; Pérez, Raul

    2015-01-01

    Roč. 61, JAN (2015), s. 259-269 ISSN 0025-5408 R&D Projects: GA ČR(CZ) GAP106/12/1116 Institutional support: RVO:61388980 Keywords : Nanostructured oxides * Stoichiometric degradation * Trimethyl phosphate Subject RIV: CA - Inorganic Chemistry Impact factor: 2.435, year: 2015

  14. Passivating electron contact based on highly crystalline nanostructured silicon oxide layers for silicon solar cells

    Stuckelberger, J.; Nogay, G.; Wyss, P.; Jeangros, Q.; Allebe, Ch.; Debrot, F.; Niquille, X.; Ledinský, Martin; Fejfar, Antonín; Despeisse, M.; Haug, F.J.; Löper, P.; Ballif, C.

    2016-01-01

    Roč. 158, Dec (2016), s. 2-10 ISSN 0927-0248 R&D Projects: GA MŠk LM2015087 Institutional support: RVO:68378271 Keywords : surface passivation * passivating contact * nanostructure * silicon oxide * nanocrystalline * microcrystalline * poly-silicon * crystallization * Raman * transmission line measurement Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 4.784, year: 2016

  15. Nanostructures in a ferritic and an oxide dispersion strengthened steel induced by dynamic plastic deformation

    Zhang, Zhenbo

    fission and fusion reactors. In this study, two candidate steels for nuclear reactors, namely a ferritic/martensitic steel (modified 9Cr-1Mo steel) and an oxide dispersion strengthened (ODS) ferritic steel (PM2000), were nanostructured by dynamic plastic deformation (DPD). The resulting microstructure...

  16. Life cycle assessment of facile microwave-assisted zinc oxide (ZnO) nanostructures

    Papadaki, D

    2017-05-01

    Full Text Available The life cycle assessment of several zinc oxide (ZnO) nanostructures, fabricated by a facile microwave technique, is presented. Key synthesis parameters such as annealing temperature, varied from 90 °C to 220 °C, and microwave power, varied from 110...

  17. Investigation on CO catalytic oxidation reaction kinetics of faceted perovskite nanostructures loaded with Pt

    Yin, S. M.

    2017-01-18

    Perovskite lead titanate nanostructures with specific {111}, {100} and {001} facets exposed, have been employed as supports to investigate the crystal facet effect on the growth and CO catalytic activity of Pt nanoparticles. The size, distribution and surface chemical states of Pt on the perovskite supports have been significantly modified, leading to a tailored conversion temperature and catalytic kinetics towards CO catalytic oxidation.

  18. Investigation on CO catalytic oxidation reaction kinetics of faceted perovskite nanostructures loaded with Pt

    Yin, S. M.; Duanmu, J. J.; Zhu, Yihan; Yuan, Y. F.; Guo, S. Y.; Yang, J. L.; Ren, Z. H.; Han, G. R.

    2017-01-01

    Perovskite lead titanate nanostructures with specific {111}, {100} and {001} facets exposed, have been employed as supports to investigate the crystal facet effect on the growth and CO catalytic activity of Pt nanoparticles. The size, distribution and surface chemical states of Pt on the perovskite supports have been significantly modified, leading to a tailored conversion temperature and catalytic kinetics towards CO catalytic oxidation.

  19. Ternary oxide nanostructures and methods of making same

    Wong, Stanislaus S [Stony Brook, NY; Park, Tae-Jin [Port Jefferson, NY

    2009-09-08

    A single crystalline ternary nanostructure having the formula A.sub.xB.sub.yO.sub.z, wherein x ranges from 0.25 to 24, and y ranges from 1.5 to 40, and wherein A and B are independently selected from the group consisting of Ag, Al, As, Au, B, Ba, Br, Ca, Cd, Ce, Cl, Cm, Co, Cr, Cs, Cu, Dy, Er, Eu, F, Fe, Ga, Gd, Ge, Hf, Ho, I, In, Ir, K, La, Li, Lu, Mg, Mn, Mo, Na, Nb, Nd, Ni, Os, P, Pb, Pd, Pr, Pt, Rb, Re, Rh, Ru, S, Sb, Sc, Se, Si, Sm, Sn, Sr, Ta, Tb, Tc, Te, Ti, Tl, Tm, U, V, W, Y, Yb, and Zn, wherein the nanostructure is at least 95% free of defects and/or dislocations.

  20. Metal oxide nanostructures: preparation, characterization and functional applications as chemical sensors.

    Zappa, Dario; Bertuna, Angela; Comini, Elisabetta; Kaur, Navpreet; Poli, Nicola; Sberveglieri, Veronica; Sberveglieri, Giorgio

    2017-01-01

    Preparation and characterization of different metal oxide (NiO, WO 3 , ZnO, SnO 2 and Nb 2 O 5 ) nanostructures for chemical sensing are presented. p-Type (NiO) and n-type (WO 3 , SnO 2 , ZnO and Nb 2 O 5 ) metal oxide nanostructures were grown on alumina substrates using evaporation-condensation, thermal oxidation and hydrothermal techniques. Surface morphologies and crystal structures were investigated through scanning electron microscopy and Raman spectroscopy. Furthermore, different batches of sensors have been prepared, and their sensing performances towards carbon monoxide and nitrogen dioxide have been explored. Moreover, metal oxide nanowires have been integrated into an electronic nose and successfully applied to discriminate between drinking and contaminated water.

  1. Modification of implant material surface properties by means of oxide nano-structured coatings deposition

    Safonov, Vladimir; Zykova, Anna; Smolik, Jerzy; Rogowska, Renata; Lukyanchenko, Vladimir; Kolesnikov, Dmitrii

    2014-08-01

    The deposition of functional coatings on the metal surface of artificial joints is an effective way of enhancing joint tribological characteristics. It is well-known that nanostructured oxide coatings have specific properties advantageous for future implant applications. In the present study, we measured the high hardness parameters, the adhesion strength and the low friction coefficient of the oxide magnetron sputtered coatings. The corrosion test results show that the oxide coating deposition had improved the corrosion resistance by a factor of ten for both stainless steel and titanium alloy substrates. Moreover, the hydrophilic nature of coated surfaces in comparison with the metal ones was investigated in the tensiometric tests. The surfaces with nanostructured oxide coatings demonstrated improved biocompatibility for in vitro and in vivo tests, attributed to the high dielectric constants and the high values of the surface free energy parameters.

  2. Colloidosome-based synthesis of a multifunctional nanostructure of silver and hollow iron oxide nanoparticles

    Pan, Yue

    2010-03-16

    Nanoparticles that self-assemble on a liquid-liquid interface serve as the building block for making heterodimeric nanostructures. Specifically, hollow iron oxide nanoparticles within hexane form colloidosomes in the aqueous solution of silver nitrate, and iron oxide exposed to the aqueous phase catalyzes the reduction of silver ions to afford a heterodimer of silver and hollow iron oxide nanoparticles. Transmission electron microscopy, selected area electron diffraction, energy-dispersive X-ray spectrometry, X-ray diffraction, UV-vis spectroscopy, and SQUID were used to characterize the heterodimers. Interestingly, the formation of silver nanoparticles helps the removal of spinglass layer on the hollow iron oxide nanoparticles. This work demonstrates a powerful yet convenient strategy for producing sophisticated, multifunctional nanostructures. © 2010 American Chemical Society.

  3. Detection of different oxidation states of individual manganese porphyrins during their reaction with oxygen at a solid/liquid interface.

    den Boer, Duncan; Li, Min; Habets, Thomas; Iavicoli, Patrizia; Rowan, Alan E; Nolte, Roeland J M; Speller, Sylvia; Amabilino, David B; De Feyter, Steven; Elemans, Johannes A A W

    2013-07-01

    Manganese porphyrins have been extensively investigated as model systems for the natural enzyme cytochrome P450 and as synthetic oxidation catalysts. Here, we report single-molecule studies of the multistep reaction of manganese porphyrins with molecular oxygen at a solid/liquid interface, using a scanning tunnelling microscope (STM) under environmental control. The high lateral resolution of the STM, in combination with its sensitivity to subtle differences in the electronic properties of molecules, allowed the detection of at least four distinct reaction species. Real-space and real-time imaging of reaction dynamics enabled the observation of active sites, immobile on the experimental timescale. Conversions between the different species could be tuned by the composition of the atmosphere (argon, air or oxygen) and the surface bias voltage. By means of extensive comparison of the results to those obtained by analogous solution-based chemistry, we assigned the observed species to the starting compound, reaction intermediates and products.

  4. Anchoring alpha-manganese oxide nanocrystallites on multi-walled carbon nanotubes as electrode materials for supercapacitor

    Li Li; Qin Zongyi, E-mail: phqin@dhu.edu.cn; Wang Lingfeng; Liu Hongjin; Zhu Meifang [Donghua University, State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, College of Materials Science and Engineering (China)

    2010-09-15

    The partial coverage of manganese oxide (MnO{sub 2}) 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 ({alpha}-MnO{sub 2}) 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 MnO{sub 2} nanocrystallites efficiently increased the contact of the electrolyte with the active materials. Thus, the highest specific capacitance of 550 F g{sup -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.

  5. Anchoring alpha-manganese oxide nanocrystallites on multi-walled carbon nanotubes as electrode materials for supercapacitor

    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.

  6. A highly efficient urea detection using flower-like zinc oxide nanostructures

    Tak, Manvi; Gupta, Vinay [Department of Physics and Astrophysics, University of Delhi, Delhi 110007 (India); Tomar, Monika, E-mail: monikatomar@gmail.com [Department of Physics, Miranda House, University of Delhi, Delhi 110007 (India)

    2015-12-01

    A novel matrix based on flower-like zinc oxide nanostructures (ZnONF) has been fabricated using hydrothermal method and exploited successfully for the development of urea biosensor. Urease (Urs) is physically immobilized onto the ZnO nanostructure matrix synthesized over platinized silicon substrate. The surface morphology and crystallographic structure of the as-grown ZnONF have been characterized using a scanning electron microscope (SEM) and X-ray diffraction (XRD) techniques. The fabricated amperometric biosensor (Urs/ZnONF/Pt/Ti/Si) exhibits a linear sensing response towards urea over the concentration range 1.65 mM to 16.50 mM with an enhanced sensitivity (~ 132 μA/mM/cm{sup 2}) and a fast response time of 4 s. The relatively low value of Michaelis–Menten constant (K{sub m}) of 0.19 mM confirms the high affinity of the immobilized urease on the nanostructured ZnONF surface towards its analyte (urea). The obtained results demonstrate that flower-like ZnO nanostructures serve as a promising matrix for the realization of efficient amperometric urea biosensor with enhanced response characteristics. - Graphical abstract: The article focuses on the synthesis of flower-like morphology possessing zinc oxide nanostructures and its application towards urea detection with high sensitivity as well as selectivity. - Highlights: • Flower-like ZnO nanostructures based urea biosensor has been fabricated. • Grown ZnO nanostructures offer an advantageous urease immobilization platform owing to its very high surface area. • High sensitivity (~ 132 μA/mM/cm{sup 2}) and low Michaelis–Menten parameter (K{sub m}) value (~ 0.19 mM) were observed.

  7. A highly efficient urea detection using flower-like zinc oxide nanostructures

    Tak, Manvi; Gupta, Vinay; Tomar, Monika

    2015-01-01

    A novel matrix based on flower-like zinc oxide nanostructures (ZnONF) has been fabricated using hydrothermal method and exploited successfully for the development of urea biosensor. Urease (Urs) is physically immobilized onto the ZnO nanostructure matrix synthesized over platinized silicon substrate. The surface morphology and crystallographic structure of the as-grown ZnONF have been characterized using a scanning electron microscope (SEM) and X-ray diffraction (XRD) techniques. The fabricated amperometric biosensor (Urs/ZnONF/Pt/Ti/Si) exhibits a linear sensing response towards urea over the concentration range 1.65 mM to 16.50 mM with an enhanced sensitivity (~ 132 μA/mM/cm 2 ) and a fast response time of 4 s. The relatively low value of Michaelis–Menten constant (K m ) of 0.19 mM confirms the high affinity of the immobilized urease on the nanostructured ZnONF surface towards its analyte (urea). The obtained results demonstrate that flower-like ZnO nanostructures serve as a promising matrix for the realization of efficient amperometric urea biosensor with enhanced response characteristics. - Graphical abstract: The article focuses on the synthesis of flower-like morphology possessing zinc oxide nanostructures and its application towards urea detection with high sensitivity as well as selectivity. - Highlights: • Flower-like ZnO nanostructures based urea biosensor has been fabricated. • Grown ZnO nanostructures offer an advantageous urease immobilization platform owing to its very high surface area. • High sensitivity (~ 132 μA/mM/cm 2 ) and low Michaelis–Menten parameter (K m ) value (~ 0.19 mM) were observed

  8. Power loss and energy density of the asymmetric ultracapacitor loaded with molybdenum doped manganese oxide

    Wang, Yue-Sheng; Tsai, Dah-Shyang; Chung, Wen-Hung; Syu, Yong-Sin; Huang, Ying-Sheng

    2012-01-01

    Highlights: ► Mo-doping (15 mol%) enhances capacitance and diminishes oxide resistance. ► Influences of Mo-doped MnO 2 are analyzed at the level of capacitor power and energy. ► Polarization loss of the asymmetric capacitor is more than that of the symmetric one. ► Pseudocapacitance benefit on energy is evaluated with power and current densities. - Abstract: Ultracapacitors of asymmetric configuration have been prepared with activated carbon (AC) and undoped or Mo-doped manganese oxide (MnO 2 ) in 1.0 M Na 2 SO 4 electrolyte. Phase analysis shows the AC powder, 1–15 μm in size, contains both disordered and graphitic structures, and the undoped and Mo-doped oxide powder, 0.05–0.20 μm in particle size, mainly involves amorphous MnO 2 and MoO 2 . CV results indicate the single electrode of AC plus 10 wt% Mo-doped MnO 2 (A9O M 1) is superior to the electrode with undoped MnO 2 or high content of doped MnO 2 , exhibiting features of double layer capacitance at high scan rate and pseudocapacitance characteristics at low scan rate. When assembled with a negative electrode of AC, the capacitor of positive A9O M 1 electrode demonstrates the least power loss among three asymmetric capacitors. This asymmetric capacitor also shows a higher capacitance than the symmetric AC capacitor when the current density is less than 8.0 A g −1 in 1.8 V potential window. But a higher electrode resistance of A9O M 1, in contrast with AC, compromises its capacitance plus. When the energy density of A9O M 1 asymmetric capacitor is compared with that of symmetric AC capacitor at the same power level, the capacitance benefit on energy density is restricted to current density ≤ 3.0 A g −1 .

  9. Manganese oxide nanoflakes/multi-walled carbon nanotubes/chitosan nanocomposite modified glassy carbon electrode as a novel electrochemical sensor for chromium (III) detection

    Salimi, Abdollah; Pourbahram, Bahareh; Mansouri-Majd, Samira; Hallaj, Rahman

    2015-01-01

    Highlights: • CNTs/chitosan/GC electrode used as platform for electrodeposition of MnO x -nanoflakes. • Modified electrode has excellent catalytic activity for oxidation of Cr 3+ at pH 3–7. • Detection limit and sensitivity of sensor for Cr 3+ detection were 0.3 μM and 18.7 nA/μM. • Sensor has good stability and high selectivity in the presence of common interferences. • Sensor applied for the detection of Cr 3+ in real samples with satisfactory results. - Abstract: In this research a nanocomposite containing chitosan (Chit) and maltiwalled carbon nanotubes (MWCNTs) was applied as platform for immobilization of electrodeposited manganese oxide (MnOx) nanostructures. First, glassy carbon (GC) electrode modified with thin film of Chitosan/MWCNTs nanocomposite. Then MnO x nanostructures was electrodeposited onto Chitosan/MWCNTs modified GC electrode using combination of constant potential step (0.6 V) and cyclic voltammetry(0.3–0.6 V) techniques. The XRD patterns and scanning electron microscope images indicated immobilization of uniformly MnOx nanoflakes with high crystallite onto MWCNTs/Chit film. The modified electrode shows a well-defined redox couple for Mn 2+ /MnO 2 system. Charge transfer coefficient (α), electron transfer rate constant (k s ) and surface concentration (Γ) were 0.394, 3.44 s −1 and 3.3 × 10 −11 mol cm −2 , respectively. The modified electrode showed excellent electrocatalytic activity toward oxidation of chromium (III) at natural pH solutions. Cyclic voltammetry and hydrodynamic amperometery were applied as measuring techniques for chromium detection. Detection limit, sensitivity and linear concentration range of the sensor were, 0.3 (μM), 18.7 nAμ M −1 and 3 μM to 200 μM, respectively. Moreover, the sensor retained about 90% of its original response toward Cr(III) after storage three months in ambient condition. Furthermore, the sensor response toward different common interferences was negligible. Finally, the

  10. Relationships among surface processing at the nanometer scale, nanostructure and optical properties of thin oxide films

    Losurdo, Maria

    2004-05-01

    Spectroscopic ellipsometry is used to study the optical properties of nanostructured semiconductor oxide thin films. Various examples of models for the dielectric function, based on Lorentzian oscillators combined with the Drude model, are given based on the band structure of the analyzed oxide. With this approach, the optical properties of thin films are determined independent of the dielectric functions of the corresponding bulk materials, and correlation between the optical properties and nanostructure of thin films is investigated. In particular, in order to discuss the dependence of optical constants on grain size, CeO{sub 2} nanostructured films are considered and parameterized by two-Lorentzian oscillators or two-Tauc-Lorentz model depending on the nanostructure and oxygen deficiency. The correlation among anisotropy, crystalline fraction and optical properties parameterized by a four-Lorentz oscillator model is discussed for nanocrystalline V{sub 2}O{sub 5} thin films. Indium tin oxide thin films are discussed as an example of the presence of graded optical properties related to interfacial reactivity activated by processing conditions. Finally, the example of ZnO shows the potential of ellipsometry in discerning crystal and epitaxial film polarity through the analysis of spectra and the detection of surface reactivity of the two polar faces, i.e. Zn-polarity and O-polarity.

  11. Functional zinc oxide nanostructures for electronic and energy applications

    Prasad, Abhishek

    ZnO has proven to be a multifunctional material with important nanotechnological applications. ZnO nanostructures can be grown in various forms such as nanowires, nanorods, nanobelts, nanocombs etc. In this work, ZnO nanostructures are grown in a double quartz tube configuration thermal Chemical Vapor Deposition (CVD) system. We focus on functionalized ZnO Nanostructures by controlling their structures and tuning their properties for various applications. The following topics have been investigated: (1) We have fabricated various ZnO nanostructures using a thermal CVD technique. The growth parameters were optimized and studied for different nanostructures. (2) We have studied the application of ZnO nanowires (ZnONWs) for field effect transistors (FETs). Unintentional n-type conductivity was observed in our FETs based on as-grown ZnO NWs. We have then shown for the first time that controlled incorporation of hydrogen into ZnO NWs can introduce p-type characters to the nanowires. We further found that the n-type behaviors remained, leading to the ambipolar behaviors of hydrogen incorporated ZnO NWs. Importantly, the detected p- and n- type behaviors are stable for longer than two years when devices were kept in ambient conditions. All these can be explained by an ab initio model of Zn vacancy-Hydrogen complexes, which can serve as the donor, acceptors, or green photoluminescence quencher, depend on the number of hydrogen atoms involved. (3) Next ZnONWs were tested for electron field emission. We focus on reducing the threshold field (Eth) of field emission from non-aligned ZnO NWs. As encouraged by our results on enhancing the conductivity of ZnO NWs by hydrogen annealing described in Chapter 3, we have studied the effect of hydrogen annealing for improving field emission behavior of our ZnO NWs. We found that optimally annealed ZnO NWs offered much lower threshold electric field and improved emission stability. We also studied field emission from ZnO NWs at moderate

  12. Topotactic reduction yielding black titanium oxide nanostructures as metallic electronic conductors.

    Tominaka, Satoshi

    2012-10-01

    Detailed analyses of reduced, single crystal, rutile-type TiO(2) via high-resolution transmission electron microscopy (TEM) are reported which reveal that the reduction proceeds topotactically via interstitial diffusion of Ti ions at low temperature, around 350 °C. This important finding encouraged the production of various nanostructured reduced titanium oxides from TiO(2) precursors with morphology retention, and in the process, the synthesis of black titanium oxide nanorods using TiO(2) nanorods was demonstrated. Interestingly, as opposed to the semiconductive behavior of Ti(2)O(3) synthesized at high temperature, topotactically synthesized Ti(2)O(3) exhibits metallic electrical resistance, and the value at room temperature is quite low (topotactically synthesized Ti(2)O(3). This work shows that topotactically reduced titanium oxides can have fascinating properties as well as nanostructures.

  13. Gold nanoparticle arrays directly grown on nanostructured indium tin oxide electrodes: Characterization and electroanalytical application

    Zhang Jingdong; Oyama, Munetaka

    2005-01-01

    This work describes an improved seed-mediated growth approach for the direct attachment and growth of mono-dispersed gold nanoparticles on nanostructured indium tin oxide (ITO) surfaces. It was demonstrated that, when the seeding procedure of our previously reported seed-mediated growth process on an ITO surface was modified, the density of gold nanospheres directly grown on the surface could be highly improved, while the emergence of nanorods was restrained. By field emission scanning electron microscopy (FE-SEM) and cyclic voltammetry, the growth of gold nanoparticles with increasing growth time on the defect sites of nanostructured ITO surface was monitored. Using a [Fe(China) 6 ] 3- /[Fe(China) 6 ] 4- redox probe, the increasingly facile heterogeneous electron transfer kinetics resulting from the deposition and growth of gold nanoparticle arrays was observed. The as-prepared gold nanoparticle arrays exhibited high catalytic activity toward the electrooxidation of nitric oxide, which could provide electroanalytical application for nitric oxide sensing

  14. Facile synthesis of nanostructured transition metal oxides as electrodes for Li-ion batteries

    Opra, Denis P.; Gnedenkov, Sergey V.; Sokolov, Alexander A.; Minaev, Alexander N.; Kuryavyi, Valery G.; Sinebryukhov, Sergey L.

    2017-09-01

    At all times, energy storage is one of the greatest scientific challenge. Recently, Li-ion batteries are under special attention due to high working voltage, long cycle life, low self-discharge, reliability, no-memory effect. However, commercial LIBs usage in medium- and large-scale energy storage are limited by the capacity of lithiated metal oxide cathode and unsafety of graphite anode at high-rate charge. In this way, new electrode materials with higher electrochemical performance should be designed to satisfy a requirement in both energy and power. As it known, nanostructured transition metal oxides are promising electrode materials because of their elevated specific capacity and high potential vs. Li/Li+. In this work, the perspective of an original facile technique of pulsed high-voltage plasma discharge in synthesis of nanostructured transition metal oxides as electrodes for lithium-ion batteries has been demonstrated.

  15. Ethanol gas sensing performance of high-dimensional fuzz metal oxide nanostructure

    Ibano, Kenzo; Kimura, Yoshihiro; Sugahara, Tohru; Lee, Heun Tae; Ueda, Yoshio

    2018-04-01

    Gas sensing ability of the He plasma induced fiber-like nanostructure, so-called fuzz structure, was firstly examined. A thin Mo layer deposited on a quartz surface was irradiated by He plasma to form the fuzz structure and oxidized by annealing in a quartz furnace. Electric conductivity of the fuzz Mo oxide layer was then measured through the Au electrodes deposited on the layer. Changes in electric conductivity by C2H5OH gas flow were examined as a function of temperature from 200 to 400 °C. Improved sensitivities were observed for the specimens after a fuzz nanostructure formation. However, the sensor developed in this study showed lower sensitivities than previously reported MoO3 nano-rod sensor, further optimization of oxidation is needed to improve the sensitivity.

  16. Effects of Silica Nanostructures in Poly(ethylene oxide)-Based Composite Polymer Electrolytes.

    Mohanta, Jagdeep; Anwar, Shahid; Si, Satyabrata

    2016-06-01

    The present work describes the synthesis of some poly(ethylene oxide)-based nanocomposite polymer electrolyte films using various silica nanostructures as the inorganic filler by simple solution mixing technique, in which the nature of the silica nanostructures play a vital role in modulating their electrochemical performances at room temperature. The silica nanostructures are prepared by ammonical hydrolysis of tetraethyl orthosilicate following the modified St6ber method. The resulting films are characterized by X-ray diffraction and differential scanning calorimeter to study their crystallinity. Room temperature AC impedance spectroscopy is utilized to determine the Li+ ion conductivity of the resulting films. The observed conductivity values of various NCPE films depend on the nature of silica filling as well as on their surface characteristics and also on the varying PEO-Li+ ratio, which is observed to be in the order of 10(-7)-10(-6) S cm(-1).

  17. Photoconductivity of oxidized nanostructured PbTe(In) films

    Dobrovolsky, A A; Ryabova, L I; Khokhlov, D R; Dashevsky, Z M; Kasiyan, V A

    2009-01-01

    Photoconductivity of as-grown and oxidized nanocrystalline PbTe(In) films has been studied in the dc and ac modes at temperatures 4.2–300 K. The electric transport in the films is defined by two mechanisms: conductivity through barriers at grain boundaries and transport along inversion channels at the grain surface. Modification of the transport mechanisms induced by oxidation is considered. Relatively weak oxidation results in an increase in the contribution of grain barriers to conductivity followed by an enhancement of the photoconductivity amplitude. Instead, this contribution drops in the case of deep oxidation resulting in a photoresponse reduction. It is shown that the main mechanism of charge transport in deeply oxidized films at low temperatures is hopping along inversion channels at the grain surface. It is demonstrated that the photoconductive response of nanocrystalline materials may be optimized by variation of the oxidation level, measurement frequency and temperature

  18. Electrochemically active manganese oxides: structural modelling, modifications induced by thermal processing and photon insertion

    Ripert, Michel

    1990-01-01

    The objective of this research study is to understand the mechanism of proton insertion into manganese dioxide. It comprised the performances of in situ discharges of two commercial samples in an electrochemical cell designed for this purpose. In order to characterise the structure of electrochemically active manganese dioxides, and particularly to elucidate the orthorhombic-hexagonal dilemma, the author proposes a crystalline-chemical approach which comprises the development of a unique structural model which takes the structure of all forms of electrochemically active manganese dioxides into account, and a numerical simulation of diffraction diagrams (X rays and neutrons) of these structures. The development of this modelling results in the development of a method which allows, from experimental diffraction diagrams, characteristic structural parameters of each sample of EMD (electrolytic manganese dioxide) or CMD (chemical manganese dioxide) to be obtained. Moreover, the observation of the structural evolution of the dioxide is possible by using in situ neutron diffraction. Reduction has been studied by using slow potential scanning voltammetry. By using these both techniques (neutron diffraction and voltammetry), it is possible to explain the structural mechanism of reduction of MnO_2 and to show the origin of the non-reversibility of the proton/MnO_2 system, to quantitatively explain the shape voltammetry curves, and to highlight experimentally for the first time the different sites of insertion of the proton

  19. Synthesis of waste cooking oil based biodiesel via ferric-manganese promoted molybdenum oxide / zirconia nanoparticle solid acid catalyst: influence of ferric and manganese dopants.

    Alhassan, Fatah H; Rashid, Umer; Taufiq-Yap, Yun Hin

    2015-01-01

    The utilization of ferric-manganese promoted molybdenum oxide/zirconia (Fe-Mn- MoO3/ZrO2) (FMMZ) solid acid catalyst for production of biodiesel was demonstrated. FMMZ is produced through impregnation reaction followed by calcination at 600°C for 3 h. The characterization of FMMZ had been done using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), thermal gravimetric analysis (TGA), temperature programmed desorption of NH3 (TPD-NH3), transmission electron microscopy(TEM) and Brunner-Emmett-Teller (BET) surface area measurement. The effect of waste cooking oil methyl esters (WCOME's) yield on the reactions variables such as reaction temperature, catalyst loading, molar ratio of methanol/oil and reusability were also assessed. The catalyst was used to convert the waste cooking oil into corresponding methyl esters (95.6%±0.15) within 5 h at 200℃ reaction temperature, 600 rpm stirring speed, 1:25 molar ratio of oil to alcohol and 4% w/w catalyst loading. The reported catalyst was successfully recycled in six connective experiments without loss in activity. Moreover, the fuel properties of WCOME's were also reported using ASTM D 6751 methods.

  20. Comparative ion insertion study into a nanostructured vanadium oxide in aqueous salt solutions

    Yuan, Q.; Ren, S. L.; Zukowski, J.; Pomeroy, M.; Soghomonian, V., E-mail: soghomon@vt.edu [Department of Physics, Virginia Tech, Blacksburg, Virginia 24061 (United States)

    2014-07-07

    We present a comparative study for the electrochemical insertion of different cations into a nanostructured vanadium oxide material. The oxide is hydrothemally synthesized and electrically characterized by variable temperature measurements. The electrochemical reactions are performed in aqueous chloride solutions of lithium, sodium, potassium, and ammonium, and the electrochemical behavior of various cycles are correlated with visual changes in the vanadium oxide nanosheets as observed by scanning electron microscopy. We note an increase in the specific charge per cycle in the cases of sodium and ammonium ions only, correlated with minimal physical changes to the nanosheets. The differing behavior of the various ions has implications for their use in electrical energy storage applications.

  1. Radiation Stability of Nanoclusters in Nano-structured Oxide Dispersion Strengthened (ODS) Steels

    Certain, Alicia G.; Kuchibhatla, Satyanarayana; Shutthanandan, V.; Allen, T. R.

    2013-01-01

    Nanostructured oxide dispersion strengthened (ODS) steels are considered candidates for nuclear fission and fusion applications at high temperature and dose. The complex oxide nanoclusters in these alloys provide high-temperature strength and are expected to afford better radiation resistance. Proton, heavy ion, and neutron irradiations have been performed to evaluate cluster stability in 14YWT and 9CrODS steel under a range of irradiation conditions. Energy-filtered transmission electron microscopy and atom probe tomography were used in this work to analyze the evolution of the oxide population.

  2. Lithium ion adsorptive properties of spinel-type manganese oxide obtained from MnOOH and Li2CO3

    Ooi, Kenta; Miyai, Yoshitaka; Katoh, Shunsaku; Abe, Mitsuo.

    1991-01-01

    Spinel-type manganese oxides were prepared by heating a mixture of MnOOH and Li 2 CO 3 (Li/Mn = 0.5) at different temperatures followed by an acid treatment with a HCl solution. Their adsorptive properties for alkali metal ions were investigated by measurement of distribution coefficient (Kd) and by pH titration. The adsorptive properties varied depending on the heating temperature. The sample obtained at 400degC showed the highest Li + adsorptivity from seawater. (author)

  3. Factors that influence the oxidation of the manganese in a growth of mangroves forest, Itacuruca, R J

    Canesin, F.P.; Bellido, A.V.B.; Lacerda, L.D.

    1999-01-01

    The kinetic behavior of the oxidation of the manganese in the growth of mangroves forest, Itacuruca, Sepetiba Bay, R J, have been studied through the incubation with the radiotracer Mn-54. We have observed the great influence of the factors that interferes in the rate oxidation with the mangrove state in the moment of the sampling. We applied statistical multivariate to verify the correlation with the tide height and the physical-chemical parameters. With the program Statistical Analysis System, SAS, the samples were classified by hierarchical conglomerate methods and Factor Analysis. Water samples were collected in the entrance of the tide channel in five campaigns in the months of August, September, November and December of 98, and January of 99, in several tide heights. As a conclusion, by the multivariate statistical analysis where variables correlations are presented in each group or cluster in a population. Therefore the variables that we are measuring as reflecting the influence the oxidation manganese in the mangroves. Although the variable tide height did not influence in the classification groups. We suppose that will need more sampling in different tide height cycle. (author)

  4. Factors that influence the oxidation of the manganese in a growth of mangroves forest, Itacuruca, R J

    Canesin, F.P.; Bellido, A.V.B. [Universidade Federal Fluminense, Niteroi, RJ (Brazil). Inst. de Quimica. Dept. de Fisico-Quimica]. E-mail: fcanesin@risc2.rmn.uff.br; alf@risc1.rmn.uff.br; Lacerda, L.D. [Universidade Federal Fluminense, Niteroi, RJ (Brazil). Dept. de Geoquimica]. E-mail: geodrud@vm.uff

    1999-07-01

    The kinetic behavior of the oxidation of the manganese in the growth of mangroves forest, Itacuruca, Sepetiba Bay, R J, have been studied through the incubation with the radiotracer Mn-54. We have observed the great influence of the factors that interferes in the rate oxidation with the mangrove state in the moment of the sampling. We applied statistical multivariate to verify the correlation with the tide height and the physical-chemical parameters. With the program Statistical Analysis System, SAS, the samples were classified by hierarchical conglomerate methods and Factor Analysis. Water samples were collected in the entrance of the tide channel in five campaigns in the months of August, September, November and December of 98, and January of 99, in several tide heights. As a conclusion, by the multivariate statistical analysis where variables correlations are presented in each group or cluster in a population. Therefore the variables that we are measuring as reflecting the influence the oxidation manganese in the mangroves. Although the variable tide height did not influence in the classification groups. We suppose that will need more sampling in different tide height cycle. (author)

  5. A 1 V supercapacitor device with nanostructured graphene oxide ...

    Polyaniline and graphene oxide composite on activated carbon cum reduced graphene oxide-supported supercapacitor electrodes are fabricated and electrochemically characterized in a three-electrode cell assembly. Attractive supercapacitor performance, namely high-power capability and cycling stability for graphene ...

  6. Annealing induced structural evolution and electrochromic properties of nanostructured tungsten oxide films

    Wu, Ching-Lin [Department of Materials Science and Engineering, National Cheng Kung University, Tainan 701, Taiwan, ROC (China); Lin, Chung-Kwei [School of Dental Technology, Taipei Medical University, Taipei City 110, Taiwan, ROC (China); Wang, Chun-Kai [Department of Materials Science and Engineering, National Cheng Kung University, Tainan 701, Taiwan, ROC (China); Wang, Sheng-Chang [Department of Mechanical Engineering, Southern Taiwan University, Tainan 710, Taiwan, ROC (China); Huang, Jow-Lay, E-mail: JLH888@mail.ncku.edu.tw [Department of Materials Science and Engineering, National Cheng Kung University, Tainan 701, Taiwan, ROC (China); Department of Chemical and Materials Engineering, National University of Kaohsiung, Kaohsiung 81148, Taiwan, ROC (China); Research Center for Energy Technology and Strategy, National Cheng Kung University, Tainan 701, Taiwan, ROC (China)

    2013-12-31

    The effect of microstructure on the optical and electrochemical properties of nanostructured tungsten oxide films was evaluated as a function of annealing temperature. The films using block copolymer as the template were prepared from peroxotungstic acid (PTA) by spin-coating onto the substrate and post-annealed at 250–400 °C to form tungsten oxide films with nanostructure. The microstructure of the films was measured by X-ray diffraction and surface electron microscopy. The films annealed at temperatures below 300 °C are characterized by amorphous or nanocrystalline structures with a pore size of less than 10 nm. The evaluated annealing temperature caused a triclinic crystalline structure and microcracks. Cyclic voltammetry measurements were performed in a LiClO{sub 4}-propylene carbonate electrolyte. The results showed that the ion inserted capacity were maximized for films annealed at 300 °C and decreased with the increasing of annealing temperature. The electrochromic properties of the nanostructured tungsten oxide films were evaluated simultaneously by potentiostat and UV–vis spectroscopy. The films annealed at 300 °C exhibit high transmission modulation (∆T ∼ 40%) at λ = 633 nm and good kinetic properties. As a result, the correlation between the microstructure and kinetic properties was established, and the electrochromic properties have been demonstrated. - Highlights: • Surfactant-assisted WO{sub 3} films have been prepared by sol–gel method. • Nanostructure of porous WO{sub 3} film is retained after crystallization. • Kinetic properties of WO{sub 3} can be improved by nanostructure and crystallinity.

  7. The effect of thermal oxidation on the luminescence properties of nanostructured silicon.

    Liu, Lijia; Sham, Tsun-Kong

    2012-08-06

    Herein is reported a detailed study of the luminescence properties of nanostructured Si using X-ray excited optical luminescence (XEOL) in combination with X-ray absorption near-edge structures (XANES). P-type Si nanowires synthesized via electroless chemical etching from Si wafers of different doping levels and porous Si synthesized using electrochemical method are examined under X-ray excitation across the Si K-, L(3,2) -, and O K-edges. It is found that while as-prepared Si nanostructures are weak light emitters, intense visible luminescence is observed from thermally oxidized Si nanowires and porous Si. The luminescence mechanism of Si upon oxidation is investigated by oxidizing nanostructured Si at different temperatures. Interestingly, the two luminescence bands observed show different response with the variation of absorption coefficient upon Si and O core-electron excitation in elemental silicon and silicon oxide. A correlation between luminescence properties and electronic structures is thus established. The implications of the finding are discussed in terms of the behavior of the oxygen deficient center (OCD) and non-bridging oxygen hole center (NBOHC). Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  8. Electrocatalytic Activity of Carbonized Nanostructured Polyanilines for Oxidation Reactions: Sensing of Nitrite Ions and Ascorbic Acid

    Micić, Darko; Šljukić, Biljana; Zujovic, Zoran; Travas-Sejdic, Jadranka; Ćirić-Marjanović, Gordana

    2014-01-01

    Highlights: • Carbonized PANIs prepared from various nanostructured PANI precursors • Electroanalytical performances of carbonized PANIs evaluated using voltammetry • Study of carbonized PANIs physico-chemical properties related to electroactivity • The lowest over-potential for NO 2 − oxidation at c-PANI (+0.87 V vs. SCE) • The lowest over-potential for ascorbic acid oxidation at both c-PANI and c-PANI-SSA - Abstract: A comparative study of the electrocatalytic activity of nitrogen-containing carbon nanomaterials, prepared by the carbonization of nanostructured polyaniline (PANI) salts, for the electrooxidation reactions is presented. Nanostructured PANI salts were synthesized by the oxidative polymerization of aniline with ammonium peroxydisulfate in an aqueous solution in the presence of 5-sulfosalicylic acid (PANI-SSA), 3,5-dinitrosalicylic acid (PANI-DNSA) as well as without added acid (PANI), and subsequently carbonized to c-PANI-SSA, c-PANI-DNSA and c-PANI, respectively. Glassy carbon tip was modified with nanostructured c-PANIs and used for the investigation of sensing of nitrite and ascorbic acid in aqueous solutions as model analytes by linear sweep voltammetry. All three types of the investigated c-PANIs gave excellent response to the nitrite ions and ascorbic acid electrooxidation. The lowest peak potential for nitrite ion oxidation exhibited c-PANI (+0.87 V vs. SCE), and for ascorbic acid oxidation both c-PANI and c-PANI-SSA (ca. + 0.13 V vs. SCE). Electrochemical data were correlated with structural and textural data obtained by Raman spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, elemental and nitrogen sorption analysis

  9. Optimized spherical manganese oxide-ferroferric oxide-tin oxide ternary composites as advanced electrode materials for supercapacitors

    Zhu, Jian; Tang, Shaochun; Vongehr, Sascha; Xie, Hao; Meng, Xiangkang

    2015-09-01

    Inexpensive MnO2 is a promising material for supercapacitors (SCs), but its application is limited by poor electrical conductivity and low specific surface area. We design and fabricate hierarchical MnO2-based ternary composite nanostructures showing superior electrochemical performance via doping with electrochemically active Fe3O4 in the interior and electrically conductive SnO2 nanoparticles in the surface layer. Optimization composition results in a MnO2-Fe3O4-SnO2 composite electrode material with 5.9 wt.% Fe3O4 and 5.3 wt.% SnO2, leading to a high specific areal capacitance of 1.12 F cm-2 at a scan rate of 5 mV s-1. This is two to three times the values for MnO2-based binary nanostructures at the same scan rate. The low amount of SnO2 almost doubles the capacitance of porous MnO2-Fe3O4 (before SnO2 addition), which is attributed to an improved conductivity and remaining porosity. In addition, the optimal ternary composite has a good rate capability and an excellent cycling performance with stable capacitance retention of ˜90% after 5000 charge/discharge cycles at 7.5 mA cm-2. All-solid-state SCs are assembled with such electrodes using polyvinyl alcohol/Na2SO4 electrolyte. An integrated device made by connecting two identical SCs in series can power a light-emitting diode indicator for more than 10 min.

  10. Facile conversion of bulk metal surface to metal oxide single-crystalline nanostructures by microwave irradiation: Formation of pure or Cr-doped hematite nanostructure arrays

    Cho, Seungho; Jeong, Haeyoon; Lee, Kun-Hong

    2010-01-01

    We report a method for converting the surfaces of bulk metal substrates (pure iron or stainless steel) to metal oxide (hematite or Cr-doped hematite) nanostructures using microwave irradiation. When microwave radiation (2.45 GHz, single-mode) was applied to a metal substrate under the flow of a gas mixture containing O 2 and Ar, metal oxide nanostructures formed and entirely covered the substrate. The nanostructures were single crystalline, and the atomic ratios of the substrate metals were preserved in the nanostructures. When a pure iron sheet was used as a substrate, hematite nanowires (1000 W microwave radiation) or nanosheets (1800 W microwave radiation) formed on the surface of the substrate. When a SUS410 sheet was used as a substrate, slightly curved rod-like nanostructures were synthesized. The oxidation states of Fe and Cr in these nanorods were Fe 3+ and Cr 3+ . Quantitative analyses revealed an average Fe/Cr atomic ratio of 9.2, nearly identical to the ratio of the metals in the SUS410 substrate.

  11. Intertwined nanocarbon and manganese oxide hybrid foam for high-energy supercapacitors.

    Wang, Wei; Guo, Shirui; Bozhilov, Krassimir N; Yan, Dong; Ozkan, Mihrimah; Ozkan, Cengiz S

    2013-11-11

    Rapid charging and discharging supercapacitors are promising alternative energy storage systems for applications such as portable electronics and electric vehicles. Integration of pseudocapacitive metal oxides with single-structured materials has received a lot of attention recently due to their superior electrochemical performance. In order to realize high energy-density supercapacitors, a simple and scalable method is developed to fabricate a graphene/MWNT/MnO2 nanowire (GMM) hybrid nanostructured foam, via a two-step process. The 3D few-layer graphene/MWNT (GM) architecture is grown on foamed metal foils (nickel foam) via ambient pressure chemical vapor deposition. Hydrothermally synthesized α-MnO2 nanowires are conformally coated onto the GM foam by a simple bath deposition. The as-prepared hierarchical GMM foam yields a monographical graphene foam conformally covered with an intertwined, densely packed CNT/MnO2 nanowire nanocomposite network. Symmetrical electrochemical capacitors (ECs) based on GMM foam electrodes show an extended operational voltage window of 1.6 V in aqueous electrolyte. A superior energy density of 391.7 Wh kg(-1) is obtained for the supercapacitor based on the GMM foam, which is much higher than ECs based on GM foam only (39.72 Wh kg(-1) ). A high specific capacitance (1108.79 F g(-1) ) and power density (799.84 kW kg(-1) ) are also achieved. Moreover, the great capacitance retention (97.94%) after 13 000 charge-discharge cycles and high current handability demonstrate the high stability of the electrodes of the supercapacitor. These excellent performances enable the innovative 3D hierarchical GMM foam to serve as EC electrodes, resulting in energy-storage devices with high stability and power density in neutral aqueous electrolyte. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  12. Electrical transport properties of manganese containing pyrochlore type semiconducting oxides using impedance analyses

    Sumi, S.; Prabhakar Rao, P.; Mahesh, S.K.; Koshy, Peter

    2012-01-01

    Graphical abstract: DC conductivity variation of CaCe 1−x Mn x SnNbO 7−δ (x = 0, 0.2, 0.4 and 0.6) with inverse of temperature. Variation of conductivity with Mn concentration at 600 °C is shown in the inset. Display Omitted Highlights: ► We have observed that the structural ordering as well as grain size increase with Mn substitution. ► Impedance analysis proved that a correlated barrier hopping type conduction mechanism is involved in the materials. ► Activation energy as well as electrical conductivity increases with increase in Mn substitution. ► Localization of electrons associated with Mn 2+ and structural ordering are the key factors for the increased activation energy with Mn substitution. ► All the materials showed good NTC thermistor properties. -- Abstract: A new series of manganese containing pyrochlore type semiconducting oxides CaCe 1−x Mn x SnNbO 7−δ (x = 0, 0.2, 0.4 and 0.6) have been synthesized to study the effect of Mn substitution on the structure, microstructure and electrical properties of these samples. X-ray diffraction and scanning electron microscopy studies revealed an increase of structural ordering and grain size respectively with increase of Mn substitution. Rietveld analysis and Raman spectroscopy were also employed to corroborate the XRD results. The bulk resistance measurements with temperature exhibit negative temperature coefficient behavior. The impedance analysis of the samples revealed a non-Debye type relaxation existed in the materials. The ac conductivity variation with temperature and frequency indicates a correlated barrier hopping type conduction mechanism in these materials. The barrier height and the intersite separation for hopping influence the electrical conductivity of these samples and are found to be a function of localization of electrons associated with the Mn 2+ ions and the unit cell volume respectively. The Mn substitution increases both electrical conductivity and activation energy

  13. Synthesizing Iron Oxide Nanostructures: The Polyethylenenemine (PEI) Role

    Mozo, Sergio Lentijo; Zuddas, Efisio; Casu, Alberto; Falqui, Andrea

    2017-01-01

    Controlled synthesis of anisotropic iron oxide nanoparticles is a challenge in the field of nanomaterial research that requires an extreme attention to detail. In particular, following up a previous work showcasing the synthesis of magnetite

  14. Sol-Gel Derived, Nanostructured Oxide Lubricant Coatings

    Taylor, Douglas

    2000-01-01

    In this program, we deposited oxide coatings of titanium and nickel by wet-chemical deposition methods, also referred to as sol-gel, which showed excellent tribological properties in previous investigations...

  15. A novel layered manganese oxide/poly(aniline-co-o-anisidine) nanocomposite and its application for electrochemical supercapacitor

    Yang Xiaofeng; Wang Gengchao; Wang Ruiyu; Li Xingwei

    2010-01-01

    A novel layered manganese oxide/poly(aniline-co-o-anisidine) nanocomposite [MnO 2 /P(An-co-oAs)] was successfully synthesized by a delamination/reassembling process using P(An-co-oAs) ionomer and layered manganese oxide in aqueous solution. This nanocomposite obtained was then characterized by Fourier transform infrared (FTIR) spectra, X-ray diffraction (XRD), electron microscopy (SEM), and thermogravimetric (TG) analysis. X-ray diffraction and electron microscope analysis showed that the MnO 2 /P(An-co-oAs) nanocomposite had a lamellar structure with increasing interlayer spacing. The MnO 2 /P(An-co-oAs) nanocomposite exhibited substantially improved conductivity, which was near 100 times greater than that of its pristine MnO 2 (3.5 x 10 -7 S cm -1 ). The specific capacitance of the MnO 2 /P(An-co-oAs) nanocomposite reached 262 F g -1 in 1 M Na 2 SO 4 at a current density of 1 A g -1 , which was significantly higher than that of either of its two pristine materials [MnO 2 (182 F g -1 ) or P(An-co-oAs) (127 F g -1 )] owing to the synergic effect between the two pristine components. The fabrication mechanism of the nanocomposite was also proposed and discussed in this paper.

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

    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.

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

    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.

  18. A New Hydrogen Sensor with Nanostructured Zinc Magnesium Oxide

    Reshma PRAKSHALE

    2013-02-01

    Full Text Available Nano structured ZnMgO was synthesized by self combustion method using glycine as a fuel. The synthesized microstructure materials were investigated by TG-DTA, XRD, SEM, TEM, and E-DAX. Observed results shows the product, is the mixture of ZnMgO, its particle size is about 45-55 nm with loosely agglomerated shape. Electrical properties of the synthesized nanoparticles were studied by AC conductivity measurement. The gas sensing properties were studied towards reducing gases viz. ammonia, hydrogen, acetone, chlorine, liquefied petroleum gas (LPG, etc. and it was observed that the nano structured ZnMgO shows high response to hydrogen at 200 °C and no cross sensitivities to other reducing gases. These nanoparticles were good I-V characteristics with ohmic nature. The quick response ( ~10 s and fast recovery (~ 20 s are the main features of these sensors. The effects of nanostructure on the gas sensing performance were studied and discussed.

  19. Sensitivity, selectivity and stability of tin oxide nanostructures on large area arrays of microhotplates

    Panchapakesan, Balaji; Cavicchi, Richard; Semancik, Steve; DeVoe, Don L.

    2006-01-01

    In this paper, the sensitivity, stability and selectivity of nanoparticle engineered tin oxide (SnO2) are reported, for microhotplate chemical sensing applications. 16 Å of metals such as nickel, cobalt, iron, copper and silver were selectively evaporated onto each column of the microhotplate array. Following evaporation, the microhotplates were heated to 500 °C and SnO2 was deposited on top of the microhotplates using a self-aligned chemical vapour deposition process. Scanning electron microscopy characterization revealed control of SnO2 nanostructures in the range of 20-121 nm. Gas sensing in seven different hydrocarbons revealed that metal nanoparticles that helped in producing faster nucleation of SnO2 resulted in smaller grain size and higher sensitivity. Sensitivity as a function of concentration and grain size is addressed for tin oxide nanostructures. Smaller grain sizes resulted in higher sensitivity of tin oxide nanostructures. Temperature programmed sensing of the devices yielded shape differences in the response between air and methanol, illustrating selectivity. Spiderweb plots were used to monitor the materials programmed selectivity. The shape differences between different gases in spiderweb plots illustrate materials selectivity as a powerful mapping approach for monitoring selectivity in various gases. Continuous monitoring in 80 ppm methanol yielded stable sensor response for more than 200 h. This comprehensive study illustrates the use of a nanoparticle engineering approach for sensitive, selective and stable gas sensing applications.

  20. Manganese, Metallogenium, and Martian Microfossils

    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.

  1. Identification of Manganese Superoxide Dismutase from Sphingobacterium sp. T2 as a Novel Bacterial Enzyme for Lignin Oxidation.

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

    2015-10-16

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

  2. Acclimation of a marine microbial consortium for efficient Mn(II) oxidation and manganese containing particle production

    Zhou, Hao; Pan, Haixia; Xu, Jianqiang; Xu, Weiping; Liu, Lifen

    2016-01-01

    Highlights: • An efficient Mn(II) oxidation marine sediments microbial community was obtained. • High-throughput sequencing indicated new Mn(II) oxidation associated genus. • Na_3MnPO_4CO_3 and MnCO_3 were synthesized by the consortium. • Consortium exhibited Mn(II) oxidation performance over a range of harsh conditions. - Abstract: Sediment contamination with metals is a widespread concern in the marine environment. Manganese oxidizing bacteria (MOB) are extensively distributed in various environments, but a marine microbial community containing MOB is rarely reported. In this study, a consortium of marine metal-contaminated sediments was acclimated using Mn(II). The shift in community structure was determined through high-throughput sequencing. In addition, the consortium resisted several harsh conditions, such as toxic metals (1 mM Cu(II) and Fe(III)), and exhibited high Mn(II) oxidation capacities even the Mn(II) concentration was up to 5 mM. Meanwhile, biogenic Mn containing particles were characterized by scanning electron microscope (SEM), X-ray powder diffraction (XRD), and N_2 adsorption/desorption. Dye removal performance of the Mn containing particles was assayed using methylene blue, and 20.8 mg g"−"1 adsorption capacity was obtained. Overall, this study revealed several new genera associated with Mn(II) oxidation and rare biogenic Na_3MnPO_4CO_3_. Results suggested the complexity of natural microbe-mediated Mn transformation.

  3. A 1 V supercapacitor device with nanostructured graphene oxide ...

    Attractive supercapacitor performance, namely high-power capability and cycling stability for graphene ... performance tested. A comparative study has also been conducted for polyaniline and graphene oxide/polyaniline composite-based 1 V supercapacitors for comprehending ..... Kluwer Academic/Plenum Publishers).

  4. Study of nano-structured ceria for catalytic CO oxidation

    Valechha, D.; Lokhande, S.; Klementová, Mariana; Šubrt, Jan; Rayalu, S.; Labhsetwar, N.

    2011-01-01

    Roč. 21, č. 11 (2011), s. 3718-3725 ISSN 0959-9428 Institutional research plan: CEZ:AV0Z40320502 Keywords : mesoporous CeO2 * titania * alumina * oxides Subject RIV: CA - Inorganic Chemistry Impact factor: 5.968, year: 2011

  5. Electrical Transport Ability of Nanostructured Potassium-Doped Titanium Oxide Film

    Lee, So-Yoon; Matsuno, Ryosuke; Ishihara, Kazuhiko; Takai, Madoka

    2011-02-01

    Potassium-doped nanostructured titanium oxide films were fabricated using a wet corrosion process with various KOH solutions. The doped condition of potassium in TiO2 was confirmed by Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). Nanotubular were synthesized at a dopant concentration of 0.27%, these structures disappeared. To investigate the electrical properties of K-doped TiO2, pseudo metal-oxide-semiconductor field-effect transistor (MOSFET) samples were fabricated. The samples exhibited a distinct electrical behavior and p-type characteristics. The electrical behavior was governed by the volume of the dopant when the dopant concentration was 0.18%.

  6. Tris(trimethylsilyl)phosphate as electrolyte additive for self-discharge suppression of layered nickel cobalt manganese oxide

    Liao, Xiaolin; Zheng, Xiongwen; Chen, Jiawei; Huang, Ziyu; Xu, Mengqing; Xing, Lidan; Liao, Youhao; Lu, Qilun; Li, Xiangfeng; Li, Weishan

    2016-01-01

    Highlights: • TMSP is effective for self-discharge suppression of the charged NCM under 4.5 V. • TMSP oxidizes preferentially forming protective cathode interface film on NCM. • The film suppresses electrolyte decomposition and prevents NCM destruction. - Abstract: Application of layered nickel cobalt manganese oxide as cathode under higher potential than conventional 4.2 V yields a significant improvement in energy density of lithium ion battery. However, the cathode fully charged under high potential suffers serious self-discharge, in which the interaction between the cathode and electrolyte proceeds without potential limitation. In this work, we use tris(trimethylsilyl)phosphate (TMSP) as an electrolyte additive to solve this problem. A representative layered nickel cobalt manganese oxide, LiNi 1/3 Co 1/3 Mn 1/3 O 2 , is considered. The effect of TMSP on self-discharge behavior of LiNi 1/3 Co 1/3 Mn 1/3 O 2 is evaluated by physical and electrochemical methods. It is found that the self-discharge of charged LiNi 1/3 Co 1/3 Mn 1/3 O 2 can be suppressed significantly by using TMSP. TMSP is oxidized preferentially in comparison with the standard electrolyte during initial charging process forming a protective cathode interface film, which avoids the interaction between cathode and electrolyte at any potential and thus prevents electrolyte decomposition and protects LiNi 1/3 Co 1/3 Mn 1/3 O 2 from structure destruction.

  7. Growth and optical properties of silver nanostructures obtained on connected anodic aluminum oxide templates

    Giallongo, G.; Durante, C.; Pilot, R.; Garoli, D.; Bozio, R.; Romanato, F.; Gennaro, A.; Rizzi, G. A.; Granozzi, G.

    2012-08-01

    Ag nanostructures are grown by AC electrodeposition on anodic alumina oxide (AAO) connected membranes acting as templates. Depending on the thickness of the template and on the voltage applied during the growth process, different Ag nanostructures with different optical properties are obtained. When AAO membranes about 1 μm thick are used, the Ag nanostructures consist in Ag nanorods, at the bottom of the pores, and Ag nanotubes departing from the nanorods and filling the pores almost for the whole length. When AAO membranes about 3 μm thick are used, the nanostructures are Ag spheroids, at the bottom of the pores, and Ag nanowires that do not reach the upper part of the alumina pores. The samples are characterized by angle resolved x-ray photoelectron spectroscopy, scanning electron microscopy and UV-vis and Raman spectroscopies. A simple NaOH etching procedure, followed by sonication in ethanol, allows one to obtain an exposed ordered array of Ag nanorods, suitable for surface-enhanced Raman spectroscopy, while in the other case (3 μm thick AAO membranes) the sample can be used in localized surface plasmon resonance sensing.

  8. Growth and optical properties of silver nanostructures obtained on connected anodic aluminum oxide templates

    Giallongo, G; Durante, C; Pilot, R; Bozio, R; Gennaro, A; Rizzi, G A; Granozzi, G; Garoli, D; Romanato, F

    2012-01-01

    Ag nanostructures are grown by AC electrodeposition on anodic alumina oxide (AAO) connected membranes acting as templates. Depending on the thickness of the template and on the voltage applied during the growth process, different Ag nanostructures with different optical properties are obtained. When AAO membranes about 1 μm thick are used, the Ag nanostructures consist in Ag nanorods, at the bottom of the pores, and Ag nanotubes departing from the nanorods and filling the pores almost for the whole length. When AAO membranes about 3 μm thick are used, the nanostructures are Ag spheroids, at the bottom of the pores, and Ag nanowires that do not reach the upper part of the alumina pores. The samples are characterized by angle resolved x-ray photoelectron spectroscopy, scanning electron microscopy and UV–vis and Raman spectroscopies. A simple NaOH etching procedure, followed by sonication in ethanol, allows one to obtain an exposed ordered array of Ag nanorods, suitable for surface-enhanced Raman spectroscopy, while in the other case (3 μm thick AAO membranes) the sample can be used in localized surface plasmon resonance sensing. (paper)

  9. Hierarchical Assembly of Multifunctional Oxide-based Composite Nanostructures for Energy and Environmental Applications

    Hui-Jan Lin

    2012-06-01

    Full Text Available Composite nanoarchitectures represent a class of nanostructured entities that integrates various dissimilar nanoscale building blocks including nanoparticles, nanowires, and nanofilms toward realizing multifunctional characteristics. A broad array of composite nanoarchitectures can be designed and fabricated, involving generic materials such as metal, ceramics, and polymers in nanoscale form. In this review, we will highlight the latest progress on composite nanostructures in our research group, particularly on various metal oxides including binary semiconductors, ABO3-type perovskites, A2BO4 spinels and quaternary dielectric hydroxyl metal oxides (AB(OH6 with diverse application potential. Through a generic template strategy in conjunction with various synthetic approaches—such as hydrothermal decomposition, colloidal deposition, physical sputtering, thermal decomposition and thermal oxidation, semiconductor oxide alloy nanowires, metal oxide/perovskite (spinel composite nanowires, stannate based nanocompostes, as well as semiconductor heterojunction—arrays and networks have been self-assembled in large scale and are being developed as promising classes of composite nanoarchitectures, which may open a new array of advanced nanotechnologies in solid state lighting, solar absorption, photocatalysis and battery, auto-emission control, and chemical sensing.

  10. Scalable high-affinity stabilization of magnetic iron oxide nanostructures by a biocompatible antifouling homopolymer

    Luongo, Giovanni

    2017-10-12

    Iron oxide nanostructures have been widely developed for biomedical applications, due to their magnetic properties and biocompatibility. In clinical application, the stabilization of these nanostructures against aggregation and non-specific interactions is typically achieved using weakly anchored polysaccharides, with better-defined and more strongly anchored synthetic polymers not commercially adopted due to complexity of synthesis and use. Here, we show for the first time stabilization and biocompatibilization of iron oxide nanoparticles by a synthetic homopolymer with strong surface anchoring and a history of clinical use in other applications, poly(2-methacryloyloxyethy phosphorylcholine) (poly(MPC)). For the commercially important case of spherical particles, binding of poly(MPC) to iron oxide surfaces and highly effective individualization of magnetite nanoparticles (20 nm) are demonstrated. Next-generation high-aspect ratio nanowires (both magnetite/maghemite and core-shell iron/iron oxide) are furthermore stabilized by poly(MPC)-coating, with nanowire cytotoxicity at large concentrations significantly reduced. The synthesis approach is exploited to incorporate functionality into the poly(MPC) chain is demonstrated by random copolymerization with an alkyne-containing monomer for click-chemistry. Taking these results together, poly(MPC) homopolymers and random copolymers offer a significant improvement over current iron oxide nanoformulations, combining straightforward synthesis, strong surface-anchoring and well-defined molecular weight.

  11. Scalable high-affinity stabilization of magnetic iron oxide nanostructures by a biocompatible antifouling homopolymer

    Luongo, Giovanni; Campagnolo, Paola; Perez, Jose E.; Kosel, Jü rgen; Georgiou, Theoni K.; Regoutz, Anna; Payne, David J; Stevens, Molly M.; Ryan, Mary P.; Porter, Alexandra E; Dunlop, Iain E

    2017-01-01

    Iron oxide nanostructures have been widely developed for biomedical applications, due to their magnetic properties and biocompatibility. In clinical application, the stabilization of these nanostructures against aggregation and non-specific interactions is typically achieved using weakly anchored polysaccharides, with better-defined and more strongly anchored synthetic polymers not commercially adopted due to complexity of synthesis and use. Here, we show for the first time stabilization and biocompatibilization of iron oxide nanoparticles by a synthetic homopolymer with strong surface anchoring and a history of clinical use in other applications, poly(2-methacryloyloxyethy phosphorylcholine) (poly(MPC)). For the commercially important case of spherical particles, binding of poly(MPC) to iron oxide surfaces and highly effective individualization of magnetite nanoparticles (20 nm) are demonstrated. Next-generation high-aspect ratio nanowires (both magnetite/maghemite and core-shell iron/iron oxide) are furthermore stabilized by poly(MPC)-coating, with nanowire cytotoxicity at large concentrations significantly reduced. The synthesis approach is exploited to incorporate functionality into the poly(MPC) chain is demonstrated by random copolymerization with an alkyne-containing monomer for click-chemistry. Taking these results together, poly(MPC) homopolymers and random copolymers offer a significant improvement over current iron oxide nanoformulations, combining straightforward synthesis, strong surface-anchoring and well-defined molecular weight.

  12. Tailoring Charge Recombination in Photoelectrodes Using Oxide Nanostructures

    Iandolo, Beniamino; Wickman, Björn; Svensson, Elin

    2016-01-01

    Optimizing semiconductor devices for solar energy conversion requires an explicit control of the recombination of photogenerated electron−hole pairs. Here we show how the recombination of charge carriers can be controlled in semiconductor thin films by surface patterning with oxide nanodisks....... The control mechanism relies on the formation of dipole-like electric fields at the interface that, depending on the field direction, attract or repel minority carriers from underneath the disks. The charge recombination rate can be controlled through the choice of oxide material and the surface coverage...... of nanodisks. We provide proof-of-principle demonstration of this approach by patterning the surface of Fe2O3, one of the most studied semiconductors for light-driven water splitting, with TiO2 and Cu2O nanodisks. We expect this method to be generally applicable to a range of semiconductor-based solar energy...

  13. Metal Oxide Nanostructured Materials for Optical and Energy Applications

    Moore, Michael Christopher

    2013-01-01

    With a rapidly growing population, dwindling resources, and increasing environmental pressures, the need for sustainable technological solutions becomes more urgent. Metal oxides make up much of the earth's crust and are typically inexpensive materials, but poor electrical and optical properties prevent them from being useful for most semiconductor applications. Recent breakthroughs in chemistry and materials science allow for the growth of high-quality materials with nanometer-scale features...

  14. Nanostructured magnesium oxide as cure activator for polychloroprene rubber.

    Kar, Sritama; Bhowmick, Anil K

    2009-05-01

    The aim of this research was to synthesize magnesium oxide nanoparticles and to use them as cure activator for polychloroprene rubber (CR). The effects of counterions of magnesium salts on the homogeneous phase precipitation reaction to control size, monodispersity, crystallinity, and morphology of Mg(OH)2 nanoparticles were also investigated. Magnesium oxide nanoparticles were synthesized by optimizing the calcination temperature of Mg(OH)2 nanoparticles. Finally, the MgO nanoparticles were dispersed in polychloroprene rubber (CR) solution along with zinc oxide (ZnO) powder. The influence of MgO nanoparticles on the mechanical, dynamic mechanical and thermal properties of the resulting nanocomposites was quantified. The modulus and strength of ZnO-cured polychloroprene rubber with 4% MgO nanoparticles appeared to be superior to those with ZnO particles or ZnO with rubber grade MgO particles. These composites were further characterized by transmission electron microscopy and infrared spectroscopy in order to understand the morphology of the resulting system and the load transfer mechanism.

  15. Power generation using spinel manganese-cobalt oxide as a cathode catalyst for microbial fuel cell applications.

    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. Molecular-Level Processes Governing the Interaction of Contaminants with Iron and Manganese Oxides - Final Report; FINAL

    Brown, G. E. Jr.; Chambers, S. A.

    1999-01-01

    Many of the inorganic and organic contaminants present in sediments at DOE sites can be altered or destroyed by reduction and oxidation (redox) reactions occurring at mineral surfaces. A fundamental understanding of such redox processes provided by molecular-level studies on structurally and compositionally well-defined mineral surfaces will lead to: (i) improved models of contaminant fate and transport in geochemical systems, and (ii) optimized manipulation of these processes for remediation purposes. To contribute to this understanding, we will study, both experimentally and theoretically, redox processes involving three important contaminants - chromate ion, carbon tetrachloride, and trichloroethene TCE, on the following iron and manganese oxides - hematite, magnetite, maghemite, and pyrolusite. These oxides and their hydroxylated analogs commonly occur as coatings on minerals or as interfaces in the subsurface environment. Single-crystal surfaces of these oxides will be synthesized in carefully controlled fashion by molecular beam epitaxy. These surfaces, as well as high surface are powdered samples of these oxides, will be used in spectroscopic and kinetic experiments in both aqueous and gas phases. Our goal is to identify products and to determine the kinetics and mechanisms of surface-catalyzed redox reaction of Cr(VI) and CR(III), and the reductive dechlorination of carbon tetrachloride and TCE. The combination of theory and experiment will provide the base information needed to scale from the molecular level to the microscopic grain level minerals

  17. A study of a ceria-zirconia-supported manganese oxide catalyst for combustion of Diesel soot particles

    Sanchez Escribano, V.; Fernandez Lopez, E.; del Hoyo Martinez, C. [Departamento de Quimica Inorganica, Facultad de Ciencias Quimicas, Pa. de la Merced s/n, E-37008 Salamanca (Spain); Gallardo-Amores, J.M. [Lab. Complutense de Altas Presiones, Departamento de Quimica Inorganica I, Universidad Complutense, Ciudad Universitaria, E-28040 Madrid (Spain); Pistarino, C.; Panizza, M.; Resini, C.; Busca, G. [Dipartimento di Ingegneria Chimica e di Processo, Universita di Genova, P.le J.F. Kennedy, Pad. D, I-16129 Genoa (Italy)

    2008-04-15

    A study has been conducted on the structural and morphological characterization of a Ce-Zr mixed oxide-supported Mn oxide as well as on its catalytic activity in the oxidation of particulate matter arising from Diesel engines. X-ray powder diffraction analysis (XRD) and FT-IR and FT-Raman spectroscopy evidence that the support is a fluorite-like ceria-zirconia solid solution, whereas the supported phase corresponds to the manganese oxide denoted as bixbyite ({alpha}-Mn{sub 2}O{sub 3}). Thermal analyses and FT-IR spectra in air at varying temperatures of soot mechanically mixed with the catalyst evidence that the combustion takes place to a total extent in the range 420-720 K, carboxylic species being detected as intermediate compounds. Moreover, the soot oxidation was studied in a flow reactor and was found to be selective to CO{sub 2}, with CO as by-product in the range 420-620 K. The amount of the generated CO decreases significantly with increasing O{sub 2} concentration in the feed. (author)

  18. The effect of Ce ion substituted OMS-2 nanostructure in catalytic activity for benzene oxidation

    Hou, Jingtao; Li, Yuanzhi; Mao, Mingyang; Zhao, Xiujian; Yue, Yuanzheng

    2014-11-01

    The nanostructure of Ce doped OMS-2 plays a very important role in its catalytic property. We demonstrate by density functional theory (DFT) calculations that the unique nanostructure of the Ce ion substituted OMS-2 with Mn vacancy in the framework is beneficial for the improvement of catalytic activity, while the nanostructure of the Ce ion substituted OMS-2 without defects are detrimental to the catalytic activity. We establish a novel and facile strategy of synthesizing these unique Ce ion substituted OMS-2 nanostructure with Mn vacancies in the framework by hydrothermal redox reaction between Ce(NO3)3 and KMnO4 with KMnO4/Ce(NO3)3 at a molar ratio of 3 : 1 at 120 °C. Compared to pure OMS-2, the produced catalyst of Ce ion substituted OMS-2 ultrathin nanorods exhibits an enormous enhancement in the catalytic activity for benzene oxidation, which is evidenced by a significant decrease (ΔT50 = 100 °C, ΔT90 = 129 °C) in the reaction temperature of T50 and T90 (corresponding to the benzene conversion = 50% and 90%), which is considerably more efficient than the expensive supported noble metal catalyst (Pt/Al2O3). We combine both theoretical and experimental evidence to provide a new physical insight into the significant effect due to the defects induced by the Ce ion substitution on the catalytic activity of OMS-2. The formation of unique Ce ion substituted OMS-2 nanostructure with Mn vacancies in the framework leads to a significant enhancement of the lattice oxygen activity, thus tremendously increasing the catalytic activity.The nanostructure of Ce doped OMS-2 plays a very important role in its catalytic property. We demonstrate by density functional theory (DFT) calculations that the unique nanostructure of the Ce ion substituted OMS-2 with Mn vacancy in the framework is beneficial for the improvement of catalytic activity, while the nanostructure of the Ce ion substituted OMS-2 without defects are detrimental to the catalytic activity. We establish a novel

  19. Fabrication of band gap engineered nanostructured tri-metallic (Mn-Co-Ti) oxide thin films

    Mansoor, Muhammad Adil; Yusof, Farazila Binti; Nay-Ming, Huang

    2018-04-01

    In continuation of our previous studies on photoelectrochemical (PEC) properties of titanium based composite oxide thin films, an effort is made to develop thin films of 1:1:2 manganese-cobalt-titanium oxide composite, Mn2O3-Co2O3-4TiO2 (MCT), using Co(OAc)2 and a bimetallic manganese-titanium complex, [Mn2Ti4(TFA)8(THF)6(OH)4(O)2].0.4THF (1), where OAc = acetato, TFA = trifluoroacetato and THF = tetrahydrofuran, via aerosol-assisted chemical vapour deposition (AACVD) technique. The X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM) and energy dispersive X-ray (EDX) spectroscopic analyses confirmed formation of thin film of Mn2O3-Co2O3-4TiO2 composite material with uniformly distributed agglomerated particles. The average size of 39.5 nm, of the particles embedded inside agglomerates, was estimated by Scherer's equation. Further, UV-Vis spectroscopy was used to estimate the band gap of 2.62 eV for MCT composite thin film.

  20. Nanostructured high valence silver oxide produced by pulsed laser deposition

    Dellasega, D.; Facibeni, A.; Di Fonzo, F.; Russo, V.; Conti, C.; Ducati, C.; Casari, C.S.; Li Bassi, A.; Bottani, C.E.

    2009-01-01

    Among silver oxides, Ag 4 O 4 , i.e. high valence Ag(I)Ag(III) oxide, is interesting for applications in high energy batteries and for the development of antimicrobial coatings. We here show that ns UV pulsed laser deposition (PLD) in an oxygen containing atmosphere allows the synthesis of pure Ag 4 O 4 nanocrystalline thin films, permitting at the same time to control the morphology of the material at the sub-micrometer scale. Ag 4 O 4 films with a crystalline domain size of the order of tens of nm can be deposited provided the deposition pressure is above a threshold (roughly 4 Pa pure O 2 or 20 Pa synthetic air). The formation of this particular high valence silver oxide is explained in terms of the reactions occurring during the expansion of the ablated species in the reactive atmosphere. In particular, expansion of the PLD plasma plume is accompanied by formation of low stability Ag-O dimers and atomic oxygen, providing reactive species at the substrate where the film grows. Evidence of reactive collisions in the expanding ablation plume is obtained by analysis of the plume visible shape in inert and reactive atmospheres. In addition, we show how the dimensionless deposition parameter L, relating the target-to-substrate distance to the ablation plume maximum expansion length, can be used to classify different growth regimes. It is thus possible to vary the stoichiometry and the morphology of the films, from compact and columnar to foam-like, by controlling both the gas pressure and the target-to-substrate distance

  1. Designing deoxidation inhibiting encapsulation of metal oxide nanostructures for fluidic and biological applications

    Ghosh, Moumita, E-mail: ghoshiisc@gmail.com [Instrumentation and Applied Physics, Indian Institute of Science, Bangalore 560012 (India); Centre for Nano Science and Engineering, Indian Institute of Science, Bangalore 560012 (India); IV. Institute of Physics, Georg-August-Universität-Göttingen, Friedrich-Hund-Platz 1, 37077 Göttingen (Germany); III. Institute of Physics – Biophysics and Complex Systems, Georg-August-Universität-Göttingen, Friedrich-Hund-Platz 1, 37077 Göttingen (Germany); Ghosh, Siddharth [III. Institute of Physics – Biophysics and Complex Systems, Georg-August-Universität-Göttingen, Friedrich-Hund-Platz 1, 37077 Göttingen (Germany); Seibt, Michael [IV. Institute of Physics, Georg-August-Universität-Göttingen, Friedrich-Hund-Platz 1, 37077 Göttingen (Germany); Schaap, Iwan A.T. [III. Institute of Physics – Biophysics and Complex Systems, Georg-August-Universität-Göttingen, Friedrich-Hund-Platz 1, 37077 Göttingen (Germany); Institute of Biological Chemistry, Biophysics and Bioengineering, Heriot-Watt University, Edinburgh EH14 4AS (United Kingdom); Schmidt, Christoph F. [III. Institute of Physics – Biophysics and Complex Systems, Georg-August-Universität-Göttingen, Friedrich-Hund-Platz 1, 37077 Göttingen (Germany); Mohan Rao, G. [Instrumentation and Applied Physics, Indian Institute of Science, Bangalore 560012 (India)

    2016-12-30

    Graphical abstract: To retain atomic structure and morphology of ZnO nanostructures (caused by deoxidation of ZnO) in water/bio-fluids, we propose and demonstrate a robust and inexpensive encapsulation technique using bio-compatible non-ionic surfactant. - Highlights: • Aqueous solutions of ZnO nanorods with and without surfactant are prepared. • With time ZnO nanorods show structural deterioration in different aqueous solutions. • Crystallinity of ZnO nanorods in absence of aqueous solution remain unaffected. • Encapsulation of bio-compatible surfactant in alchohol avoid ZnO deoxidation. • Crystallinity and structure of ZnO nanorods after encapsulation remain unaffected. - Abstract: Due to their photoluminescence, metal oxide nanostructures such as ZnO nanostructures are promising candidates in biomedical imaging, drug delivery and bio-sensing. To apply them as label for bio-imaging, it is important to study their structural stability in a bio-fluidic environment. We have explored the effect of water, the main constituent of biological solutions, on ZnO nanostructures with scanning electron microscopy (SEM) and photoluminescence (PL) studies which show ZnO nanorod degeneration in water. In addition, we propose and investigate a robust and inexpensive method to encapsulate these nanostructures (without structural degradation) using bio-compatible non-ionic surfactant in non-aqueous medium, which was not reported earlier. This new finding is an immediate interest to the broad audience of researchers working in biophysics, sensing and actuation, drug delivery, food and cosmetics technology, etc.

  2. Fabrication of electrochemical theophylline sensor based on manganese oxide nanoparticles/ionic liquid/chitosan nanocomposite modified glassy carbon electrode

    MansouriMajd, Samira; Teymourian, Hazhir; Salimi, Abdollah; Hallaj, Rahman

    2013-01-01

    In this study, the preparation of a glassy carbon (GC) electrode modified with chitosan/NH 2 -ionic liquid/manganese oxide nanoparticles (Chit/NH 2 -IL/MnO x ) was described for electrocatalytic detection of theophylline (TP). First, chitosan hydrogel (Chit) was electrodeposited on the GC electrode surface at a constant potential (−1.5 V) in acidic solution. Then, the previously synthesized amine-terminated 1-(3-Aminopropyl)-3-methylimidazolium bromide ionic liquid (NH 2 -IL) was covalently attached to the modified electrode via glutaraldehyde (GA) as linking agent. Finally, manganese oxide (MnO x ) nanoparticles were electrodeposited onto the Chit/NH 2 -IL film by potential cycling between −1.0 and 1.7 V in Mn(CH 3 COO) 2 ·4H 2 O neutral aqueous solution. Electrochemical behavior of the modified electrode was evaluated by cyclic voltammetry (CV) technique. The charge transfer coefficient (α) and electron transfer rate constant (k s ) for MnOOH/MnO 2 redox couple were calculated to be 0.35 and 1.62 s −1 , respectively. The resulting system brings new capabilities for electrochemical sensing through combining the advantages of IL and MnO x nanoparticles. The differential pulse voltammetric (DPV) results indicated the high ability of GC/Chit/NH 2 -IL/MnO x modified electrode to catalyze the oxidation of TP. DPV determination of TP in acetate buffer solution (pH 5) gave linear responses over the concentration range up to 120 μM with the detection limit of 50 nM and sensitivity of 804 nA μM −1 . Furthermore, the applicability of the sensor for TP analysis in pharmaceutical samples has been successfully demonstrated

  3. Novel synthesis of manganese and vanadium mixed oxide (V2O5/OMS-2) as an efficient and selective catalyst for the oxidation of alcohols in liquid phase

    Mahdavi, Vahid; Soleimani, Shima

    2014-01-01

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

  4. Substrate specificity and copper loading of the manganese-oxidizing multicopper oxidase Mnx from Bacillus sp. PL-12.

    Butterfield, Cristina N; Tebo, Bradley M

    2017-02-22

    Manganese(ii) oxidation in the environment is thought to be driven by bacteria because enzymatic catalysis is many orders of magnitude faster than the abiotic processes. The heterologously purified Mn oxidase (Mnx) from marine Bacillus sp. PL-12 is made up of the multicopper oxidase (MCO) MnxG and two small Cu and heme-binding proteins of unknown function, MnxE and MnxF. Mnx binds Cu and oxidizes both Mn(ii) and Mn(iii), generating Mn(iv) oxide minerals that resemble those found on the Bacillus spore surface. Spectroscopic techniques have illuminated details about the metallo-cofactors of Mnx, but very little is known about their requirement for catalytic activity, and even less is known about the substrate specificity of Mnx. Here we quantify the canonical MCO Cu and persistent peripheral Cu bound to Mnx, and test Mnx oxidizing ability toward different substrates at varying pH. Mn(ii) appears to be the best substrate in terms of k cat , but its oxidation does not follow Michaelis-Menten kinetics, instead showing a sigmoidal cooperative behavior. Mnx also oxidizes Fe(ii) substrate, but in a Michaelis-Menten manner and with a decreased activity, as well as organic substrates. The reduced metals are more rapidly consumed than the larger organic substrates, suggesting the hypothesis that the Mnx substrate site is small and tuned for metal oxidation. Of biological relevance is the result that Mnx has the highest catalytic efficiency for Mn(ii) at the pH of sea water, especially when the protein is loaded with greater than the requisite four MCO copper atoms, suggesting that the protein has evolved specifically for Mn oxidation.

  5. Structural, optical, and magnetic studies of manganese-doped zinc oxide hierarchical microspheres by self-assembly of nanoparticles.

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

    2012-02-02

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

  6. Mesoporous iron–manganese oxides for sulphur mustard and soman degradation

    Štengl, Václav; Matys Grygar, Tomáš; Bludská, Jana; Opluštil, F.; Němec, T.

    2012-01-01

    Roč. 47, č. 12 (2012), s. 4291-4299 ISSN 0025-5408 R&D Projects: GA ČR(CZ) GAP106/12/1116 Institutional support: RVO:61388980 Keywords : nanostructures * chemical synthesis * microstructure * surface poroperties Subject RIV: CA - Inorganic Chemistry Impact factor: 1.913, year: 2012

  7. A self-seeded, surfactant-directed hydrothermal growth of single crystalline lithium manganese oxide nanobelts from the commercial bulky particles.

    Zhang, Lizhi; Yu, Jimmy C; Xu, An-Wu; Li, Quan; Kwong, Kwan Wai; Wu, Ling

    2003-12-07

    Single crystalline lithium manganese oxide nanobelts were obtained through a self-seeded, surfactant-directed growth process from the commercial bulky particles under hydrothermal treatment. A possible mechanism was proposed to explain the growth of the nanobelts. This new process could be extended to prepare other one-dimensional nanomaterials such as Se nanorods, Te nanotubes, and MnO2 nanowires.

  8. Combined cycling and calendar capacity fade modeling of a Nickel-Manganese-Cobalt Oxide Cell with real-life profile validation

    de Hoog, Joris; Timmermans, Jean-Marc; Stroe, Daniel-Ioan

    2017-01-01

    This paper presents the development of a semi-empirical combined lifetime model for a Nickel Manganese Cobalt Oxide (NMC) cathode and a graphite anode based cell, considered as one of the most promising candidates for the automotive industry. The development of this model was based on a thorough...

  9. Origin of the chemical shift in X-ray absorption near-edge spectroscopy at the Mn K-Edge in manganese oxide compounds

    de Vries, AH; Hozoi, L.; Broer, R.

    2003-01-01

    The absorption edge in Mn K-edge X-ray absorption spectra of manganese oxide compounds shows a shift of several electronvolts in going from MnO through LaMnO3 to CaMnO3. On the other hand, in X-ray photoelectron spectra much smaller shifts are observed. To identify the mechanisms that cause the

  10. Formation of superhydrophobic/superhydrophilic patterns by combination of nanostructure-imprinted perfluoropolymer and nanostructured silicon oxide for biological droplet generation

    Kobayashi, Taizo; Shimizu, Kazunori; Kaizuma, Yoshihiro; Konishi, Satoshi

    2011-03-01

    In this letter, we report a technology for fabricating superhydrophobic/superhydrophilic patterns using a combination of a nanostructure-imprinted perfluoropolymer and nanostructured silicon oxide. In our previous study, we used a combination of hydrophobic and superhydrophilic materials. However, it was difficult to split low-surface-tension liquids such as biological liquids into droplets solely using hydrophobic/hydrophilic patterns. In this study, the contact angle of the hydrophobic region was enhanced from 109.3° to 155.6° by performing nanostructure imprinting on a damage-reduced perfluoropolymer. The developed superhydrophobic/superhydrophilic patterns allowed the splitting of even those media that contained fetal bovine serum into droplets of a desired shape.

  11. Copper and Zinc Oxide Composite Nanostructures for Solar Energy Harvesting

    Wu, Fei

    Solar energy is a clean and sustainable energy source to counter global environmental issues of rising atmospheric CO2 levels and depletion of natural resources. To extract useful work from solar energy, silicon-based photovoltaic devices are extensively used. The technological maturity and the high quality of silicon (Si) make it a material of choice. However limitations in Si exist, ranging from its indirect band gap to low light absorption coefficient and energy and capital intensive crystal growth schemes. Therefore, alternate materials that are earth-abundant, benign and simpler to process are needed for developing new platforms for solar energy harvesting applications. In this study, we explore oxides of copper (CuO and Cu2O) in a nanowire morphology as alternate energy harvesting materials. CuO has a bandgap of 1.2 eV whereas Cu2O has a bandgap of 2.1 eV making them ideally suited for absorbing solar radiation. First, we develop a method to synthesize vertical, single crystalline CuO and Cu2O nanowires of ~50 microm length and aspect ratios of ~200. CuO nanowire arrays are synthesized by thermal oxidation of Cu foils. Cu2O nanowire arrays are synthesized by thermal reduction of CuO nanowires. Next, surface engineering of these nanowires is achieved using atomic layer deposition (ALD) of ZnO. By depositing 1.4 nm of ZnO, a highly defective surface is produced on the CuO nanowires. These defects are capable of trapping charge as is evident through persistent photoconductivity measurements of ZnO coated CuO nanowires. The same nanowires serve as efficient photocatalysts reducing CO2 to CO with a yield of 1.98 mmol/g-cat/hr. Finally, to develop a robust platform for flexible solar cells, a protocol to transfer vertical CuO nanowires inside flexible polydimethylsiloxane (PDMS) is demonstrated. Embedded CuO nanowires-ZnO pn junctions show a VOC of 0.4 V and a JSC of 10.4 microA/cm2 under white light illumination of 5.7 mW/cm2. Thus, this research provides broad

  12. Dye-sensitized solar cells based on nanostructured zinc oxide

    Conradt, Jonas; Maier-Flaig, Florian; Sartor, Janos; Fallert, Johannes [Karlsruhe Institute of Technology (KIT), Karlsruhe (Germany); Szmytkowski, Jedrzej; Kalt, Heinz [Karlsruhe Institute of Technology (KIT), Karlsruhe (Germany); Center for Functional Nanostructures (CFN), Karlsruhe (Germany); Reinhard, Manuel; Colsmann, Alexander [Karlsruhe Institute of Technology (KIT), Lichttechnisches Institut, Karlsruhe (Germany); Lemmer, Uli [Center for Functional Nanostructures (CFN), Karlsruhe (Germany); Karlsruhe Institute of Technology (KIT), Lichttechnisches Institut, Karlsruhe (Germany); Balaban, Teodor Silviu [Center for Functional Nanostructures (CFN), Karlsruhe (Germany); Karlsruhe Institute of Technology (KIT), Institute for Nanotechnology, Karlsruhe (Germany)

    2009-07-01

    Hybrid solar cells represent a promising (cost-efficient) alternative to pure inorganic solar cells. We present dye-sensitized solar cells (DSSC) which are based on a zinc oxide (ZnO) electrode covered with a ruthenium dye. Our work focuses on the morphology of the ZnO electrode and its impact on the photovoltaic performance of the solar cell. Nanocrystalline ZnO powder layers and arrays of nanorods are incorporated into the DSSCs. The ZnO nanorods are grown by vapor transport deposition. The morphology and doping concentration of the rods can be controlled by the choice of substrate material, growth condition and catalytic metal layers. The nanorod arrays are expected to fasten the electron transport towards the anode and thereby improve the solar cell efficiency. In addition, novel self-assembling (porphyrin) dyes are tested as sensitizer within a DSSC.

  13. Nanostructured Scrolls from Graphene Oxide for Microjet Engines.

    Yao, Kun; Manjare, Manoj; Barrett, Christopher A; Yang, Bo; Salguero, Tina T; Zhao, Yiping

    2012-08-16

    Layered heterostructures containing graphene oxide (GO) nanosheets and 20-35 nm bimetal coatings can detach easily from a Si substrate upon sonication-spontaneously forming freestanding, micrometer-sized scrolls with GO on the outside-due to a combination of material stresses and weak bonding between GO layers. Simple procedures can tune the scroll diameters by varying the thicknesses of the metal films, and these results are confirmed by both experiment and modeling. The selection of materials determines the stresses that control the rolling behavior, as well as the functionality of the structures. In the GO/Ti/Pt system, the Pt is located within the interior of the scrolls, which can become self-propelled microjet engines through O2 bubbling when suspended in aqueous H2O2.

  14. Self-cleaning glasses containing nanostructured titanium oxide

    Araujo, A.; Alves, A.K.; Berutti, F.A.; Bergmann, C.P.

    2010-01-01

    Using the electrospinning technique nanofibers of titanium oxide were synthesized. As precursor materials, titanium propoxide and a solution of polyvinylpyrrolidone were used. After the electrospinning process, the non-tissue material obtained was heat treated and characterized by X-ray diffraction to determine the phase crystallinity, and SEM to analyze the microstructure of the fibers. After ultrasound dispersion of this material in isopropyl alcohol, the glass coatings were made by dip-coating methodology. The removal velocity was kept constant, but the solution composition was varied to obtain a transparent and photo active film. The film was characterized by the contact angle of a water droplet in its surface (hydrophilicity), the transparency was evaluated using a spectrophotometer and the photocatalytic activity of the film was also evaluated. (author)

  15. High temperature oxidation behaviour of nanostructured cermet coatings in a mixed CO2 - O2 environment

    Farrokhzad, M. A.; Khan, T. I.

    2014-06-01

    Nanostructured ceramic-metallic (cermet) coatings composed of nanosized ceramic particles (α-Al2O3 and TiO2) dispersed in a nickel matrix were co-electrodeposited and then oxidized at 500°C, 600°C and 700°C in a mixed gas using a Thermo-gravimetric Analysis (TGA) apparatus. The mixed gas was composed of 15% CO2, 10% O2 and 75% N2. This research investigates the effects of CO2 and O2 partial pressures on time-depended oxidation rates for coatings and compared them to the results from atmospheric oxidation under similar temperatures. The increase in partial pressure of oxygen due to the presence of CO2 at each tested temperature was calculated and correlated to the oxidation rate of the coatings. The results showed that the presence of CO2 in the system increased the oxidation rate of cermet coatings when compared to atmospheric oxidation at the same temperature. It was also shown that the increase in the oxidation rate is not the result of CO2 acting as the primary oxidant but as a secondary oxidant which results in an increase of the total partial pressure of oxygen and consequently higher oxidation rates. The WDS and XRD analyses results showed that the presence of nanosized TiO2 particles in a nickel matrix can improve oxidation behaviour of the coatings by formation of Ni-Ti compounds on oxidizing surface of the coating which was found beneficiary in reducing the oxidation rates for cermet coatings.

  16. Supported manganese oxide on TiO{sub 2} for total oxidation of toluene and polycyclic aromatic hydrocarbons (PAHs): Characterization and catalytic activity

    Aboukaïs, Antoine, E-mail: aboukais@univ-littoral.fr [Univ Lille Nord de France, 59000 Lille (France); Equipe Catalyse, UCEIV, EA 4492, MREI, ULCO, 59140 Dunkerque (France); Abi-Aad, Edmond [Univ Lille Nord de France, 59000 Lille (France); Equipe Catalyse, UCEIV, EA 4492, MREI, ULCO, 59140 Dunkerque (France); Taouk, Bechara [Laboratoire de Sécurité des procédés Chimiques (LSPC), EA 4704, INSA Rouen, Avenue de l' Université, 76801 Saint Etienne du Rouvray (France)

    2013-11-01

    Manganese oxide catalysts supported on titania (TiO{sub 2}) were prepared by incipient wetness impregnation method in order to elaborate catalysts for total oxidation of toluene and PAHs. These catalysts have been characterized by means of X-ray diffraction (XRD), electron paramagnetic resonance (EPR), temperature programmed reduction (TPR) and temperature programmed desorption (TPD). It has been shown that for the 5%Mn/TiO{sub 2} catalyst the reducibility and the mobility of oxygen are higher compared, in one side, to other x%Mn/TiO{sub 2} samples and, in another side, to catalysts where TiO{sub 2} support was replaced by γ-Al{sub 2}O{sub 3} or SiO{sub 2}. It has been shown that the content of manganese loading on TiO{sub 2} has an effect on the catalytic activity in the toluene oxidation. A maximum of activity was obtained for the 5%Mn/TiO{sub 2} catalyst where the total conversion of toluene was reached at 340 °C. This activity seems to be correlated to the presence of the Mn{sup 3+}/Mn{sup 4+} redox couple in the catalyst. When the Mn content increases, large particles of Mn{sub 2}O{sub 3} appear leading then to the decrease in the corresponding activity. In addition, compared to both other supports, TiO{sub 2} seems to be the best to give the best catalytic activity for the oxidation of toluene when it is loaded with 5% of manganese. For this reason, the latter catalyst was tested for the abatement of some PAHs. The light off temperature of PAHs compounds increases with increasing of benzene rings number and with decreasing of H/C ratio. All of PAHs are almost completely oxidized and converted at temperatures lower than 500 °C. - Highlights: • Preparation of x%MnO{sub 2}/TiO{sub 2} catalysts. • Catalytic oxidation tests of toluene and PAHs. • EPR, TPR and TPD characterizations of Mn(II) and Mn(IV) ions.

  17. Bio-templated synthesis of lithium manganese oxide microtubes and their application in Li{sup +} recovery

    Yu, Qianqian, E-mail: qianqianyu09@gmail.com; Sasaki, Keiko; Hirajima, Tsuyoshi

    2013-11-15

    Highlights: • Biogenic birnessite was used to synthesize microtube-type Li{sup +} ion sieve. • The biomineral facilitates LMO formation at a lower temperature. • HMO-MT with high Li{sup +} uptake capacity was obtained. • Temperature effects on properties of HMO-MTs were studied. -- Abstract: Microbial transformations, a primary pathway for the Mn oxides formation in nature, provide potential for material-oriented researchers to fabricate new materials. Using Mn oxidizing fungus Paraconiothyrium sp. WL-2 as a bio-oxidizer as well as a bio-template, a special lithium ion sieve with microtube morphology was prepared through a solid-state transformation. Varying the calcination temperature from 300 to 700 °C was found to influence sample properties and consequently, the adsorption of Li{sup +}. Lithium manganese oxide microtube (LMO-MTs) calcined at different temperatures as well as their delithiated products (HMO-MTs) were characterized by X-ray diffraction (XRD), X-ray absorption fine structure (XAFS) spectroscopy, scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Calcination temperatures affect not only the content but also the crystal structure of LMO spinel, which is important in Li{sup +} adsorption. The optimized sample was obtained after calcination at 500 °C for 4 h, which shows higher Li{sup +} adsorption capacity than particulate materials.

  18. Surface properties of nanostructured NiO undergoing electrochemical oxidation in 3-methoxy-propionitrile

    Bonomo, Matteo; Marrani, Andrea Giacomo; Novelli, Vittoria; Awais, Muhammad; Dowling, Denis P.; Vos, Johannes G.; Dini, Danilo

    2017-05-01

    Nanostructured nickel oxide (NiO) was deposited in the configuration of thin film (thickness, l = 2-6 μm) onto fluorine-doped tin oxide (FTO) substrates via plasma-assisted rapid discharge sintering (RDS). Electrochemical cycling of RDS NiO in 3-methoxy-propionitrile (3-MPN) revealed two characteristic peaks of NiO oxidation which were associated to the surface-confined redox processes Ni(II) → Ni(III) and Ni(III) → Ni(IV). Grazing angle X-ray photoelectron spectroscopy (XPS) was conducted ex-situ on NiO electrodes in both pristine and oxidized states. Oxidized NiO samples for XPS experiments were obtained in the potentiostatic mode through the polarization of NiO at its two characteristic potentials of oxidation. The XPS analysis allowed to ascertain the electronic structure of the nanoporous NiO framework, and verify the adsorption of perchlorate and chloride anions onto NiO surface due to the compensation of the charge stored in oxidized NiO. XPS also revealed that the spectrum within the region characteristic of Ni 2p ionization does not vary considerably with the state of charge of the nickel centres. This finding is in evident contrast to what has been observed for the same system when it undergoes electrochemical oxidation in aqueous electrolyte.

  19. Treatment of dye wastewater with permanganate oxidation and in situ formed manganese dioxides adsorption: cation blue as model pollutant.

    Liu, Ruiping; Liu, Huijuan; Zhao, Xu; Qu, Jiuhui; Zhang, Ran

    2010-04-15

    This study investigated the process of potassium permanganate (KMnO(4)) oxidation and in situ formed hydrous manganese dioxides (deltaMnO(2)) (i.e., KMnO(4) oxidation and deltaMnO(2) adsorption) for the treatment of dye wastewater. The effectiveness of decolorization, removing dissolved organic carbon (DOC), and increasing biodegradable oxygen demand (BOD) were compared among these processes of KMnO(4) oxidation, deltaMnO(2) adsorption, and KMnO(4) oxidation and deltaMnO(2) adsorption. DeltaMnO(2) adsorption contributed to the maximum DOC removal of 65.0%, but exhibited limited capabilities of decolorizing and increasing biodegradability. KMnO(4) oxidation alone at pH 0.5 showed satisfactory decrease of UV-vis absorption peaks, and the maximum BOD(5)/DOC value of 1.67 was achieved. Unfortunately, the DOC removal was as low as 27.4%. Additionally, the great amount of acid for pH adjustment and the much too low pH levels limited its application in practice. KMnO(4) oxidation and deltaMnO(2) adsorption at pH 2.0 was the best strategy prior to biological process, in balancing the objectives of decolorization, DOC removal, and BOD increase. The optimum ratio of KMnO(4) dosage to X-GRL concentration (R(KMnO(4)/X-GRL)) was determined to be 2.5, at which KMnO(4) oxidation and deltaMnO(2) adsorption contributed to the maximal DOC removal of 53.4%. Additionally, the optimum pH for X-GRL treatment was observed to be near 3.0. 2009 Elsevier B.V. All rights reserved.

  20. Thermocatalytic Behavior of Manganese (IV Oxide as Nanoporous Material on the Dissociation of a Gas Mixture Containing Hydrogen Peroxide

    Zaid B. Jildeh

    2018-04-01

    Full Text Available In this article, we present an overview on the thermocatalytic reaction of hydrogen peroxide (H 2 O 2 gas on a manganese (IV oxide (MnO 2 catalytic structure. The principle of operation and manufacturing techniques are introduced for a calorimetric H 2 O 2 gas sensor based on porous MnO 2 . Results from surface analyses by X-ray photoelectron spectroscopy (XPS and scanning electron microscopy (SEM of the catalytic material provide indication of the H 2 O 2 dissociation reaction schemes. The correlation between theory and the experiments is documented in numerical models of the catalytic reaction. The aim of the numerical models is to provide further information on the reaction kinetics and performance enhancement of the porous MnO 2 catalyst.

  1. Thermocatalytic Behavior of Manganese (IV) Oxide as Nanoporous Material on the Dissociation of a Gas Mixture Containing Hydrogen Peroxide.

    Jildeh, Zaid B; Oberländer, Jan; Kirchner, Patrick; Wagner, Patrick H; Schöning, Michael J

    2018-04-21

    In this article, we present an overview on the thermocatalytic reaction of hydrogen peroxide (H 2 O 2 ) gas on a manganese (IV) oxide (MnO 2 ) catalytic structure. The principle of operation and manufacturing techniques are introduced for a calorimetric H 2 O 2 gas sensor based on porous MnO 2 . Results from surface analyses by X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) of the catalytic material provide indication of the H 2 O 2 dissociation reaction schemes. The correlation between theory and the experiments is documented in numerical models of the catalytic reaction. The aim of the numerical models is to provide further information on the reaction kinetics and performance enhancement of the porous MnO 2 catalyst.

  2. Water-soluble Manganese and Iron Mesotetrakis(carboxyl)porphyrin: DNA Binding, Oxidative Cleavage, and Cytotoxic Activities.

    Shi, Lei; Jiang, Yi-Yu; Jiang, Tao; Yin, Wei; Yang, Jian-Ping; Cao, Man-Li; Fang, Yu-Qi; Liu, Hai-Yang

    2017-06-29

    Two new water-soluble metal carboxyl porphyrins, manganese (III) meso -tetrakis (carboxyl) porphyrin and iron (III) meso -tetrakis (carboxyl) porphyrin, were synthesized and characterized. Their interactions with ct-DNA were investigated by UV-Vis titration, fluorescence spectra, viscosity measurement and CD spectra. The results showed they can strongly bind to ct-DNA via outside binding mode. Electrophoresis experiments revealed that both complexes can cleave pBR322 DNA efficiently in the presence of hydrogen peroxide, albeit 2-Mn exhibited a little higher efficiency. The inhibitor tests suggest the oxidative DNA cleavage by these two complexes may involve hydroxyl radical active intermediates. Notably, 2-Mn exhibited considerable photocytotoxicity against Hep G2 cell via triggering a significant generation of ROS and causing disruption of MMP after irradiation.

  3. Synthesizing Iron Oxide Nanostructures: The Polyethylenenemine (PEI) Role

    Mozo, Sergio Lentijo

    2017-01-12

    Controlled synthesis of anisotropic iron oxide nanoparticles is a challenge in the field of nanomaterial research that requires an extreme attention to detail. In particular, following up a previous work showcasing the synthesis of magnetite nanorods (NRs) using a two-step approach that made use of polyethylenenemine (PEI) as a capping ligand to synthesize intermediate β-FeOOH NRs, we studied the effect and influence of the capping ligand on the formation of β-FeOOH NRs. By comparing the results reported in the literature with those we obtained from syntheses performed (1) in the absence of PEI or (2) by using PEIs with different molecular weight, we showed how the choice of different PEIs determines the aspect ratio and the structural stability of the β-FeOOH NRs and how this affects the final products. For this purpose, a combination of XRD, HRTEM, and direct current superconducting quantum interference device (DC SQUID) magnetometry was used to identify the phases formed in the final products and study their morphostructural features and related magnetic behavior.

  4. NANOSTRUCTURED METAL OXIDE CATALYSTS VIA BUILDING BLOCK SYNTHESES

    Craig E. Barnes

    2013-03-05

    A broadly applicable methodology has been developed to prepare new single site catalysts on silica supports. This methodology requires of three critical components: a rigid building block that will be the main structural and compositional component of the support matrix; a family of linking reagents that will be used to insert active metals into the matrix as well as cross link building blocks into a three dimensional matrix; and a clean coupling reaction that will connect building blocks and linking agents together in a controlled fashion. The final piece of conceptual strategy at the center of this methodology involves dosing the building block with known amounts of linking agents so that the targeted connectivity of a linking center to surrounding building blocks is obtained. Achieving targeted connectivities around catalytically active metals in these building block matrices is a critical element of the strategy by which single site catalysts are obtained. This methodology has been demonstrated with a model system involving only silicon and then with two metal-containing systems (titanium and vanadium). The effect that connectivity has on the reactivity of atomically dispersed titanium sites in silica building block matrices has been investigated in the selective oxidation of phenols to benezoquinones. 2-connected titanium sites are found to be five times as active (i.e. initial turnover frequencies) than 4-connected titanium sites (i.e. framework titanium sites).

  5. Electrospray-printed nanostructured graphene oxide gas sensors

    Taylor, Anthony P.; Velásquez-García, Luis F.

    2015-12-01

    We report low-cost conductometric gas sensors that use an ultrathin film made of graphene oxide (GO) nanoflakes as transducing element. The devices were fabricated by lift-off metallization and near-room temperature, atmospheric pressure electrospray printing using a shadow mask. The sensors are sensitive to reactive gases at room temperature without requiring any post heat treatment, harsh chemical reduction, or doping with metal nanoparticles. The sensors’ response to humidity at atmospheric pressure tracks that of a commercial sensor, and is linear with changes in humidity in the 10%-60% relative humidity range while consuming recipes yielded nearly identical response characteristics, suggesting that intrinsic properties of the film control the sensing mechanism. The gas sensors successfully detected ammonia at concentrations down to 500 ppm (absolute partial pressure of ˜5 × 10-4 T) at ˜1 T pressure, room temperature conditions. The sensor technology can be used in a great variety of applications including air conditioning and sensing of reactive gas species in vacuum lines and abatement systems.

  6. Electrospray-printed nanostructured graphene oxide gas sensors

    Taylor, Anthony P; Velásquez-García, Luis F

    2015-01-01

    We report low-cost conductometric gas sensors that use an ultrathin film made of graphene oxide (GO) nanoflakes as transducing element. The devices were fabricated by lift-off metallization and near-room temperature, atmospheric pressure electrospray printing using a shadow mask. The sensors are sensitive to reactive gases at room temperature without requiring any post heat treatment, harsh chemical reduction, or doping with metal nanoparticles. The sensors’ response to humidity at atmospheric pressure tracks that of a commercial sensor, and is linear with changes in humidity in the 10%–60% relative humidity range while consuming <6 μW. Devices with GO layers printed by different deposition recipes yielded nearly identical response characteristics, suggesting that intrinsic properties of the film control the sensing mechanism. The gas sensors successfully detected ammonia at concentrations down to 500 ppm (absolute partial pressure of ∼5 × 10"−"4 T) at ∼1 T pressure, room temperature conditions. The sensor technology can be used in a great variety of applications including air conditioning and sensing of reactive gas species in vacuum lines and abatement systems. (paper)

  7. Self-limiting and complete oxidation of silicon nanostructures produced by laser ablation in water

    Vaccaro, L.; Messina, F.; Camarda, P.; Gelardi, F. M.; Cannas, M., E-mail: marco.cannas@unipa.it [Dipartimento di Fisica e Chimica, Università di Palermo, Via Archirafi 36, I-90123 Palermo (Italy); Popescu, R.; Schneider, R.; Gerthsen, D. [Laboratory for Electron Microscopy, Karlsruhe Institute of Technology, Engesserstrasse 7, 76131 Karlsruhe (Germany)

    2016-07-14

    Oxidized Silicon nanomaterials produced by 1064 nm pulsed laser ablation in deionized water are investigated. High-resolution transmission electron microscopy coupled with energy dispersive X-ray spectroscopy allows to characterize the structural and chemical properties at a sub-nanometric scale. This analysis clarifies that laser ablation induces both self-limiting and complete oxidation processes which produce polycrystalline Si surrounded by a layer of SiO{sub 2} and amorphous fully oxidized SiO{sub 2}, respectively. These nanostructures exhibit a composite luminescence spectrum which is investigated by time-resolved spectroscopy with a tunable laser excitation. The origin of the observed luminescence bands agrees with the two structural typologies: Si nanocrystals emit a μs-decaying red band; defects of SiO{sub 2} give rise to a ns-decaying UV band and two overlapping blue bands with lifetime in the ns and ms timescale.

  8. Electrostatic Spray Deposition-Based Manganese Oxide Films-From Pseudocapacitive Charge Storage Materials to Three-Dimensional Microelectrode Integrands.

    Agrawal, Richa; Adelowo, Ebenezer; Baboukani, Amin Rabiei; Villegas, Michael Franc; Henriques, Alexandra; Wang, Chunlei

    2017-07-26

    In this study, porous manganese oxide (MnO x ) thin films were synthesized via electrostatic spray deposition (ESD) and evaluated as pseudocapacitive electrode materials in neutral aqueous media. Very interestingly, the gravimetric specific capacitance of the ESD-based electrodes underwent a marked enhancement upon electrochemical cycling, from 72 F∙g -1 to 225 F∙g -1 , with a concomitant improvement in kinetics and conductivity. The change in capacitance and resistivity is attributed to a partial electrochemical phase transformation from the spinel-type hausmannite Mn₃O₄ to the conducting layered birnessite MnO₂. Furthermore, the films were able to retain 88.4% of the maximal capacitance after 1000 cycles. Upon verifying the viability of the manganese oxide films for pseudocapacitive applications, the thin films were integrated onto carbon micro-pillars created via carbon microelectromechanical systems (C-MEMS) for examining their application as potential microelectrode candidates. In a symmetric two-electrode cell setup, the MnO x /C-MEMS microelectrodes were able to deliver specific capacitances as high as 0.055 F∙cm -2 and stack capacitances as high as 7.4 F·cm -3 , with maximal stack energy and power densities of 0.51 mWh·cm -3 and 28.3 mW·cm -3 , respectively. The excellent areal capacitance of the MnO x -MEs is attributed to the pseudocapacitive MnO x as well as the three-dimensional architectural framework provided by the carbon micro-pillars.

  9. Electrostatic Spray Deposition-Based Manganese Oxide Films—From Pseudocapacitive Charge Storage Materials to Three-Dimensional Microelectrode Integrands

    Richa Agrawal

    2017-07-01

    Full Text Available In this study, porous manganese oxide (MnOx thin films were synthesized via electrostatic spray deposition (ESD and evaluated as pseudocapacitive electrode materials in neutral aqueous media. Very interestingly, the gravimetric specific capacitance of the ESD-based electrodes underwent a marked enhancement upon electrochemical cycling, from 72 F∙g−1 to 225 F∙g−1, with a concomitant improvement in kinetics and conductivity. The change in capacitance and resistivity is attributed to a partial electrochemical phase transformation from the spinel-type hausmannite Mn3O4 to the conducting layered birnessite MnO2. Furthermore, the films were able to retain 88.4% of the maximal capacitance after 1000 cycles. Upon verifying the viability of the manganese oxide films for pseudocapacitive applications, the thin films were integrated onto carbon micro-pillars created via carbon microelectromechanical systems (C-MEMS for examining their application as potential microelectrode candidates. In a symmetric two-electrode cell setup, the MnOx/C-MEMS microelectrodes were able to deliver specific capacitances as high as 0.055 F∙cm−2 and stack capacitances as high as 7.4 F·cm−3, with maximal stack energy and power densities of 0.51 mWh·cm−3 and 28.3 mW·cm−3, respectively. The excellent areal capacitance of the MnOx-MEs is attributed to the pseudocapacitive MnOx as well as the three-dimensional architectural framework provided by the carbon micro-pillars.

  10. Nanoscale Structural/Chemical Characterization of Manganese Oxide Surface Layers and Nanoparticles, and the Associated Implications for Drinking Water

    Michel Eduardo Vargas Vallejo

    Water treatment facilities commonly reduce soluble contaminants, such as soluble manganese (Mn2+), in water by oxidation and subsequent filtration. Previous studies have shown that conventional porous filter system removes Mn2+ from drinking water by developing Mn-oxides (MnO x(s)) bearing coating layers on the surface of filter media. Multiple models have been developed to explain this Mn2+ removal process and the formation mechanism of MnOx(s) coatings. Both, experimental and theoretical studies to date have been largely focused on the micrometer to millimeter scale range; whereas, coating layers are composed of nanoscale particles and films. Hence, understanding the nanoscale particle and film formation mechanisms is essential to comprehend the complexity of soluble contaminant removal processes. The primary objective of this study was to understand the initial MnOx(s) coating formation mechanisms and evaluate the influence of filter media characteristics on these processes. We pursued this objective by characterizing at the micro and nanoscale MnO x(s) coatings developed on different filter media by bench-scale column tests with simulating inorganic aqueous chemistry of a typical coagulation fresh water treatment plant, where free chlorine is present across filter bed. Analytical SEM and TEM, powder and synchrotron-based XRD, XPS, and ICPMS were used for characterization of coatings, filter media and water solution elemental chemistry. A secondary objective was to model how surface coating formation occurred and its correlation with experimentally observed physical characteristics. This modeling exercise indicates that surface roughness and morphology of filtering media are the major contributing factors in surface coating formation process. Contrary to previous models that assumed a uniform distribution and growth of surface coating, the experimental results showed that greater amounts of coating were developed in rougher areas. At the very early stage of

  11. Degradation of lithium ion batteries employing graphite negatives and nickel-cobalt-manganese oxide + spinel manganese oxide positives: Part 2, chemical-mechanical degradation model

    Purewal, Justin; Wang, John; Graetz, Jason; Soukiazian, Souren; Tataria, Harshad; Verbrugge, Mark W.

    2014-12-01

    Capacity fade is reported for 1.5 Ah Li-ion batteries containing a mixture of Li-Ni-Co-Mn oxide (NCM) + Li-Mn oxide spinel (LMO) as positive electrode material and a graphite negative electrode. The batteries were cycled at a wide range of temperatures (10 °C-46 °C) and discharge currents (0.5C-6.5C). The measured capacity losses were fit to a simple physics-based model which calculates lithium inventory loss from two related mechanisms: (1) mechanical degradation at the graphite anode particle surface caused by diffusion-induced stresses (DIS) and (2) chemical degradation caused by lithium loss to continued growth of the solid-electrolyte interphase (SEI). These two mechanisms are coupled because lithium is consumed through SEI formation on newly exposed crack surfaces. The growth of crack surface area is modeled as a fatigue phenomenon due to the cyclic stresses generated by repeated lithium insertion and de-insertion of graphite particles. This coupled chemical-mechanical degradation model is consistent with the observed capacity loss features for the NCM + LMO/graphite cells.

  12. Enhanced photocatalytic performance of ZnO nanostructures by electrochemical hybridization with graphene oxide

    Pruna, A.; Wu, Z.; Zapien, J. A.; Li, Y. Y.; Ruotolo, A.

    2018-05-01

    Synthesis of zinc oxide (ZnO) nanostructures is reported by electrochemical deposition from an aqueous electrolyte in presence of graphene oxide (GO) with varying oxidation degree. The properties of hybrids were investigated by scanning electron microscopy, X-ray diffraction, Raman, Fourier-Transform Infrared and X-ray photoelectron spectroscopy techniques and photocatalytic measurements. The results indicated the electrodeposition of ZnO in presence of GO with increased oxygen content led to marked differences in the morphology while Raman measurements indicated an increased defect level both in the ZnO and the electrochemically reduced GO (ErGO) within the hybrids. The decrease in C/O atomic ratio of GO (from 0.79 to 0.71) employed for the electrodeposition of ZnO resulted in an increase in photocatalytic efficiency for methylene blue degradation under UV irradiation from 4-folds to 10-folds with respect to non-hybridized ZnO. The observed synergetic effect of cathodic deposition potential and oxygen content in GO towards improving the photocatalytic activity of immobilized ZnO is expected to contribute to further development of more effective deposition approaches for the preparation of high performance hybrid nanostructures.

  13. Promotion of Water-mediated Carbon Removal by Nanostructured Barium Oxide/nickel Interfaces

    L Yang; Y Choi; W Qin; H Chen; K Blinn; M Liu; P Liu; J Bai; T Tyson; M Liu

    2011-12-31

    The existing Ni-yttria-stabilized zirconia anodes in solid oxide fuel cells (SOFCs) perform poorly in carbon-containing fuels because of coking and deactivation at desired operating temperatures. Here we report a new anode with nanostructured barium oxide/nickel (BaO/Ni) interfaces for low-cost SOFCs, demonstrating high power density and stability in C{sub 3}H{sub 8}, CO and gasified carbon fuels at 750 C. Synchrotron-based X-ray analyses and microscopy reveal that nanosized BaO islands grow on the Ni surface, creating numerous nanostructured BaO/Ni interfaces that readily adsorb water and facilitate water-mediated carbon removal reactions. Density functional theory calculations predict that the dissociated OH from H2O on BaO reacts with C on Ni near the BaO/Ni interface to produce CO and H species, which are then electrochemically oxidized at the triple-phase boundaries of the anode. This anode offers potential for ushering in a new generation of SOFCs for efficient, low-emission conversion of readily available fuels to electricity.

  14. Studies on the optoelectronic properties of the thermally evaporated tin-doped indium oxide nanostructures

    Pan, Ko-Ying [Department of Materials Science and Engineering, National Tsing Hua University, Hsinchu 300, Taiwan, ROC (China); Lin, Liang-Da [Institute of Materials Science and Nanotechnology, Chinese Culture University, Taipei 111, Taiwan, ROC (China); Chang, Li-Wei [Department of Materials Science and Engineering, National Tsing Hua University, Hsinchu 300, Taiwan, ROC (China); Shih, Han C., E-mail: hcshih@mx.nthu.edu.tw [Department of Materials Science and Engineering, National Tsing Hua University, Hsinchu 300, Taiwan, ROC (China); Institute of Materials Science and Nanotechnology, Chinese Culture University, Taipei 111, Taiwan, ROC (China)

    2013-05-15

    Indium oxide (In{sub 2}O{sub 3}) nanorods, nanotowers and tin-doped (Sn:In = 1:100) indium oxide (ITO) nanorods have been fabricated by thermal evaporation. The morphology, microstructure and chemical composition of these three nanoproducts are characterized by FE-SEM, HRTEM and XPS. To further investigate the optoelectronic properties, the I–V curves and cathodoluminescence (CL) spectra are measured. The electrical resistivity of In{sub 2}O{sub 3} nanorods, nanotowers and ITO nanorods are 1.32 kΩ, 0.65 kΩ and 0.063 kΩ, respectively. CL spectra of these three nanoproducts clearly indicate that tin-doped (Sn:In = 1:100) indium oxide (ITO) nanorods cause a blue shift. No doubt ITO nanorods obtain the highest performance among these three nanoproducts, and this also means that Sn-doped In{sub 2}O{sub 3} nanostructures would be the best way to enhance the optoelectronic properties. Additionally, the growing mechanism and the optoelectronic properties of these three nanostructures are discussed. This study is beneficial to the applications of In{sub 2}O{sub 3} nanorods, nanotowers and ITO nanorods in optoelectronic nanodevices.

  15. Solid-state Water-mediated Transport Reduction of Nanostructured Iron Oxides

    Smirnov, Vladimir M.; Povarov, Vladimir G.; Voronkov, Gennadii P.; Semenov, Valentin G.; Murin, Igor' V.; Gittsovich, Viktor N.; Sinel'nikov, Boris M.

    2001-01-01

    The Fe 2+ /Fe 3+ ratio in two-dimensional iron oxide nanosructures (nanolayers with a thickness of 0.3-1.5 nm on silica surface) may be precisely controlled using the transport reduction (TR) technique. The species ≡-O-Fe(OH) 2 and (≡Si-O-) 2 -FeOH forming the surface monolayer are not reduced at 400-600 deg. C because of their covalent bonding to the silica surface, as demonstrated by Moessbauer spectroscopy. Iron oxide microparticles (microstructures) obtained by the impregnation technique, being chemically unbound to silica, are subjected to reduction at T ≥ 500 deg. C with formation of metallic iron in the form of α-Fe. Transport reduction of supported nanostructures (consisting of 1 or 4 monolayers) at T ≥ 600 deg. C produces bulk iron(II) silicate and metallic iron phases. The structural-chemical transformations occurring in transport reduction of supported iron oxide nanolayers are proved to be governed by specific phase processes in the nanostructures themselves

  16. Multivariate data analysis approach to understand magnetic properties of perovskite manganese oxides

    Imamura, N.; Mizoguchi, T.; Yamauchi, H.; Karppinen, M.

    2008-01-01

    Here we apply statistical multivariate data analysis techniques to obtain some insights into the complex structure-property relations in antiferromagnetic (AFM) and ferromagnetic (FM) manganese perovskite systems, AMnO 3 . The 131 samples included in the present analyses are described by 21 crystal-structure or crystal-chemical (CS/CC) parameters. Principal component analysis (PCA), carried out separately for the AFM and FM compounds, is used to model and evaluate the various relationships among the magnetic properties and the various CS/CC parameters. Moreover, for the AFM compounds, PLS (partial least squares projections to latent structures) analysis is performed so as to predict the magnitude of the Neel temperature on the bases of the CS/CC parameters. Finally, so-called PLS-DA (PLS discriminant analysis) method is employed to find out the most influential/characteristic CS/CC parameters that differentiate the two classes of compounds from each other. - Graphical abstract: Statistical multivariate data analysis techniques are applied to detect structure-property relations in antiferromagnetic (AFM) and ferromagnetic (FM) manganese perovskites. For AFM compounds, partial least squares projections to latent structures analysis predict the magnitude of the Neel temperature on the bases of structural parameters only. Moreover, AFM and FM compounds are well separated by means of so-called partial least squares discriminant analysis method

  17. Novel mode of microbial energy metabolism: organic carbon oxidation coupled to dissimilatory reduction of iron or manganese.

    Lovley, D R; Phillips, E J

    1988-06-01

    A dissimilatory Fe(III)- and Mn(IV)-reducing microorganism was isolated from freshwater sediments of the Potomac River, Maryland. The isolate, designated GS-15, grew in defined anaerobic medium with acetate as the sole electron donor and Fe(III), Mn(IV), or nitrate as the sole electron acceptor. GS-15 oxidized acetate to carbon dioxide with the concomitant reduction of amorphic Fe(III) oxide to magnetite (Fe(3)O(4)). When Fe(III) citrate replaced amorphic Fe(III) oxide as the electron acceptor, GS-15 grew faster and reduced all of the added Fe(III) to Fe(II). GS-15 reduced a natural amorphic Fe(III) oxide but did not significantly reduce highly crystalline Fe(III) forms. Fe(III) was reduced optimally at pH 6.7 to 7 and at 30 to 35 degrees C. Ethanol, butyrate, and propionate could also serve as electron donors for Fe(III) reduction. A variety of other organic compounds and hydrogen could not. MnO(2) was completely reduced to Mn(II), which precipitated as rhodochrosite (MnCO(3)). Nitrate was reduced to ammonia. Oxygen could not serve as an electron acceptor, and it inhibited growth with the other electron acceptors. This is the first demonstration that microorganisms can completely oxidize organic compounds with Fe(III) or Mn(IV) as the sole electron acceptor and that oxidation of organic matter coupled to dissimilatory Fe(III) or Mn(IV) reduction can yield energy for microbial growth. GS-15 provides a model for how enzymatically catalyzed reactions can be quantitatively significant mechanisms for the reduction of iron and manganese in anaerobic environments.

  18. Acclimation of a marine microbial consortium for efficient Mn(II) oxidation and manganese containing particle production

    Zhou, Hao, E-mail: zhouhao@dlut.edu.cn [Key Laboratory of Industrial Ecology and Environmental Engineering (Ministry of Education), School of Food and Environment, Dalian University of Technology, Panjin 124221 (China); Pan, Haixia [Key Laboratory of Industrial Ecology and Environmental Engineering (Ministry of Education), School of Food and Environment, Dalian University of Technology, Panjin 124221 (China); Xu, Jianqiang [School of Life Science and Medicine, Dalian University of Technology, Panjin 124221 (China); Xu, Weiping; Liu, Lifen [Key Laboratory of Industrial Ecology and Environmental Engineering (Ministry of Education), School of Food and Environment, Dalian University of Technology, Panjin 124221 (China)

    2016-03-05

    Highlights: • An efficient Mn(II) oxidation marine sediments microbial community was obtained. • High-throughput sequencing indicated new Mn(II) oxidation associated genus. • Na{sub 3}MnPO{sub 4}CO{sub 3} and MnCO{sub 3} were synthesized by the consortium. • Consortium exhibited Mn(II) oxidation performance over a range of harsh conditions. - Abstract: Sediment contamination with metals is a widespread concern in the marine environment. Manganese oxidizing bacteria (MOB) are extensively distributed in various environments, but a marine microbial community containing MOB is rarely reported. In this study, a consortium of marine metal-contaminated sediments was acclimated using Mn(II). The shift in community structure was determined through high-throughput sequencing. In addition, the consortium resisted several harsh conditions, such as toxic metals (1 mM Cu(II) and Fe(III)), and exhibited high Mn(II) oxidation capacities even the Mn(II) concentration was up to 5 mM. Meanwhile, biogenic Mn containing particles were characterized by scanning electron microscope (SEM), X-ray powder diffraction (XRD), and N{sub 2} adsorption/desorption. Dye removal performance of the Mn containing particles was assayed using methylene blue, and 20.8 mg g{sup −1} adsorption capacity was obtained. Overall, this study revealed several new genera associated with Mn(II) oxidation and rare biogenic Na{sub 3}MnPO{sub 4}CO{sub 3.} Results suggested the complexity of natural microbe-mediated Mn transformation.

  19. Mechanistic Understanding of Tungsten Oxide In-Plane Nanostructure Growth via Sequential Infiltration Synthesis

    Kim, Jae Jin; Suh, Hyo Seon; Zhou, Chun; Mane, Anil U.; Lee, Byeongdu; Kim, Soojeong; Emery, Jonathan D.; Elam, Jeffrey W.; Nealey, Paul F.; Fenter, Paul; Fister, Timothy T.

    2018-02-21

    Tungsten oxide (WO3-x) nanostructures with hexagonal in-plane arrangements were fabricated by sequential infiltration synthesis (SIS), using the selective interaction of gas phase precursors with functional groups in one domain of a block copolymer (BCP) self-assembled template. Such structures are highly desirable for various practical applications and as model systems for fundamental studies. The nanostructures were characterized by cross-sectional scanning electron microscopy, grazing-incidence small/wide-angle X-ray scattering (GISAXS/GIWAXS), and X-ray absorption near edge structure (XANES) measurements at each stage during the SIS process and subsequent thermal treatments, to provide a comprehensive picture of their evolution in morphology, crystallography and electronic structure. In particular, we discuss the critical role of SIS Al2O3 seeds toward modifying the chemical affinity and free volume in a polymer for subsequent infiltration of gas phase precursors. The insights into SIS growth obtained from this study are valuable to the design and fabrication of a wide range of targeted nanostructures.

  20. Formation of Self-assembled Nanostructure on Noble Metal Islands Based on Anodized Aluminum Oxide

    Park, Jong Bae; Kim, Young Sic; Kim, Seong Kyu; Lee, Hae Seong

    2004-01-01

    We have developed the methodology to produce nanoscale gold rods using an AAO template. Each gold rod was generated in every AAO pore. This nanoislands array of gold formed over the AAO pores can be used as corner stones for building nanostructures. We demonstrated this by forming a nanostructure on the Au/AAO by binding a self-assembly class of molecules onto the metal islands. Anodized aluminum oxide (AAO) has been considered an attractive template for simple fabrication of highly-ordered nanostructures. It provides a 2-dimensional array of hexagonal cells with pores of uniform diameter and inter-pore distance that are adjustable in the range of a few tens to hundreds of nanometers. It can be easily grown on an aluminum sheet with high purity by a sequence of several electrochemical steps; electro-polishing, the 1st anodization, etching, and the 2nd anodization. The pores are grown vertically with respect to the AAO surface. The regularity of the pore structure is usually limited by the inherent grain domain in the aluminum sheet to a few micrometers, but can be improved to cover many millimeters of monodomain by pre-indenting the aluminum sheet with SiC 7 or Si 3 N 4 molds. Although fabrication of such molds requires elaborate and costly processes with e-beam nanolithography, such potentially superb regularity can be practically applied to fabrication of nanoscale devices in electronics, optics, biosensors, etc

  1. Mesoporous silicon oxide films and their uses as templates in obtaining nanostructured conductive polymers

    Salgado, R.; Arteaga, G. C.; Arias, J. M.

    2018-04-01

    Obtaining conductive polymers (CPs) for the manufacture of OLEDs, solar cells, electrochromic devices, sensors, etc., has been possible through the use of electrochemical techniques that allow obtaining films of controlled thickness with positive results in different applications. Current trends point towards the manufacture of nanomaterials, and therefore it is necessary to develop methods that allow obtaining CPs with nanostructured morphology. This is possible by using a porous template to allow the growth of the polymeric materials. However, prior and subsequent treatments are required to separate the material from the template so that it can be evaluated in the applications mentioned above. This is why mesoporous silicon oxide films (template) are essential for the synthesis of nanostructured polymers since both the template and the polymer are obtained on the electrode surface, and therefore it is not necessary to separate the material from the template. Thus, the material can be evaluated directly in the applications mentioned above. The dimensions of the resulting nanostructures will depend on the power, time and technique used for electropolymerization as well as the monomer and the surfactant of the mesoporous film.

  2. Micro- and Nanostructured Metal Oxide Chemical Sensors for Volatile Organic Compounds

    Alim, M. A.; Penn, B. G.; Currie, J. R., Jr.; Batra, A. K.; Aggarwal, M. D.

    2008-01-01

    Aeronautic and space applications warrant the development of chemical sensors which operate in a variety of environments. This technical memorandum incorporates various kinds of chemical sensors and ways to improve their performance. The results of exploratory investigation of the binary composite polycrystalline thick-films such as SnO2-WO3, SnO2-In2O3, SnO2-ZnO for the detection of volatile organic compound (isopropanol) are reported. A short review of the present status of the new types of nanostructured sensors such as nanobelts, nanorods, nanotube, etc. based on metal oxides is presented.

  3. Oxide nanostructures on a Nb surface and related systems: experiments and ab initio calculations

    Kuznetsov, Mikhail V; Razinkin, A S; Ivanovskii, Alexander L

    2011-01-01

    This review discusses the state of the art in two related research areas: the surfaces of niobium and of its related group IV-VI transition metals, and surface (primarily oxide) nanostructures that form on niobium (and group IV-VI d-metals) due to gas adsorption or impurity diffusion from the bulk. Experimental (X-ray photoelectron spectroscopy, photoelectron diffraction, scanning tunneling microscopy) and theoretical (ab initio simulation) results on d-metal surfaces are summarized and reviewed. (reviews of topical problems)

  4. Near-field effects and energy transfer in hybrid metal-oxide nanostructures.

    Herr, Ulrich; Kuerbanjiang, Balati; Benel, Cahit; Papageorgiou, Giorgos; Goncalves, Manuel; Boneberg, Johannes; Leiderer, Paul; Ziemann, Paul; Marek, Peter; Hahn, Horst

    2013-01-01

    One of the big challenges of the 21st century is the utilization of nanotechnology for energy technology. Nanoscale structures may provide novel functionality, which has been demonstrated most convincingly by successful applications such as dye-sensitized solar cells introduced by M. Grätzel. Applications in energy technology are based on the transfer and conversion of energy. Following the example of photosynthesis, this requires a combination of light harvesting, transfer of energy to a reaction center, and conversion to other forms of energy by charge separation and transfer. This may be achieved by utilizing hybrid nanostructures, which combine metallic and nonmetallic components. Metallic nanostructures can interact strongly with light. Plasmonic excitations of such structures can cause local enhancement of the electrical field, which has been utilized in spectroscopy for many years. On the other hand, the excited states in metallic structures decay over very short lifetimes. Longer lifetimes of excited states occur in nonmetallic nanostructures, which makes them attractive for further energy transfer before recombination or relaxation sets in. Therefore, the combination of metallic nanostructures with nonmetallic materials is of great interest. We report investigations of hybrid nanostructured model systems that consist of a combination of metallic nanoantennas (fabricated by nanosphere lithography, NSL) and oxide nanoparticles. The oxide particles were doped with rare-earth (RE) ions, which show a large shift between absorption and emission wavelengths, allowing us to investigate the energy-transfer processes in detail. The main focus is on TiO2 nanoparticles doped with Eu(3+), since the material is interesting for applications such as the generation of hydrogen by photocatalytic splitting of water molecules. We use high-resolution techniques such as confocal fluorescence microscopy for the investigation of energy-transfer processes. The experiments are

  5. Metal oxide core shell nanostructures as building blocks for efficient light emission (SISGR)

    Chang, Jane P [Univ. of California, Los Angeles, CA (United States); Dorman, James [Univ. of California, Los Angeles, CA (United States); Cheung, Cyrus [Univ. of California, Los Angeles, CA (United States)

    2016-01-12

    The objective of this research is to synthesize core-shell nano-structured metal oxide materials and investigate their structural, electronic and optical properties to understand the microscopic pathways governing the energy conversion process, thereby controlling and improving their efficiency. Specifically, the goal is to use a single metal oxide core-shell nanostructure and a single excitation source to generate photons with long emission lifetime over the entire visible spectrum and when controlled at the right ratio, generating white light. In order to achieve this goal, we need to control the energy transfer between light emitting elements, which dictates the control of their interatomic spacing and spatial distribution. We developed an economical wet chemical process to form the nanostructured core and to control the thickness and composition of the shell layers. With the help from using DOE funded synchrotron radiation facility, we delineated the growth mechanism of the nano-structured core and the shell layers, thereby enhancing our understanding of structure-property relation in these materials. Using the upconversion luminescence and the lifetime measurements as effective feedback to materials sysnthes is and integration, we demonstrated improved luminescence lifetimes of the core-shell nano-structures and quantified the optimal core-multi-shell structure with optimum shell thickness and composition. We developed a rare-earths co-doped LaPO4 core-multishell structure in order to produce a single white light source. It was decided that the mutli-shell method would produce the largest increase in luminescence efficiency while limiting any energy transfer that may occur between the dopant ions. All samples resulted in emission spectra within the accepted range of white light generation based on the converted CIE color coordinates. The white light obtained varied between warm and cool white depending on the layering architecture, allowing for the

  6. Peroxymonosulfate activation and pollutants degradation over highly dispersed CuO in manganese oxide octahedral molecular sieve

    Li, Jun; Ye, Peng; Fang, Jia; Wang, Manye; Wu, Deming; Xu, Aihua; Li, Xiaoxia

    2017-11-01

    Manganese oxide octahedral molecular sieves (OMS-2) supported CuO catalysts were synthesized, characterized and used in the removal of Acid Orange 7 (AO7) in aqueous solution by an oxidation process involving peroxymonosulfate (PMS). It was found that the CuO species were highly dispersed in OMS-2 with a high ratio of easily reduced surface oxygen species. The synergetic effect between CuO and OMS-2 significantly improved the dye degradation rate and catalytic stability, compared with CuO, OMS-2 and supported CuO on other materials. About 97% of the dye was removed within 15 min at neutral solution pH by using 0.2 g/L of CuO/OMS-2 and PMS. The effect of initial solution pH, PMS concentration, reaction temperature and CuO content in the composites on AO7 degradation was also investigated. Mechanism study indicated that SO4-rad radicals generated from the interaction between PMS and Mn and Cu species with different oxidation states, mainly accounted for the degradation.

  7. Mobilization of manganese by basalt associated Mn(II)-oxidizing bacteria from the Indian Ridge System

    Sujith, P.P.; Mourya, B.S.; Krishnamurthi, S.; Meena, R.M.; LokaBharathi, P.A.

    The Indian Ridge System basalt bearing Mn-oxide coatings had todorokite as the major and birnesite as the minor mineral. We posit that microorganisms associated with these basalts participate in the oxidation of Mn and contribute to mineral...

  8. Nanostructured cerium oxide catalyst support: Effects of morphology on the electro activity of gold toward oxidative sensing of glucose

    Gougis, Maxime; Tabet-Aoul, Amel; Ma, Dongling; Mohamedi, Mohamed

    2014-01-01

    We report on the fabrication of nanostructured CeO 2 -gold electrodes by means of laser ablation. The synthetic conditions were varied in order to obtain different morphologies of CeO 2 . The physical and chemical properties of the samples were studied by scanning electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. The effect of the morphology of CeO 2 on the electrocatalytic oxidation of glucose were studied by cyclic voltammetry and square-wave voltammetry. Among the various electrodes fabricated, the CeO 2 coating produced under 10 mTorr of oxygen showed the best supporting catalytic properties for gold by displaying 44 μA cm −2 mM −1 sensitivity for glucose oxidation at near neutral pH values. The detection limit is as low as 10 μM. This electrochemical activity makes the optimized nanostructured electrode potentially useful for non-enzymatic sensing of glucose. (author)

  9. A Hollow-Structured Manganese Oxide Cathode for Stable Zn-MnO₂ Batteries.

    Guo, Xiaotong; Li, Jianming; Jin, Xu; Han, Yehu; Lin, Yue; Lei, Zhanwu; Wang, Shiyang; Qin, Lianjie; Jiao, Shuhong; Cao, Ruiguo

    2018-05-05

    Aqueous rechargeable zinc-manganese dioxide (Zn-MnO₂) batteries are considered as one of the most promising energy storage devices for large scale-energy storage systems due to their low cost, high safety, and environmental friendliness. However, only a few cathode materials have been demonstrated to achieve stable cycling for aqueous rechargeable Zn-MnO₂ batteries. Here, we report a new material consisting of hollow MnO₂ nanospheres, which can be used for aqueous Zn-MnO₂ batteries. The hollow MnO₂ nanospheres can achieve high specific capacity up to ~405 mAh g −1 at 0.5 C. More importantly, the hollow structure of birnessite-type MnO₂ enables long-term cycling stability for the aqueous Zn-MnO₂ batteries. The excellent performance of the hollow MnO₂ nanospheres should be due to their unique structural properties that enable the easy intercalation of zinc ions.

  10. Structure, morphology and electrochemical behaviour of manganese oxides prepared by controlled decomposition of permanganate

    Donne, S.W.; Jones, B.C. [Discipline of Chemistry, University of Newcastle, Callaghan, NSW 2308 (Australia); Hollenkamp, A.F. [CSIRO Energy Technology, Box 312, Clayton South, Vic. 3169 (Australia)

    2010-01-01

    Hydrothermal decomposition of permanganate, conducted in a range of pH-controlled solutions (from strongly acidic to strongly basic), is used to prepare manganese dioxides that are well-suited for use as supercapacitor electrode materials. While permanganate is thermodynamically unstable, the kinetics of its decomposition in an aqueous environment are very slow, until the temperature is raised to {proportional_to}200 C. Although the resultant materials are relatively crystalline and have low total pore volume, their prominent meso-porosity leads to good electrochemical performance. Best behaviour is obtained for material from permanganate decomposition in 0.01 M H{sub 2}SO{sub 4} solution, for which composite electrodes (150 {mu}m thick) yield {proportional_to}150 F g{sup -1} at 5 mV s{sup -1} in a 9 M KOH electrolyte. (author)

  11. Multifunctional nanosheets based on folic acid modified manganese oxide for tumor-targeting theranostic application

    Hao, Yongwei; Wang, Lei; Zhang, Bingxiang; Zhao, Hongjuan; Niu, Mengya; Hu, Yujie; Zheng, Cuixia; Zhang, Hongling; Chang, Junbiao; Zhang, Zhenzhong; Zhang, Yun

    2016-01-01

    It is highly desirable to develop smart nanocarriers with stimuli-responsive drug-releasing and diagnostic-imaging functions for cancer theranostics. Herein, we develop a reduction and pH dual-responsive tumor theranostic platform based on degradable manganese dioxide (MnO2) nanosheets. The MnO2 nanosheets with a size of 20-60 nm were first synthesized and modified with (3-Aminopropyl) trimethoxysilane (APTMS) to get amine-functionalized MnO2, and then functionalized by NH2-PEG2000-COOH (PEG). The tumor-targeting group, folic acid (FA), was finally conjugated with the PEGylated MnO2 nanosheets. Then, doxorubicin (DOX), a chemotherapeutic agent, was loaded onto the modified nanosheets through a physical adsorption, which was designated as MnO2-PEG-FA/DOX. The prepared MnO2-PEG-FA/DOX nanosheets with good biocompatibility can not only efficiently deliver DOX to tumor cells in vitro and in vivo, leading to enhanced anti-tumor efficiency, but can also respond to a slightly acidic environment and high concentration of reduced glutathione (GSH), which caused degradation of MnO2 into manganese ions enabling magnetic resonance imaging (MRI). The longitudinal relaxation rate r 1 was 2.26 mM-1 s-1 at pH 5.0 containing 2 mM GSH. These reduction and pH dual-responsive biodegradable nanosheets combining efficient MRI and chemotherapy provide a novel and promising platform for tumor-targeting theranostic application.

  12. Fabrication of Acrylonitrile-Butadiene-Styrene Nanostructures with Anodic Alumina Oxide Templates, Characterization and Biofilm Development Test for Staphylococcus epidermidis.

    Camille Desrousseaux

    Full Text Available Medical devices can be contaminated by microbial biofilm which causes nosocomial infections. One of the strategies for the prevention of such microbial adhesion is to modify the biomaterials by creating micro or nanofeatures on their surface. This study aimed (1 to nanostructure acrylonitrile-butadiene-styrene (ABS, a polymer composing connectors in perfusion devices, using Anodic Alumina Oxide templates, and to control the reproducibility of this process; (2 to characterize the physico-chemical properties of the nanostructured surfaces such as wettability using captive-bubble contact angle measurement technique; (3 to test the impact of nanostructures on Staphylococcus epidermidis biofilm development. Fabrication of Anodic Alumina Oxide molds was realized by double anodization in oxalic acid. This process was reproducible. The obtained molds present hexagonally arranged 50 nm diameter pores, with a 100 nm interpore distance and a length of 100 nm. Acrylonitrile-butadiene-styrene nanostructures were successfully prepared using a polymer solution and two melt wetting methods. For all methods, the nanopicots were obtained but inside each sample their length was different. One method was selected essentially for industrial purposes and for better reproducibility results. The flat ABS surface presents a slightly hydrophilic character, which remains roughly unchanged after nanostructuration, the increasing apparent wettability observed in that case being explained by roughness effects. Also, the nanostructuration of the polymer surface does not induce any significant effect on Staphylococcus epidermidis adhesion.

  13. Thin, Flexible Supercapacitors Made from Carbon Nanofiber Electrodes Decorated at Room Temperature with Manganese Oxide Nanosheets

    Nataraj, S. K.; Song, Q.; Al-Muhtaseb, S. A.; Dutton, S. E.; Zhang, Q.; Sivaniah, E.

    2013-01-01

    We report the fabrication and electrochemical performance of a flexible thin film supercapacitor with a novel nanostructured composite electrode. The electrode was prepared by in situ coprecipitation of two-dimensional (2D) MnO2 nanosheets at room temperature in the presence of carbon nanofibers (CNFs). The highest specific capacitance of 142 F/g was achieved for CNFs-MnO2 electrodes in sandwiched assembly with PVA-H4SiW12O40nH2O polyelectrolyte separator. Peer Reviewed

  14. Thin, Flexible Supercapacitors Made from Carbon Nanofiber Electrodes Decorated at Room Temperature with Manganese Oxide Nanosheets

    S. K. Nataraj

    2013-01-01

    Full Text Available We report the fabrication and electrochemical performance of a flexible thin film supercapacitor with a novel nanostructured composite electrode. The electrode was prepared by in situ coprecipitation of two-dimensional (2D MnO2 nanosheets at room temperature in the presence of carbon nanofibers (CNFs. The highest specific capacitance of 142 F/g was achieved for CNFs-MnO2 electrodes in sandwiched assembly with PVA-H4SiW12O40·nH2O polyelectrolyte separator.

  15. Synthesis and electrochemical properties of high performance polyhedron sphere like lithium manganese oxide for lithium ion batteries

    Guo, Donglei; Wei, Xiuge; Chang, Zhaorong; Tang, Hongwei; Li, Bao; Shangguan, Enbo; Chang, Kun; Yuan, Xiao-Zi; Wang, Haijiang

    2015-01-01

    Graphical abstract: Polyhedron structured sphere-like LiMn 2 O 4 synthesized from β-MnO 2 nanorod precursor via a solid state reaction at a temperature of 800 °C exhibits excellent rate capability and cycling performance at both 25 °C and 55 °C. - Highlights: • Polyhedron sphere-like LiMn 2 O 4 was synthesized from β-MnO 2 nanorod precursor. • The polyhedron sphere-like LiMn 2 O 4 exhibits excellent rate capability and cycling performance. • The polyhedron sphere-like structure spinel LiMn 2 O 4 suppresses the dissolution of manganese ions. • The polyhedron sphere-like LiMn 2 O 4 has high diffusion coefficient of Li + . - Abstract: Polyhedron structured sphere-like lithium manganese oxide (LiMn 2 O 4 ) is successfully synthesized from β-MnO 2 nanorod precursor via a solid state reaction at a temperature of 800 °C. For comparison, LiMn 2 O 4 materials with nanorod and octahedron structures are also obtained from β-MnO 2 nanorod precursor at temperatures of 700 °C and 900 °C, respectively. The galvanostatic charge–discharge result shows that the polyhedron sphere-like LiMn 2 O 4 sample exhibits the best electrochemical performance at high rate and high temperature. After 100 cycles at 5 C, this electrode is able to maintain 94% of its capacity at 25 °C and 81% at 55 °C. This is attributed to that the polyhedron sphere-like spinel LiMn 2 O 4 can suppress the dissolution of manganese ions. Based on Brunauer Emmett Teller (BET), cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS), the polyhedron sphere-like LiMn 2 O 4 sample has the lowest BET surface area, largest diffusion coefficient of Li + and least charge transfer resistance. This study provides an insight into the capacity fading of LiMn 2 O 4 electrodes and the polyhedron structured sphere-like LiMn 2 O 4 can be a promising material for lithium ion batteries

  16. Nanostructured hydrophobic DC sputtered inorganic oxide coating for outdoor glass insulators

    Dave, V. [Department of Electrical Engineering, Indian Institute of Technology Roorkee, Roorkee 247667 (India); Institute Instrumentation Centre, Indian Institute of Technology, Roorkee, Roorkee 247667 (India); Gupta, H.O. [Department of Electrical Engineering, Indian Institute of Technology Roorkee, Roorkee 247667 (India); Chandra, R., E-mail: ramesfic@gmail.com [Institute Instrumentation Centre, Indian Institute of Technology, Roorkee, Roorkee 247667 (India)

    2014-03-01

    Graphical abstract: - Highlights: • Deposition of contamination on outdoor glass insulators and its physical and economical consequences were discussed. • Synthesis of nanostructured hydrophobic HfO{sub 2} film on glass as a remedial measure by varying DC sputtering power. • Investigated and correlated structural, optical, electrical and hydrophobic properties of HfO{sub 2} films with respect to power. • Optimum results were obtained at a 50 W DC sputtering power. - Abstract: We report the structural, optical and electrical properties of nanostructured hydrophobic inorganic hafnium oxide coating for outdoor glass insulator using DC sputtering technique to combat contamination problem. The properties were studied as a function of DC power. The characterization of the films was done using X-ray diffraction, EDS, surface profilometer, AFM, impedance analyser and water contact angle measurement system. The DC power was varied from 30 to 60 W and found to have a great impact on the properties of hafnium oxide. All the deposited samples were polycrystalline with nanostructured hydrophobic surfaces. The intensity of crystallinity of the film was found to be dependent on sputtering power and hydrophobicity was correlated to the nanoscale roughness of the films. The optical property reveals 80% average transmission for all the samples. The refractive index was found in the range of 1.85–1.92, near to the bulk value. The band gap calculated from transmission data was >5.3 eV for all deposited samples ensuring dielectric nature of the films. Surface energy calculated by two methods was found minimum for the film deposited at 50 W sputtering power. The resistivity was also high enough (∼10{sup 4} Ω cm) to hinder the flow of leakage current through the film. The dielectric constant (ε) was found to be thickness dependent and also high enough (ε{sub max} = 23.12) to bear the large electric field of outdoor insulators.

  17. Nanostructure of propylammonium nitrate in the presence of poly(ethylene oxide) and halide salts

    Stefanovic, Ryan; Webber, Grant B.; Page, Alister J.

    2018-05-01

    Nanoscale structure of protic ionic liquids is critical to their utility as molecular electrochemical solvents since it determines the capacity to dissolve salts and polymers such as poly(ethylene oxide) (PEO). Here we use quantum chemical molecular dynamics simulations to investigate the impact of dissolved halide anions on the nanostructure of an archetypal nanostructured protic ionic liquid, propylammonium nitrate (PAN), and how this impacts the solvation of a model PEO polymer. At the molecular level, PAN is nanostructured, consisting of charged/polar and uncharged/nonpolar domains. The charged domain consists of the cation/anion charge groups, and is formed by their electrostatic interaction. This domain solvophobically excludes the propyl chains on the cation, which form a distinct, self-assembled nonpolar domain within the liquid. Our simulations demonstrate that the addition of Cl- and Br- anions to PAN disrupts the structure within the PAN charged domain due to competition between nitrate and halide anions for the ammonium charge centre. This disruption increases with halide concentration (up to 10 mol. %). However, at these concentrations, halide addition has little effect on the structure of the PAN nonpolar domain. Addition of PEO to pure PAN also disrupts the structure within the charged domain of the liquid due to hydrogen bonding between the charge groups and the terminal PEO hydroxyl groups. There is little other association between the PEO structure and the surrounding ionic liquid solvent, with strong PEO self-interaction yielding a compact, coiled polymer morphology. Halide addition results in greater association between the ionic liquid charge centres and the ethylene oxide components of the PEO structure, resulting in reduced conformational flexibility, compared to that observed in pure PAN. Similarly, PEO self-interactions increase in the presence of Cl- and Br- anions, compared to PAN, indicating that the addition of halide salts to PAN

  18. Supported 3-D Pt nanostructures: the straightforward synthesis and enhanced electrochemical performance for methanol oxidation in an acidic medium

    Li, Zesheng; Ji, Shan; Pollet, Bruno G.; Shen, Pei Kang

    2013-01-01

    Noble metal nanostructures with branched morphologies [i.e., 3-D Pt nanoflowers (NFs)] by tri-dimensionally integrating onto conductive carbon materials are proved to be an efficient and durable electrocatalysts for methanol oxidation. The well-supported 3-D Pt NFs are readily achieved by an efficient cobalt-induced/carbon-mediated galvanic reaction approach. Due to the favorable nanostructures (3-D Pt configuration allowing a facile mass transfer) and supporting effects (including framework stabilization, spatially separate feature, and improved charge transport effects), these 3-D Pt NFs manifest much higher electrocatalytic activity and stability toward methanol oxidation than that of the commercial Pt/C and Pt-based electrocatalysts

  19. Supported 3-D Pt nanostructures: the straightforward synthesis and enhanced electrochemical performance for methanol oxidation in an acidic medium

    Li, Zesheng [Sun Yat-sen University, The State Key Laboratory of Optoelectronic Materials and Technologies, and Guangdong Province Key Laboratory of Low-carbon Chemistry and Energy Conservation, School of Physics and Engineering (China); Ji, Shan; Pollet, Bruno G. [University of the Western Cape, South African Institute for Advanced Materials Chemistry (SAIAMC) (South Africa); Shen, Pei Kang, E-mail: stsspk@mail.sysu.edu.cn [Sun Yat-sen University, The State Key Laboratory of Optoelectronic Materials and Technologies, and Guangdong Province Key Laboratory of Low-carbon Chemistry and Energy Conservation, School of Physics and Engineering (China)

    2013-10-15

    Noble metal nanostructures with branched morphologies [i.e., 3-D Pt nanoflowers (NFs)] by tri-dimensionally integrating onto conductive carbon materials are proved to be an efficient and durable electrocatalysts for methanol oxidation. The well-supported 3-D Pt NFs are readily achieved by an efficient cobalt-induced/carbon-mediated galvanic reaction approach. Due to the favorable nanostructures (3-D Pt configuration allowing a facile mass transfer) and supporting effects (including framework stabilization, spatially separate feature, and improved charge transport effects), these 3-D Pt NFs manifest much higher electrocatalytic activity and stability toward methanol oxidation than that of the commercial Pt/C and Pt-based electrocatalysts.

  20. Vinylene carbonate and tris(trimethylsilyl) phosphite hybrid additives to improve the electrochemical performance of spinel lithium manganese oxide/graphite cells at 60 °C

    Koo, Bonjae; Lee, Jeongmin; Lee, Yongwon; Kim, Jun Ki; Choi, Nam-Soon

    2015-01-01

    Highlights: •The combination of tris(trimethylsilyl) phosphite and vinylene carbonate improves the electrochemical performance of lithium manganese oxide/graphite cells at 60 °C. •Removal of hydrogen fluoride and water by tris(trimethylsilyl) phosphite suppresses manganese dissolution from lithium manganese oxide. -- Abstract: The organophosphorus compounds tris(trimethylsilyl) phosphite (TMSP) and vinylene carbonate (VC) have been considered for use as functional additives to improve the electrochemical performance of Li 1.1 Mn 1.86 Mg 0.04 O 4 (LMO)/graphite full cells. Our investigation reveals that the combination of VC and TMSP as additives enhances the cycling properties and storage performance of full cells at 60 °C. The unique functions of the TMSP additive in the VC electrolyte are investigated via ex situ X-ray photoelectron spectroscopy (XPS) and 19 F nuclear magnetic resonance (NMR) measurements. The TMSP additive effectively eliminates trace water and hydrogen fluoride (HF) and produces a protective film on the LMO cathode that alleviates manganese dissolution at 60 °C