Electrochemically driven three-phase interlines into insulator compounds: electroreduction of solid SiO2 in molten CaCl2.

PubMed

Xiao, Wei; Jin, Xianbo; Deng, Yuan; Wang, Dihua; Hu, Xiaohong; Chen, George Z

2006-08-11

The electrochemical reduction of solid SiO2 (quartz) to Si is studied in molten CaCl2 at 1173 K. Experimental observations are compared and agree well with a novel penetration model in relation with electrochemistry at the dynamic conductor|insulator|electrolyte three-phase interlines. The findings show that the reduction of a cylindrical quartz pellet at certain potentials is mainly determined by the diffusion of the O(2-) ions and also the ohmic polarisation in the reduction-generated porous silicon layer. The reduction rate increases with the overpotential to a maximum after which the process is retarded, most likely due to precipitation of CaO in the reaction region (cathodic passivation). Data are reported on the reduction rate, current efficiency and energy consumption during the electroreduction of quartz under potentiostatic conditions. These theoretical and experimental findings form the basis for an in-depth discussion on the optimisation of the electroreduction method for the production of silicon.

Combined Ceria Reduction and Methane Reforming in a Solar-Driven Particle-Transport Reactor.

PubMed

Welte, Michael; Warren, Kent; Scheffe, Jonathan R; Steinfeld, Aldo

2017-09-20

We report on the experimental performance of a solar aerosol reactor for carrying out the combined thermochemical reduction of CeO 2 and reforming of CH 4 using concentrated radiation as the source of process heat. The 2 kW th solar reactor prototype utilizes a cavity receiver enclosing a vertical Al 2 O 3 tube which contains a downward gravity-driven particle flow of ceria particles, either co-current or counter-current to a CH 4 flow. Experimentation under a peak radiative flux of 2264 suns yielded methane conversions up to 89% at 1300 °C for residence times under 1 s. The maximum extent of ceria reduction, given by the nonstoichiometry δ (CeO 2-δ ), was 0.25. The solar-to-fuel energy conversion efficiency reached 12%. The syngas produced had a H 2 :CO molar ratio of 2, and its calorific value was solar-upgraded by 24% over that of the CH 4 reformed.

Combined Ceria Reduction and Methane Reforming in a Solar-Driven Particle-Transport Reactor

PubMed Central

2017-01-01

We report on the experimental performance of a solar aerosol reactor for carrying out the combined thermochemical reduction of CeO2 and reforming of CH4 using concentrated radiation as the source of process heat. The 2 kWth solar reactor prototype utilizes a cavity receiver enclosing a vertical Al2O3 tube which contains a downward gravity-driven particle flow of ceria particles, either co-current or counter-current to a CH4 flow. Experimentation under a peak radiative flux of 2264 suns yielded methane conversions up to 89% at 1300 °C for residence times under 1 s. The maximum extent of ceria reduction, given by the nonstoichiometry δ (CeO2−δ), was 0.25. The solar-to-fuel energy conversion efficiency reached 12%. The syngas produced had a H2:CO molar ratio of 2, and its calorific value was solar-upgraded by 24% over that of the CH4 reformed. PMID:28966440

The influence of NH3 on NO2 conversion in a dc corona discharge in N2:O2:CO2:NO2:NH3 mixture

NASA Astrophysics Data System (ADS)

Dors, Mirosław; Mizeraczyk, Jerzy; Czech, Tadeusz; Konieczka, Jerzy

1996-10-01

The aim of this paper is to investigate the influence of NH3 additive (540-1470 ppm) on the conversion of NO2 and the creation of NO and N2O in a mixture of N2:O2:CO2: NO2:NH3 subjected to the so-called direct current (dc) corona discharge. The dc corona discharge was generated in a needle-to-plate reactor. Seven positively polarized needles were used as one electrode and a stainless steel plate as the other. The time-averaged discharge current was varied from 0 to 7 mA. It was found that the dc corona discharge decomposed NO2 and produced NO and N2O. The reduction of NO2 was higher without NH3 additive if the residence time of the operating gas was relatively short. However, in a longer corona discharge processing the NH3 additive may be useful for reduction of NO2.

Mg-Doped CuFeO 2 Photocathodes for Photoelectrochemical Reduction of Carbon Dioxide

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

Gu, Jing; Wuttig, Anna; Krizan, Jason W.

2013-05-22

Mg-doped CuFeO 2 delafossite is reported to be photoelectrochemically active for CO 2 reduction. The material was prepared via conventional solid-state methods, and subsequently assembled into an electrode as a pressed pellet. Addition of a Mg 2+ dopant is found to substantially improve the conductivity of the material, with 0.05% Mg-doped CuFeO 2 electrodes displaying photocathodic currents under visible irradiation. Photocurrent is found to onset at irradiation wavelengths of ~800 nm with the incident photon-to-current efficiency reaching a value of 14% at 340 nm using an applied electrode potential of –0.4 V vs SCE. Photoelectrodes were determined to have amore » –1.1 V vs SCE conduction band edge and were found capable of the reduction of CO 2 to formate at 400 mV of underpotential. The conversion efficiency is maximized at –0.9 V vs SCE, with H 2 production contributing as a considerable side reaction. Lastly, these results highlight the potential to produce Mg-doped p-type metal oxide photocathodes with a band structure tuned to optimize CO 2 reduction.« less

RAPID COMMUNICATION: Effect of strain, magnetic field and field angle on the critical current density of Y Ba2Cu3O7-δ coated conductors

NASA Astrophysics Data System (ADS)

van der Laan, D. C.; Ekin, J. W.; Douglas, J. F.; Clickner, C. C.; Stauffer, T. C.; Goodrich, L. F.

2010-07-01

A large, magnetic-field-dependent, reversible reduction in critical current density with axial strain in Y Ba2Cu3O7-δ coated conductors at 75.9 K has been measured. This effect may have important implications for the performance of Y Ba2Cu3O7-δ coated conductors in applications where the conductor experiences large stresses in the presence of a magnetic field. Previous studies have been performed only under tensile strain and could provide only a limited understanding of the in-field strain effect. We now have constructed a device for measuring the critical current density as a function of axial compressive and tensile strain and applied magnetic field as well as magnetic field angle, in order to determine the magnitude of this effect and to create a better understanding of its origin. The reversible reduction in critical current density with strain becomes larger with increasing magnetic field at all field angles. At 76 K the critical current density is reduced by about 30% at - 0.5% strain when a magnetic field of 5 T is applied parallel to the c-axis of the conductor or 8 T is applied in the ab-plane, compared to a reduction of only 13% in self-field. Differences in the strain response of the critical current density at various magnetic field angles indicate that the pinning mechanisms in Y Ba2Cu3O7-δ coated conductors are uniquely affected by strain. Contribution of NIST, not subject to US copyright.

Effect of high-pressure H{sub 2}O treatment on elimination of interfacial GeO{sub X} layer between ZrO{sub 2} and Ge stack

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

Huang, Chen-Shuo; Liu, Po-Tsun

2011-08-22

This investigation demonstrates the effect of high-pressure H{sub 2}O treatment on the elimination of the interfacial germanium suboxide (GeO{sub X}) layer between ZrO{sub 2} and Ge. The formation of GeO{sub X} interlayer increases the gate-leakage current and worsen the controllability of the gate during deposition or thermal cycles. X-ray photoelectron spectroscopy and high-resolution transmission electron microscopy reveal that high-pressure H{sub 2}O treatment eliminates the interfacial GeO{sub X} layer. The physical mechanism involves the oxidation of non-oxidized Zr with H{sub 2}O and the reduction of GeO{sub X} by H{sub 2}. Treatment with H{sub 2}O reduces the gate-leakage current of a ZrO{submore » 2}/Ge capacitor by a factor of 1000.« less

The O2 reduction at the IFC modified O2 fuel cell electrode

NASA Technical Reports Server (NTRS)

Fielder, William L.; Singer, Joseph; Baldwin, Richard S.; Johnson, Richard E.

1992-01-01

The International Fuel Corporation (IFC) state of the art (SOA) O2 electrode (Au-10 percent Pt electrocatalyst by weight) is currently being used in the alkaline H2-O2 fuel cell in the NASA Space Shuttle. Recently, IFC modified O2 electrode, as a possible replacement for the SOA electrode. In the present study, O2 reduction data were obtained for the modified electrode at temperatures between 23.3 and 91.7 C. BET measurements gave an electrode BET surface area of about 2070 sq. cm/sq. cm of geometric surface area. The Tafel data could be fitted to two straight line regions. The slope for the lower region, designated as the 0.04 V/decade region, was temperature dependent, and the transfer coefficient was about 1.5. The 'apparent' energy of activation for this region was about 19 kcal/mol. An O2 reduction mechanism for this 0.04 region is presented. In the upper region, designated as the 0.08 V/decade region, diffusion may be the controlling process. Tafel data are presented to illustrate the increase in performance with increasing temperature.

Hydrogen peroxide-induced reduction of delayed rectifier potassium current in hippocampal neurons involves oxidation of sulfhydryl groups.

PubMed

Hasan, Sonia M K; Redzic, Zoran B; Alshuaib, Waleed B

2013-07-03

This study examined the effect of H2O2 on the delayed rectifier potassium current (IKDR) in isolated hippocampal neurons. Whole-cell voltage-clamp experiments were performed on freshly dissociated hippocampal CA1 neurons of SD rats before and after treatment with H2O2. To reveal the mechanism behind H2O2-induced changes in IKDR, cells were treated with different oxidizing and reducing agents. External application of membrane permeable H2O2 reduced the amplitude and voltage-dependence of IKDR in a concentration dependent manner. Desferoxamine (DFO), an iron-chelator that prevents hydroxyl radical (OH) generation, prevented H2O2-induced reduction in IKDR. Application of the sulfhydryl-oxidizing agent 5,5 dithio-bis-nitrobenzoic acid (DTNB) mimicked the effect of H2O2. Sulfhydryl-reducing agents dithiothreitol (DTT) and glutathione (GSH) alone did not affect IKDR; however, DTT and GSH reversed and prevented the H2O2-induced inhibition of IKDR, respectively. Membrane impermeable agents GSH and DTNB showed effects only when added intracellularly identifying intracellular sulfhydryl groups as potential targets for hydroxyl-mediated oxidation. However, the inhibitory effects of DTNB and H2O2 at the positive test potentials were completely and partially abolished by DTT, respectively, suggesting an additional mechanism of action for H2O2, that is not shared by DTNB. In summary, this study provides evidence for the redox modulation of IKDR, identifies hydroxyl radical as an intermediate oxidant responsible for the H2O2-induced decrease in current amplitude and identifies intracellular sulfhydryl groups as an oxidative target. Copyright © 2013 Elsevier B.V. All rights reserved.

Silicon Photoelectrode Thermodynamics and Hydrogen Evolution Kinetics Measured by Intensity-Modulated High-Frequency Resistivity Impedance Spectroscopy

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

Anderson, Nicholas C.; Carroll, Gerard M.; Pekarek, Ryan T.

Here, we present an impedance technique based on light intensity-modulated high-frequency resistivity (IMHFR) that provides a new way to elucidate both the thermodynamics and kinetics in complex semiconductor photoelectrodes. We apply IMHFR to probe electrode interfacial energetics on oxide-modified semiconductor surfaces frequently used to improve the stability and efficiency of photoelectrochemical water splitting systems. Combined with current density-voltage measurements, the technique quantifies the overpotential for proton reduction relative to its thermodynamic potential in Si photocathodes coated with three oxides (SiO x, TiO 2, and Al 2O 3) and a Pt catalyst. In pH 7 electrolyte, the flatband potentials of TiOmore » 2- and Al 2O 3-coated Si electrodes are negative relative to samples with native SiO x, indicating that SiO x is a better protective layer against oxidative electrochemical corrosion than ALD-deposited crystalline TiO 2 or Al 2O 3. Adding a Pt catalyst to SiO x/Si minimizes proton reduction overpotential losses but at the expense of a reduction in available energy characterized by a more negative flatband potential relative to catalyst-free SiO x/Si.« less

Silicon Photoelectrode Thermodynamics and Hydrogen Evolution Kinetics Measured by Intensity-Modulated High-Frequency Resistivity Impedance Spectroscopy

DOE PAGES

Anderson, Nicholas C.; Carroll, Gerard M.; Pekarek, Ryan T.; ...

2017-10-05

Here, we present an impedance technique based on light intensity-modulated high-frequency resistivity (IMHFR) that provides a new way to elucidate both the thermodynamics and kinetics in complex semiconductor photoelectrodes. We apply IMHFR to probe electrode interfacial energetics on oxide-modified semiconductor surfaces frequently used to improve the stability and efficiency of photoelectrochemical water splitting systems. Combined with current density-voltage measurements, the technique quantifies the overpotential for proton reduction relative to its thermodynamic potential in Si photocathodes coated with three oxides (SiO x, TiO 2, and Al 2O 3) and a Pt catalyst. In pH 7 electrolyte, the flatband potentials of TiOmore » 2- and Al 2O 3-coated Si electrodes are negative relative to samples with native SiO x, indicating that SiO x is a better protective layer against oxidative electrochemical corrosion than ALD-deposited crystalline TiO 2 or Al 2O 3. Adding a Pt catalyst to SiO x/Si minimizes proton reduction overpotential losses but at the expense of a reduction in available energy characterized by a more negative flatband potential relative to catalyst-free SiO x/Si.« less

The Development of Models for Carbon Dioxide Reduction Technologies for Spacecraft Air Revitalization

NASA Technical Reports Server (NTRS)

Swickrath, Michael J.; Anderson, Molly

2012-01-01

Through the respiration process, humans consume oxygen (O2) while producing carbon dioxide (CO2) and water (H2O) as byproducts. For long term space exploration, CO2 concentration in the atmosphere must be managed to prevent hypercapnia. Moreover, CO2 can be used as a source of oxygen through chemical reduction serving to minimize the amount of oxygen required at launch. Reduction can be achieved through a number of techniques. NASA is currently exploring the Sabatier reaction, the Bosch reaction, and co- electrolysis of CO2 and H2O for this process. Proof-of-concept experiments and prototype units for all three processes have proven capable of returning useful commodities for space exploration. All three techniques have demonstrated the capacity to reduce CO2 in the laboratory, yet there is interest in understanding how all three techniques would perform at a system level within a spacecraft. Consequently, there is an impetus to develop predictive models for these processes that can be readily rescaled and integrated into larger system models. Such analysis tools provide the ability to evaluate each technique on a comparable basis with respect to processing rates. This manuscript describes the current models for the carbon dioxide reduction processes under parallel developmental efforts. Comparison to experimental data is provided were available for verification purposes.

Effect of Rapid Thermal Annealing on the Electrical Characteristics of ZnO Thin-Film Transistors

NASA Astrophysics Data System (ADS)

Remashan, Kariyadan; Hwang, Dae-Kue; Park, Seong-Ju; Jang, Jae-Hyung

2008-04-01

Thin-film transistors (TFTs) with a bottom-gate configuration were fabricated with an RF magnetron sputtered undoped zinc oxide (ZnO) channel layer and plasma-enhanced chemical vapor deposition (PECVD) grown silicon nitride as a gate dielectric. Postfabrication rapid thermal annealing (RTA) and subsequent nitrous oxide (N2O) plasma treatment were employed to improve the performance of ZnO TFTs in terms of on-current and on/off current ratio. The RTA treatment increases the on-current of the TFT significantly, but it also increases its off-current. The off-current of 2×10-8 A and on/off current ratio of 3×103 obtained after the RTA treatment were improved to 10-10 A and 105, respectively, by the subsequent N2O plasma treatment. The better device performance can be attributed to the reduction of oxygen vacancies at the top region of the channel due to oxygen incorporation from the N2O plasma. X-ray photoelectron spectroscopy (XPS) analysis of the TFT samples showed that the RTA-treated ZnO surface has more oxygen vacancies than as-deposited samples, which results in the increased drain current. The XPS study also showed that the subsequent N2O plasma treatment reduces oxygen vacancies only at the surface of ZnO so that the better off-current and on/off current ratio can be obtained.

Role of Cu-Ion Doping in Cu-α-MnO 2 Nanowire Electrocatalysts for the Oxygen Reduction Reaction

DOE PAGES

Davis, Danae J.; Lambert, Timothy N.; Vigil, Julian A.; ...

2014-07-09

The role of Cu-ion doping in α-MnO 2 electrocatalysts for the oxygen reduction reaction in alkaline electrolyte was investigated. Copper doped α-MnO 2 nanowires (Cu-α-MnO 2) were prepared with varying amounts of Cu 2+ using a solvothermal method. The electrocatalytic dataindicates that Cu-α-MnO 2 nanowires have higher terminal current densities, enhanced kinetic rate constants, and improved charge transfer resistances that trend with Cu-content, exceeding values attained by α-MnO 2 alone. The observed improvement in catalytic behavior correlates with an increase in Mn 3+ content for the Cu-α-MnO 2 nanowires. The Mn 3+/Mn 4+ couple is themediator for the rate-limiting redoxmore » driven O 2 -/OH - exchange. It is proposed that O 2 adsorbs viaan axial site (the e g orbital on the Mn 3+ d 4 ion) at the surface, or at edge defects, of the nanowireand that the increase in covalent nature of the nanowire with Cu-ion doping leads to stabilization of O 2 adsorbates and faster rates of reduction. This work is applicable to other manganese oxide electrocatalysts and shows for the first time there is a correlation for manganese oxides between electrocatalytic activity for the ORR in alkaline electrolyte and an increase in Mn 3+ character of the oxide.« less

Chemical and Electrochemical Processing of Aluminum Dross Using Molten Salts

NASA Astrophysics Data System (ADS)

Yan, Xiao Y.

2008-04-01

A novel molten salt process was investigated, where Al, as metal or contained in Al2O3 and AlN, was recovered from Al dross by chemical or direct electrochemical reduction in electrolytic cells. Electrolysis experiments were carried out under argon at temperatures from 1123 to 1243 K. In order to better understand the reduction behavior, the as-received Al dross was simulated using simplified systems, including pure Al2O3, pure AlN, an Al2O3/AlN binary mixture, and an Al2O3/AlN/Al ternary mixture. The reduction of the as-received dross was also studied experimentally. The studies showed that solid Al2O3 was chemically reduced by the Ca in a Ca-saturated Ca-CaCl2 melt to form Al2Ca or electrochemically reduced to Al-rich Al-Ca alloys and that the Al value in the Al2O3 was easily recovered from the Al drosses. It was found experimentally that solid AlN in the drosses could not be calciothermically reduced to any extent, consistent with thermodynamic evaluations. It was also found that the direct electrochemical reduction of the AlN in the drosses was confined to three phase boundaries (3PBs) between the AlN, the electrolyte, and the current collector and could not be enhanced by using the LiCl-containing chloride melt or the chloride-fluoride melts studied. The presence of Al powder in the Al2O3/AlN mixture facilitated the direct electrochemical reduction of both Al2O3 and AlN. The reduction mechanisms are discussed based upon the present experimental observations. Flow sheets for recovering the metallic Al and the Al in the Al2O3 and AlN from Al dross are finally proposed.

Enhanced Photoelectrocatalytic Decomplexation of Cu-EDTA and Cu Recovery by Persulfate Activated by UV and Cathodic Reduction.

PubMed

Zeng, Huabin; Liu, Shanshan; Chai, Buyu; Cao, Di; Wang, Yan; Zhao, Xu

2016-06-21

In order to enhance Cu-EDTA decomplexation and copper cathodic recovery via the photoelectrocatalytic (PEC) process, S2O8(2-) was introduced into the PEC system with a TiO2/Ti photoanode. At a current density of 0.2 mA/cm(2) and initial solution pH of 3.0, the decomplexation ratio of Cu complexes was increased from 47.5% in the PEC process to 98.4% with 5 mM S2O8(2-) addition into the PEC process (PEC/S2O8(2-)). Correspondently, recovery percentage of Cu was increased to 98.3% from 47.4% within 60 min. It was observed that nearly no copper recovery occurred within the initial reaction period of 10 min. Combined with the analysis of ESR and electrochemical LSV curves, it was concluded that activation of S2O8(2-) into SO4(·-) radicals by cathodic reduction occurred, which was prior to the reduction of liberated Cu(2+) ions. UV irradiation of S2O8(2-) also led to the production of SO4(·-). The generated SO4(·-) radicals enhanced the oxidation of Cu-EDTA. After the consumption of S2O8(2-), the Cu recovery via cathodic reduction proceeded quickly. Acidification induced by the transformation of SO4(·-) to OH· favored the copper cathodic recovery. The combined PEC/S2O8(2-) process was also efficient for the TOC removal from a real electroplating wastewater with the Cu recovery efficiency higher than 80%.

A Perspective on the Selective Catalytic Reduction (SCR) of NO with NH 3 by Supported V 2O 5 –WO 3/TiO 2 Catalysts

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

Lai, Jun-Kun; Wachs, Israel E.

We report the selective catalytic reduction (SCR) of NO x with NH 3 to harmless N 2 and H 2O plays a crucial role in reducing highly undesirable NO x acid gas emissions from large utility boilers, industrial boilers, municipal waste plants, and incinerators. The supported V 2O 5 –WO 3/TiO 2 catalysts have become the most widely used industrial catalysts for these SCR applications since introduction of this technology in the early 1970s. Lastly, this Perspective examines the current fundamental understanding and recent advances of the supported V 2O 5 –WO 3/TiO 2 catalyst system: (i) catalyst synthesis, (ii)more » molecular structures of titaniasupported vanadium and tungsten oxide species, (iii) surface acidity, (iv) catalytic active sites, (v) surface reaction intermediates, (vi) reaction mechanism, (vii) ratedetermining- step, and (viii) reaction kinetics.« less

A Perspective on the Selective Catalytic Reduction (SCR) of NO with NH 3 by Supported V 2O 5 –WO 3/TiO 2 Catalysts

DOE PAGES

Lai, Jun-Kun; Wachs, Israel E.

2018-06-04

We report the selective catalytic reduction (SCR) of NO x with NH 3 to harmless N 2 and H 2O plays a crucial role in reducing highly undesirable NO x acid gas emissions from large utility boilers, industrial boilers, municipal waste plants, and incinerators. The supported V 2O 5 –WO 3/TiO 2 catalysts have become the most widely used industrial catalysts for these SCR applications since introduction of this technology in the early 1970s. Lastly, this Perspective examines the current fundamental understanding and recent advances of the supported V 2O 5 –WO 3/TiO 2 catalyst system: (i) catalyst synthesis, (ii)more » molecular structures of titaniasupported vanadium and tungsten oxide species, (iii) surface acidity, (iv) catalytic active sites, (v) surface reaction intermediates, (vi) reaction mechanism, (vii) ratedetermining- step, and (viii) reaction kinetics.« less

The Development of Models for Carbon Dioxide Reduction Technologies for Spacecraft Air Revitalization

NASA Technical Reports Server (NTRS)

Swickrath, Michael J.; Anderson, Molly

2011-01-01

Through the respiration process, humans consume oxygen (O2) while producing carbon dioxide (CO2) and water (H2O) as byproducts. For long term space exploration, CO2 concentration in the atmosphere must be managed to prevent hypercapnia. Moreover, CO2 can be used as a source of oxygen through chemical reduction serving to minimize the amount of oxygen required at launch. Reduction can be achieved through a number of techniques. The National Aeronautics and Space Administration (NASA) is currently exploring the Sabatier reaction, the Bosch reaction, and co-electrolysis of CO2 and H2O for this process. Proof-of-concept experiments and prototype units for all three processes have proven capable of returning useful commodities for space exploration. While all three techniques have demonstrated the capacity to reduce CO2 in the laboratory, there is interest in understanding how all three techniques would perform at a system-level within a spacecraft. Consequently, there is an impetus to develop predictive models for these processes that can be readily re-scaled and integrated into larger system models. Such analysis tools provide the ability to evaluate each technique on a comparable basis with respect to processing rates. This manuscript describes the current models for the carbon dioxide reduction processes under parallel developmental e orts. Comparison to experimental data is provided were available for veri cation purposes.

Electrochemical pretreatment of amino-carbon nanotubes on graphene support as a novel platform for bilirubin oxidase with improved bioelectrocatalytic activity towards oxygen reduction.

PubMed

Navaee, Aso; Salimi, Abdollah; Jafari, Fereydoon

2015-03-23

The electrochemical conditioning of amino-carbon nanotubes (CNTs) on a graphene support in an alkaline solution is used to produce -NHOH as hydrophilic functional groups for the efficient immobilization of bilirubin oxidase enzyme. The application of the immobilized enzyme for the direct electrocatalytic reduction of O2 is investigated. The onset potential of 0.81 V versus NHE and peak current density of 2.3 mA cm(-2) for rotating modified electrode at 1250 rpm, indicate improved biocatalytic activity of the proposed system for O2 reduction. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Cu2O-tipped ZnO nanorods with enhanced photoelectrochemical performance for CO2 photoreduction

NASA Astrophysics Data System (ADS)

Iqbal, Muzaffar; Wang, Yanjie; Hu, Haifeng; He, Meng; Hassan Shah, Aamir; Lin, Lin; Li, Pan; Shao, Kunjuan; Reda Woldu, Abebe; He, Tao

2018-06-01

The design of Cu2O-tipped ZnO nanorods is proposed here aiming at enhanced photoelectrochemical properties. The tip-selective deposition of Cu2O is confirmed by scanning transmission electron microscopy (STEM). The photoinduced charge behavior like charge generation, separation and transport has been thoroughly studied by UV-vis absorption analysis and different photoelectrochemical characterizations, including transient photocurrent, incident photon-to-current efficiency (IPCE), electrochemical impedance spectroscopy (EIS), intensity-modulated photocurrent spectroscopy (IMPS), and Mott-Schottky measurements. The photoelectrochemical characterizations clearly indicate that ZnO/Cu2O structures exhibit much higher performance than pristine ZnO, due to the formation of p-n junction, as well as the tip selective growth of Cu2O on ZnO. Photocatalytic CO2 reduction in aqueous solution under UV-visible light illumination shows that CO is the main product, and with the increase of the Cu2O content in the heterostructure, the CO yield increases. This work shows that Cu2O-tipped ZnO nanorods possess improved behavior of charge generation, separation and transport, which may work as a potential candidate for photocatalytic CO2 reduction.

Photoassisted Oxygen Reduction Reaction in H2 -O2 Fuel Cells.

PubMed

Zhang, Bingqing; Wang, Shengyang; Fan, Wenjun; Ma, Weiguang; Liang, Zhenxing; Shi, Jingying; Liao, Shijun; Li, Can

2016-11-14

The oxygen reduction reaction (ORR) is a key step in H 2 -O 2 fuel cells, which, however, suffers from slow kinetics even for state-of-the-art catalysts. In this work, by making use of photocatalysis, the ORR was significantly accelerated with a polymer semiconductor (polyterthiophene). The onset potential underwent a positive shift from 0.66 to 1.34 V, and the current was enhanced by a factor of 44 at 0.6 V. The improvement was further confirmed in a proof-of-concept light-driven H 2 -O 2 fuel cell, in which the open circuit voltage (V oc ) increased from 0.64 to 1.18 V, and the short circuit current (J sc ) was doubled. This novel tandem structure combining a polymer solar cell and a fuel cell enables the simultaneous utilization of photo- and electrochemical energy, showing promising potential for applications in energy conversion and storage. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Forchlorfenuron detection based on its inhibitory effect towards catalase immobilized on boron nitride substrate.

PubMed

Xu, Qin; Cai, Lijuan; Zhao, Huijie; Tang, Jiaqian; Shen, Yuanyuan; Hu, Xiaoya; Zeng, Haibo

2015-01-15

An enzymatic procedure based on a catalase biosensor for the detection of forchlorfenuron (CPPU) has been reported in this work. Catalase was immobilized on boron nitride (BN) sheets dispersed in chitosan by adsorption. The immobilized catalase exhibited direct electron transfer character and excellent electrocatalytic activity towards H2O2 reduction. After introducing CPPU into the H2O2 containing phosphate buffer solution, the catalase-catalyzed H2O2 reduction current decreased. By measuring the current decrease, CPPU can be determined in the range of 0.5-10.0 µM with the detection limit of 0.07 μM. The non-competitive inhibition behavior of CPPU towards catalase was verified by the Lineweaver-Burk plots. Long stability character has been ascribed to this biosensor. Possible use of this biosensor in flow systems is illustrated. The proposed biosensor has been successfully applied to CPPU determination in fruits samples with satisfactory results. Copyright © 2014 Elsevier B.V. All rights reserved.

Thermal and electrochemical behaviour of C/Li xCoO 2 cell during safety test

NASA Astrophysics Data System (ADS)

Doh, Chil-Hoon; Kim, Dong-Hun; Kim, Hyo-Suck; Shin, Hye-Min; Jeong, Young-Dong; Moon, Seong-In; Jin, Bong-Soo; Eom, Seung Wook; Kim, Hyun-Soo; Kim, Ki-Won; Oh, Dae-Hee; Veluchamy, Angathevar

Thermal and electrochemical processes in a 1000 mAh lithium-ion pouch cell with a graphite anode and a Li xCoO 2 cathode during a safety test are examined. In overcharge tests, the forced current shifts the cell voltage to above 4.2 V. This causes a cell charged at the 1 C rate to lose cycleability and a cell charged at the 3 C rate to undergo explosion. In nail penetration and impact tests, a high discharge current passing through the cells gives rise to thermal runaway. These overcharge and high discharge currents promote joule heat within the cells and leads to decomposition and release of oxygen from the de-lithiated Li xCoO 2 and combustion of carbonaceous materials. X-ray diffraction analysis reveals the presence of Co 3O 4 in the cathode material of a 4.5 V cell heated to 400 °C. The major cathode product formed after the combustion process cells abused by forced current is Co 3O 4 and by discharge current the products are LiCoO 2 and Co 3O 4. The formation of a trace quantity of CoO through the reduction of Co 3O 4 by virtue of the reducing power of the organic solvent is also discussed.

Study of Electrocatalytic Properties of Metal–Organic Framework PCN-223 for the Oxygen Reduction Reaction

DOE PAGES

Usov, Pavel M.; Huffman, Brittany; Epley, Charity C.; ...

2017-03-27

Here, a highly robust metal–organic framework (MOF) constructed from Zr 6 oxo clusters and Fe(III) porphyrin linkers, PCN-223-Fe was investigated as a heterogeneous catalyst for oxygen reduction reaction (ORR). Films of the framework were grown on a conductive FTO substrate and showed a high catalytic current upon application of cathodic potentials and achieved high H 2O/H 2O 2 selectivity. In addition, the effect of the proton source on the catalytic performance was also investigated.

Low-Temperature Molten-Salt Production of Silicon Nanowires by the Electrochemical Reduction of CaSiO3.

PubMed

Dong, Yifan; Slade, Tyler; Stolt, Matthew J; Li, Linsen; Girard, Steven N; Mai, Liqiang; Jin, Song

2017-11-13

Silicon is an extremely important technological material, but its current industrial production by the carbothermic reduction of SiO 2 is energy intensive and generates CO 2 emissions. Herein, we developed a more sustainable method to produce silicon nanowires (Si NWs) in bulk quantities through the direct electrochemical reduction of CaSiO 3 , an abundant and inexpensive Si source soluble in molten salts, at a low temperature of 650 °C by using low-melting-point ternary molten salts CaCl 2 -MgCl 2 -NaCl, which still retains high CaSiO 3 solubility, and a supporting electrolyte of CaO, which facilitates the transport of O 2- anions, drastically improves the reaction kinetics, and enables the electrolysis at low temperatures. The Si nanowire product can be used as high-capacity Li-ion battery anode materials with excellent cycling performance. This environmentally friendly strategy for the practical production of Si at lower temperatures can be applied to other molten salt systems and is also promising for waste glass and coal ash recycling. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Applications of Tunable TiO2 Nanotubes as Nanotemplate and Photovoltaic Device

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

Li, Dongdong; Chang, Pai-Chun; Chien, Chung-Jen

2010-10-26

Highly ordered anodic titanium oxide (ATO) TiO{sub 2} nanotube film has been synthesized via a typical two-step anodization method. Following a reductive doping approach, metallic materials (copper and nickel) can be efficiently electrodeposited into the nanotubes. This versatile process yields reproducible tubular structures in ATO membranes, because of the conductive nature of crystallized TiO{sub 2}, yielding promising potential for nanotemplate applications. In this paper, we present a dye-sensitized solar cell constructed by employing such ATO films. It is observed that the reductive doping treatment can also enhance the solar cell’s short current density and fill factor, resulting in an improvedmore » energy conversion efficiency.« less

Temperature Dependence of the Oxygen Reduction Mechanism in Nonaqueous Li–O 2 Batteries

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

Liu, Bin; Xu, Wu; Zheng, Jianming

The temperature dependence of the oxygen reduction mechanism in Li-O 2 batteries was investigated using carbon nanotube-based air electrodes and 1,2-dimethoxyethane-based electrolyte within a temperature range of 20C to 40C. It is found that the discharge capacity of the Li-O 2 batteries decreases from 7,492 mAh g -1 at 40C to 2,930 mAh g -1 at 0C. However, a sharp increase in capacity was found when the temperature was further decreased and a very high capacity of 17,716 mAh g -1 was observed at 20C at a current density of 0.1 mA cm-2. When the temperature increases from 20C tomore » 40C, the morphologies of the Li 2O 2 formed varied from ultra-small spherical particles to small flakes and then to large flake-stacked toroids. The lifetime of superoxide and the solution pathway play a dominate role on the battery capacity in the temperature range of -20C to 0C, but the electrochemical kinetics of oxygen reduction and the surface pathway dominate the discharge behavior in the temperature range of 0C to 40C. These findings provide fundamental understanding on the temperature dependence of oxygen reduction process in a Li-O 2 battery and will enable a more rational design of Li-O 2 batteries.« less

Mechanism of sodium chloride in promoting reduction of high-magnesium low-nickel oxide ore

PubMed Central

Zhou, Shiwei; Wei, Yonggang; Li, Bo; Wang, Hua; Ma, Baozhong; Wang, Chengyan

2016-01-01

Sodium chloride has been proved that it is an effective promoter for the reduction of high-magnesium, low-nickel oxide ore. The aim of current work is to clarify the promotion behavior of sodium chloride in the roasting reduction process. The influence of moisture on the reduction of ore in the presence of sodium chloride is studied to get clear comprehension of promotion process. In the presence of moisture, the HCl is produced by pyrohydrolysis of sodium chloride for chlorinating nickel and iron oxides, moreover, interactions between metallic oxides and sodium chloride are also a way for chlorination at high temperature (>802 °C); subsequently, the metal chloride would be reduced by reductant. In the absence of moisture, the magnetic separation results show that the recoveries of iron and nickel have a significant increase; moreover, olivine structure would be destroyed gradually with the increase of roasting temperature in the action of sodium chloride, and the sodium chloride existed in high-magnesium, low-nickel oxide ore could make the NiO isolate from NiO-bearing minerals. The NiO reacts with Fe2O3 at high temperature to form NiFe2O4, which is conductive to the formation of Ni-Fe alloy during the reduction process. PMID:27374991

Mechanism of sodium chloride in promoting reduction of high-magnesium low-nickel oxide ore.

PubMed

Zhou, Shiwei; Wei, Yonggang; Li, Bo; Wang, Hua; Ma, Baozhong; Wang, Chengyan

2016-07-04

Sodium chloride has been proved that it is an effective promoter for the reduction of high-magnesium, low-nickel oxide ore. The aim of current work is to clarify the promotion behavior of sodium chloride in the roasting reduction process. The influence of moisture on the reduction of ore in the presence of sodium chloride is studied to get clear comprehension of promotion process. In the presence of moisture, the HCl is produced by pyrohydrolysis of sodium chloride for chlorinating nickel and iron oxides, moreover, interactions between metallic oxides and sodium chloride are also a way for chlorination at high temperature (>802 °C); subsequently, the metal chloride would be reduced by reductant. In the absence of moisture, the magnetic separation results show that the recoveries of iron and nickel have a significant increase; moreover, olivine structure would be destroyed gradually with the increase of roasting temperature in the action of sodium chloride, and the sodium chloride existed in high-magnesium, low-nickel oxide ore could make the NiO isolate from NiO-bearing minerals. The NiO reacts with Fe2O3 at high temperature to form NiFe2O4, which is conductive to the formation of Ni-Fe alloy during the reduction process.

Defective Carbon-Based Materials for the Electrochemical Synthesis of Hydrogen Peroxide

DOE PAGES

Chen, Shucheng; Chen, Zhihua; Siahrostami, Samira; ...

2017-10-30

Hydrogen peroxide (H 2O 2), an important industrial chemical, is currently produced through an energy-intensive anthraquinone process that is limited to large-scale facilities. Small-scale decentralized electrochemical production of H 2O 2 via a two-electron oxygen reduction reaction (ORR) offers unique opportunities for sanitization applications and the purification of drinking water. The development of inexpensive, efficient, and selective catalysts for this reaction remains a challenge. Here in this paper, we examine two different porous carbon-based electrocatalysts and show that they exhibit high selectivity for H 2O 2 under alkaline conditions. By rationally varying synthetic methods, we explore the effect of poremore » size on electrocatalytic performance. Furthermore, by means of density functional calculations, we point out the critical role of carbon defects. Our theory results show that the majority of defects in graphene are naturally selective for the two-electron reduction of O 2 to H 2O 2, and we identify the types of defects with high activity.« less

Catalysts for ultrahigh current density oxygen cathodes for space fuel cell applications

NASA Technical Reports Server (NTRS)

Tryk, Donald A.; Yeager, E.

1992-01-01

The objective was to identify promising electrocatalyst/support systems for oxygen cathodes capable of operating at ultrahigh current densities in alkaline fuel cells. Such cells will require operation at relatively high temperatures and O2 pressures. A number of materials were prepared, including Pb-Ru and Pb-Ir pyrochlores, RuO2 and Pt-doped RuO2, lithiated NiO and La-Ni perovskites. Several of these materials were prepared using techniques that had not been previously used to prepare them. Particularly interesting was the use of the alkaline solution technique to prepare Pt-doped and Pb-Ru pyrochlores in high area form. Also interesting was the use of the fusion (melt) method for preparing the Pb-Ru pyrochlore. Several of the materials were also deposited with platinum. Well-crystallized Pb2Ru2O(7-y) was used to fabricate very high performance O2 cathodes with good stability in room temperature KOH. This material was also found to be stable over a useful potential range at approx. 140 C in concentrated KOH. For some of the samples, fabrication of the gas-fed electrodes could not be fully optimized during this project period. Future work may be directed at this problem. Pyrochlores that were not well-crystallized were found to be unstable in alkaline solution. Very good O2 reduction performance and stability were observed with Pb2RuO(7-y) in a carbon-based gas-fed electrode with an anion-conducting membrane placed on the electrolyte side of the electrode. The performance came within a factor of about two of that observed without carbon. High area platinum and gold supported on several conductive metal oxide supports were examined. Only small improvements in O2 reduction performance at room temperature were observed for Pb2Ru2O(7-y) as a support because of the high intrinsic activity of the pyrochlore. In contrast, a large improvement was observed for Li-doped NiO as a support for Pt. Very poor performance was observed for Au deposited on Li-NiO at approx. 150 C. Nearly reversible behavior was observed for the O2/OH(-) couple for Li-doped NiO at approx. 200 C. The temperature dependence for the O2 reduction was examined.

Role of heteroatoms in S, N-codoped nanoporous carbons in CO2 (photo)electrochemical reduction.

PubMed

Bandosz, Teresa; Li, Wanlu

2018-06-19

Thiourea-modified wood-based activated carbons were evaluated as catalysts for CO2 electrochemical reduction reaction (CO2ERR). The materials obtained at 950oC showed a long stability. The results indicated that thiophenic sulfur provides catalytic activity for CO formation. However, it was not as active for CH4 formation as was pyridinic-N. Tafel plots suggested that the nanoporous structure enhanced the kinetics for CO2 reduction. The electric conductivity limited the activity for CO2ERR in the materials modified at 600, 800 and 900oC. The effect of visible light on CO2ERR was also investigated in this study. Upon irradiation, photocurrent was generated, and a current density increased during CO2 reduction process. Combined with a band-gap alignment, the results indicate that thiophenic-S in the carbon matrix contributed to sample's photoactivity in visible light. These species enhance the overall reduction process promoting both hydrogen evolution reaction and CO2 reduction to CO. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

High Performance Reduction of H2O2 with an Electron Transport Decaheme Cytochrome on a Porous ITO Electrode

PubMed Central

2017-01-01

The decaheme cytochrome MtrC from Shewanella oneidensis MR-1 immobilized on an ITO electrode displays unprecedented H2O2 reduction activity. Although MtrC showed lower peroxidase activity in solution compared to horseradish peroxidase, the ten heme cofactors enable excellent electronic communication and a superior activity on the electrode surface. A hierarchical ITO electrode enabled optimal immobilization of MtrC and a high current density of 1 mA cm–2 at 0.4 V vs SHE could be obtained at pH 6.5 (Eonset = 0.72 V). UV–visible and Resonance Raman spectroelectrochemical studies suggest the formation of a high valent iron-oxo species as the catalytic intermediate. Our findings demonstrate the potential of multiheme cytochromes to catalyze technologically relevant reactions and establish MtrC as a new benchmark in biotechnological H2O2 reduction with scope for applications in fuel cells and biosensors. PMID:28221032

Nitrous Oxide Metabolism in Nitrate-Reducing Bacteria: Physiology and Regulatory Mechanisms.

PubMed

Torres, M J; Simon, J; Rowley, G; Bedmar, E J; Richardson, D J; Gates, A J; Delgado, M J

2016-01-01

Nitrous oxide (N2O) is an important greenhouse gas (GHG) with substantial global warming potential and also contributes to ozone depletion through photochemical nitric oxide (NO) production in the stratosphere. The negative effects of N2O on climate and stratospheric ozone make N2O mitigation an international challenge. More than 60% of global N2O emissions are emitted from agricultural soils mainly due to the application of synthetic nitrogen-containing fertilizers. Thus, mitigation strategies must be developed which increase (or at least do not negatively impact) on agricultural efficiency whilst decrease the levels of N2O released. This aim is particularly important in the context of the ever expanding population and subsequent increased burden on the food chain. More than two-thirds of N2O emissions from soils can be attributed to bacterial and fungal denitrification and nitrification processes. In ammonia-oxidizing bacteria, N2O is formed through the oxidation of hydroxylamine to nitrite. In denitrifiers, nitrate is reduced to N2 via nitrite, NO and N2O production. In addition to denitrification, respiratory nitrate ammonification (also termed dissimilatory nitrate reduction to ammonium) is another important nitrate-reducing mechanism in soil, responsible for the loss of nitrate and production of N2O from reduction of NO that is formed as a by-product of the reduction process. This review will synthesize our current understanding of the environmental, regulatory and biochemical control of N2O emissions by nitrate-reducing bacteria and point to new solutions for agricultural GHG mitigation. © 2016 Elsevier Ltd. All rights reserved.

Effect of annealing process on the heterostructure CuO/Cu2O as a highly efficient photocathode for photoelectrochemical water reduction

NASA Astrophysics Data System (ADS)

Du, Fan; Chen, Qing-Yun; Wang, Yun-Hai

2017-05-01

CuO/Cu2O photocathodes were successfully prepared via simply annealing the electrodeposited Cu2O on fluoride doped tin oxide (FTO) substrate. They were characterized by X-ray diffraction, scanning electron microscopy (SEM), transmission electron microscope (TEM), UV-vis absorption spectra and X-ray photoelectron spectroscopy (XPS). The results showed that the heterojunction of CuO/Cu2O was formed during the annealing process and presented the nature of p-type semiconductor. The photocurrent density and photoelectrochemical (PEC) stability of the p-type heterostructure CuO/Cu2O photocathode was improved greatly compared with the pure Cu2O, which was greatly affected by annealing time and temperature. The highest photo current density of -0.451 mA/cm2 and highest stability was obtained via annealing at 650 °C for 15 min (at -0.3 V vs. Ag/AgCl), which gave a remarkable improvement than the as-deposited Cu2O (-0.08 mA/cm2). This suggested that the CuO/Cu2O heterojunction facilitated the electron-hole pair separation and improved the photocathode's current and stability.

Graphene oxide electrocatalyst on MnO2 air cathode as an efficient electron pump for enhanced oxygen reduction in alkaline solution

NASA Astrophysics Data System (ADS)

Basirun, Wan Jeffrey; Sookhakian, Mehran; Baradaran, Saeid; Endut, Zulkarnain; Mahmoudian, Mohammad Reza; Ebadi, Mehdi; Yousefi, Ramin; Ghadimi, Hanieh; Ahmed, Sohail

2015-03-01

Graphene oxide (GO) was deposited on the surface of a MnO2 air cathode by thermal evaporation at 50°C from a GO colloidal suspension. Fourier transformed infrared spectroscopy and field emission scanning electron microscopy confirmed the presence of GO on the MnO2 air cathode (GO-MnO2). Voltammetry and chrono-amperometry showed increased currents for the oxygen reduction reaction (ORR) in 6 M KOH solution for GO-MnO2 compared to the MnO2 cathode. The GO-MnO2 was used as an air cathode in an alkaline tin-air cell and produced a maximum power density of 13 mW cm-2, in contrast to MnO2, which produced a maximum power density of 9.2 mW cm-2. The electrochemical impedance spectroscopy results suggest that the chemical step for the ORR is the rate determining step, as proposed earlier by different researchers. It is suggested that the presence of GO and electrochemically reduced graphene oxide (ERGO) on the MnO2 surface are responsible for the increased rate of this step, whereby GO and ERGO accelerate the process of electron donation to the MnO2 and to adsorbed oxygen atoms.

An investigation of the reduction of carbon dioxide in a silent electric discharge

NASA Technical Reports Server (NTRS)

Luce, R. S.; Greenough, B. (Editor)

1978-01-01

The reduction of CO2 to O2 and CO in a silent electric discharge was studied. It was found that current alone (in the ionized plasma induced by the silent electric discharge) was reponsible for the CO2 reduction process. Voltage and frequency were important only in so far as they induced current in the plasma. Pressure and temperature were of minimum influence in the process. The large power consumption in the process was recognized as resulting from the low power factor of the reactor vessel which electrically behaved like a capacitor. The power factor was subsequently improved by adding an inductive element to make the reactor vessel capacitance part of a resonant circuit. It was found that the CO2 reduction process was most efficient in terms of power vs reduction rate when a voltage was employed that was only slightly higher than that needed to induce the plasma.

Cyanide oxidation by singlet oxygen generated via reaction between H2O2 from cathodic reduction and OCl(-) from anodic oxidation.

PubMed

Tian, Shichao; Li, Yibing; Zeng, Huabin; Guan, Wei; Wang, Yan; Zhao, Xu

2016-11-15

Cyanide is widely present in electroplating wastewater or metallurgical effluents. In the present study, the electrochemical destruction of cyanide with various anode and cathode compositions under alkaline conditions was investigated. The results indicated that the electrochemical system using RuO2/Ti as anode and activated carbon fiber (ACF) as cathode in the presence of sodium chloride was efficient for the cyanide removal. In this system, in situ generation of HClO by anodic oxidation of Cl(-) at RuO2/Ti anode occurred with the H2O2 generation by O2 reduction at ACF cathode. As confirmed by the electron spin resonance technique, the reaction between HClO and H2O2 led to the generation of singlet oxygen, which was responsible for the cyanide removal. Further experiment indicated that the cyanide removal efficiency increased with the increase of the current density or the sodium chloride concentration. Cyanate was identified as main product in the system. Besides, the system exhibited good stability for the cyanide removal, which was beneficial to its practical application. Copyright © 2016. Published by Elsevier Inc.

One-pot synthesis of La0.7Sr0.3MnO3 supported on flower-like CeO2 as electrocatalyst for oxygen reduction reaction in aluminum-air batteries

NASA Astrophysics Data System (ADS)

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

2017-08-01

A novel La0.7Sr0.3MnO3-CeO2 (LSM-CeO2) hybrid catalyst for oxygen reduction reaction (ORR) has been synthesized by a facile one-pot method. The flower-like CeO2 with the diameter of about 3 μm is formed by the agglomeration of nanosheets with the thickness of about 40 nm. The LSM particles with the diameter of about 150 nm are well distributed on the flower-like CeO2, thus the interaction between LSM and CeO2 is built. Therefore, the LSM-CeO2 composite catalyst exhibits the much higher catalytic activity toward ORR with the direct four-electron transfer mechanism in alkaline solution than LSM or CeO2. Furthermore, the stability of LSM-CeO2 is superior to that of Pt/C, and the current retention is 93% after 100000 s. The maximum power density of the aluminum-air battery using LSM-CeO2 as the ORRC can reach 238 mW cm-2, which is about 29% higher than that with LSM (184 mW cm-2). It indicates that LSM-CeO2 composite material is a promising cathodic electrocatalyst for metal-air batteries.

77 FR 61473 - Proposed Collection; Comment Request for Voluntary Customer Surveys To Implement E.O. 12862...

Federal Register 2010, 2011, 2012, 2013, 2014

2012-10-09

... Voluntary Customer Surveys To Implement E.O. 12862 Coordinated by the Corporate Planning and Performance... required by the Paperwork Reduction Act of 1995, Public Law 104-13 (44 U.S.C. 3506(c)(2)(A)). Currently... Coordinated by [[Page 61474

Evolution of resistive switching mechanism through H2O2 sensing by using TaOx-based material in W/Al2O3/TaOx/TiN structure

NASA Astrophysics Data System (ADS)

Chakrabarti, Somsubhra; Panja, Rajeswar; Roy, Sourav; Roy, Anisha; Samanta, Subhranu; Dutta, Mrinmoy; Ginnaram, Sreekanth; Maikap, Siddheswar; Cheng, Hsin-Ming; Tsai, Ling-Na; Chang, Ya-Ling; Mahapatra, Rajat; Jana, Debanjan; Qiu, Jian-Tai; Yang, Jer-Ren

2018-03-01

Understanding of resistive switching mechanism through H2O2 sensing and improvement of switching characteristics by using TaOx-based material in W/Al2O3/TaOx/TiN structure have been reported for the first time. Existence of amorphous Al2O3/TaOx layer in the RRAM devices has been confirmed by transmission electron microscopy. By analyzing the oxidation states of Ta2+/Ta5+ for TaOx switching material and W0/W6+ for WOx layer at the W/TaOx interface through X-ray photoelectron spectroscopy and H2O2 sensing, the reduction-oxidation mechanism under Set/Reset occurs only in the TaOx layer for the W/Al2O3/TaOx/TiN structures. This leads to higher Schottky barrier height at the W/Al2O3 interface (0.54 eV vs. 0.46 eV), higher resistance ratio, and long program/erase endurance of >108 cycles with 100 ns pulse width at a low operation current of 30 μA. Stable retention of more than 104 s at 85 °C is also obtained. Using conduction mechanism and reduction-oxidation reaction, current-voltage characteristic has been simulated. Both TaOx and WOx membranes have high pH sensitivity values of 47.65 mV/pH and 49.25 mV/pH, respectively. Those membranes can also sense H2O2 with a low concentration of 1 nM in an electrolyte-insulator-semiconductor structure because of catalytic activity, while the Al2O3 membrane does not show sensing. The TaOx material in W/Al2O3/TaOx/TiN structure does not show only a path towards high dense, small size memory application with understanding of switching mechanism but also can be used for H2O2 sensors.

Fe(III) oxides accelerate microbial nitrate reduction and electricity generation by Klebsiella pneumoniae L17.

PubMed

Liu, Tongxu; Li, Xiaomin; Zhang, Wei; Hu, Min; Li, Fangbai

2014-06-01

Klebsiella pneumoniae L17 is a fermentative bacterium that can reduce iron oxide and generate electricity under anoxic conditions, as previously reported. This study reveals that K. pneumoniae L17 is also capable of dissimilatory nitrate reduction, producing NO2(-), NH4(+), NO and N2O under anoxic conditions. The presence of Fe(III) oxides (i.e., α-FeOOH, γ-FeOOH, α-Fe2O3 and γ-Fe2O3) significantly accelerates the reduction of nitrate and generation of electricity by K. pneumoniae L17, which is similar to a previous report regarding another fermentative bacterium, Bacillus. No significant nitrate reduction was observed upon treatment with Fe(2+) or α-FeOOH+Fe(2+), but a slight facilitation of nitrate reduction and electricity generation was observed upon treatment with L17+Fe(2+). This result suggests that aqueous Fe(II) or mineral-adsorbed Fe(II) cannot reduce nitrate abiotically but that L17 can catalyze the reduction of nitrate and generation of electricity in the presence of Fe(II) (which might exist as cell surface-bound Fe(II)). To rule out the potential effect of Fe(II) produced by L17 during microbial iron reduction, treatments with the addition of TiO2 or Al2O3 instead of Fe(III) oxides also exhibited accelerated microbial nitrate reduction and electricity generation, indicating that cell-mineral sorption did account for the acceleration effect. However, the acceleration caused by Fe(III) oxides is only partially attributed to the cell surface-bound Fe(II) and cell-mineral sorption but may be driven by the iron oxide conduction band-mediated electron transfer from L17 to nitrate or an electrode, as proposed previously. The current study extends the diversity of bacteria of which nitrate reduction and electricity generation can be facilitated by the presence of iron oxides and confirms the positive role of Fe(III) oxides on microbial nitrate reduction and electricity generation by particular fermentative bacteria in anoxic environments. Copyright © 2014 Elsevier Inc. All rights reserved.

Cathodic current enhancement via manganese and oxygen related reactions in marine biofilms

NASA Astrophysics Data System (ADS)

Strom, Matthew James

Corrosion is a threat that has economic, and environmental impacts worldwide. Many types of corrosive attack are the subject of ongoing research. One of these areas of research is microbiologically influenced corrosion, which is the enhancement and/or initiation of corrosion events caused by microorganisms. It is well known that colonies of microorganisms can enhance cathodic currents through biofilm formation. The aim of the present work was to elucidate the role of manganese in enhancing cathodic currents in the presence of biofilms. Repeated polarizations conducted in Delaware Bay waters, on biofilm coated Cr identified potentially sustainable reduction reactions. The reduction of MnO2 and the enhancement of the oxygen reduction reaction (ORR) were proven to be factors that influence cathodic current enhancement. The removal of ambient oxygen during polarizations resulted in a shutdown of cathodic current enhancement. These field data led to an exploration of the synergistic relationship between MnO2 and the ORR. Laboratory studies of the catalysis of peroxide disproportionation by MnO2 were monitored using a hanging mercury drop electrode. Experiments were run at an ambient sweater pH of 8 and pH 9, which simulated the near-surface conditions typical of cathodes immersed in seawater. Rapid reoxidation at the more basic pH was shown to allow manganese to behave as a persistent catalyst under the typical electrochemical surface conditions of a cathode. As a result a mechanism for ORR enhancement by manganese was proposed as a unique mechanism for cathodic current enhancement in biofilms. A separate field study of Delaware biofilms on stainless steel coupled to a sacrificial Al anode was carried out to identify the ORR enhancement mechanism and sustainable redox reactions at the cathode. Chemical treatments of glutaraldehyde and formaldoxime were applied to cathodes with biofilms to distinguish between enzymatic and MnO2 related ORR enhancement. The results ruled out the enzymatic catalysis of ORR and supported the catalysis by MnO2. Sustainable redox reactions at the cathode were evaluated by monitoring the cathodic current of biofilm coated stainless steel for a year under different polarization intensities. The results showed that sustainable cathodic reactions were present in marine biofilms but their influence on the cathodic current was negligible until a potential was reached where the ORR could take place. Additionally seasonal variability was observed in the enhanced cathodic current in Delaware Bay biofilms. This was attributed to the seasonal variability of manganese in the water column.

Mass and charge transport relevant to the formation of toroidal lithium peroxide nanoparticles in an aprotic lithium-oxygen battery: An experimental and theoretical modeling study

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

Luo, Xiangyi; Amine, Rachid; Lau, Kah Chun

2017-05-26

The discharge and charge mechanisms of rechargeable Li-O-2 batteries have been the subject of extensive investigation recently. However, they are not fully understood yet. Here we report a systematic study of the morphological transition of Li2O2 from a single crystalline structure to a toroid like particle during the discharge-charge cycle, with the help of a theoretical model to explain the evolution of the Li2O2 at different stages of this process. The model suggests that the transition starts in the first monolayer of Li2O2, and is subsequently followed by a transition from particle growth to film growth if the applied currentmore » exceeds the exchange current for the oxygen reduction reaction in a Li-O-2 cell. Furthermore, a sustainable mass transport of the diffusive active species (e.g., O-2 and Li+) and evolution of the underlying interfaces are critical to dictate desirable oxygen reduction (discharge) and evolution (charge) reactions in the porous carbon electrode of a Li-O-2 cell.« less

Directing the Branching Growth of Cuprous Oxide by OH- Ions

NASA Astrophysics Data System (ADS)

Chen, Kunfeng; Si, Yunfei; Xue, Dongfeng

The effect of OH- ions on the branching growth of cuprous oxide microcrystals was systematically studied by a reduction route, where copper-citrate complexes were reduced by glucose under alkaline conditions. Different copper salts including Cu(NO3)2, CuCl2, CuSO4, and Cu(Ac)2 were used in this work. The results indicate that the Cu2O branching growth habit is closely correlated to the concentration of OH- ions, which plays an important role in directing the diffusion-limited branching growth of Cu2O and influencing the reduction power of glucose. A variety of Cu2O branching patterns including 6-pod, 8-pod and 24-pod branches, have been achieved without using template and surfactant. The current method can provide a good platform for studying the growth mechanism of microcrystal branching patterns.

Bipolar resistance switching in Pt/CuO x /Pt via local electrochemical reduction

DOE PAGES

D'Aquila, Kenneth; Phatak, Charudatta; Holt, Martin V.; ...

2014-06-17

We investigated the local changes in copper oxidation state and the corresponding resistance changes in Pt/CuO x/Pt nanoscale heterostructures using x-ray nanoprobe spectro-microscopy and current-voltage characterization. After gentle electroforming, during which the current-voltage behavior remains non-linear, the low resistance state was reached, and we also observed regions of 160 nm width that show an increase in Cu K-alpha fluorescence intensity, indicative of partial reduction of the CuO x. Analysis of the current voltage curves showed that the dominant conduction mechanism is Schottky emission and that the resistance state is correlated with the Schottky barrier height. We also propose that themore » reversible resistivity change in these Pt/CuO x/Pt heterostructures occurs through local electrochemical reduction leading to change of the Schottky barrier height at the interface between Pt and the reduced CuO x layers and to change of the CuO x resistivity within laterally confined portions of the CuO x layer. Our experiments reveal important insights into the mechanism of resistance switching of Pt/CuO x/Pt performed in a current and voltage regime that does not create a metallic conduction path.« less

Electrocatalytic CO2 reduction near the theoretical potential in water using Ru complex supported on carbon nanotubes

NASA Astrophysics Data System (ADS)

Sato, Shunsuke; Arai, Takeo; Morikawa, Takeshi

2018-01-01

We successfully developed a highly efficient electrode for CO2 reduction using a Ru-complex catalyst ([Ru]) supported on carbon paper coated with multi-walled carbon nanotubes (CPCNT/[Ru]). The CPCNT/[Ru] electrode promoted the CO2 reduction reaction in aqueous solution near the theoretical potential, and produced formate linearly with a current density of greater than 0.9 mA cm-2 at -0.15 V (versus RHE) for at least 24 h. Due to the outstandingly low overpotential, a monolithic tablet-shaped photo-device was realized by coupling the CPCNT/[Ru] catalyst with amorphous SiGe-jn as a light absorber and IrO x as a water oxidation catalyst, and the device produced formate from CO2 and water in a single-compartment reactor. The nanotubes enhanced the rate for CO2 reduction at [Ru], and accordingly a solar-to-chemical conversion efficiency of 4.3% for formate production was achieved when the CO2 reduction and H2O oxidation sites had the same area.

Achieving High Current Density of Perovskite Solar Cells by Modulating the Dominated Facets of Room-Temperature DC Magnetron Sputtered TiO2 Electron Extraction Layer.

PubMed

Huang, Aibin; Lei, Lei; Zhu, Jingting; Yu, Yu; Liu, Yan; Yang, Songwang; Bao, Shanhu; Cao, Xun; Jin, Ping

2017-01-25

The short circuit current density of perovskite solar cell (PSC) was boosted by modulating the dominated plane facets of TiO 2 electron transport layer (ETL). Under optimized condition, TiO 2 with dominant {001} facets showed (i) low incident light loss, (ii) highly smooth surface and excellent wettability for precursor solution, (iii) efficient electron extraction, and (iv) high conductivity in perovskite photovoltaic application. A current density of 24.19 mA cm -2 was achieved as a value near the maximum limit. The power conversion efficiency was improved to 17.25%, which was the record value of PSCs with DC magnetron sputtered carrier transport layer. What is more, the room-temperature process had a great significance for the cost reduction and flexible application of PSCs.

Oxygen Vacancies in ZnO Nanosheets Enhance CO2 Electrochemical Reduction to CO.

PubMed

Geng, Zhigang; Kong, Xiangdong; Chen, Weiwei; Su, Hongyang; Liu, Yan; Cai, Fan; Wang, Guoxiong; Zeng, Jie

2018-05-22

As electron transfer to CO 2 is generally considered to be the critical step during the activation of CO 2 , it is important to develop approaches to engineer the electronic properties of catalysts to improve their performance in CO 2 electrochemical reduction. Herein, we developed an efficient strategy to facilitate CO 2 activation by introducing oxygen vacancies into electrocatalysts with electronic-rich surface. ZnO nanosheets rich in oxygen vacancies exhibited a current density of -16.1 mA cm -2 with a Faradaic efficiency of 83 % for CO production. Based on density functional theory (DFT) calculations, the introduction of oxygen vacancies increased the charge density of ZnO around the valence band maximum, resulting in the enhanced activation of CO 2 . Mechanistic studies further revealed that the enhancement of CO production by introducing oxygen vacancies into ZnO nanosheets originated from the increased binding strength of CO 2 and the eased CO 2 activation. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Reduction mechanism of surface oxide films and characterization of formations on pulse electric-current sintered Al Mg alloy powders

NASA Astrophysics Data System (ADS)

Xie, Guoqiang; Ohashi, Osamu; Song, Minghui; Mitsuishi, Kazutaka; Furuya, Kazuo

2005-02-01

The microstructure of interfaces between powder particles in Al-Mg alloy specimens sintered by pulse electric-current sintering (PECS) process was characterized using high resolution transmission electron microscopy (HRTEM) and energy dispersive X-ray spectroscopy (EDS). The crystalline precipitates with nano-size in the interface were observed in all of Al-Mg alloy specimens. The composition was determined to be MgAl 2O 4 or MgO, or both of them, which depended on Mg content in alloy powder and sintering temperature. The precipitates were suggested to contribute to reduction reaction of Mg with oxide films originally covered at powder particles surface.

Green electrochemical modification of RVC foam electrode and improved H2O2 electrogeneration by applying pulsed current for pollutant removal.

PubMed

Zhou, Wei; Ding, Yani; Gao, Jihui; Kou, Kaikai; Wang, Yan; Meng, Xiaoxiao; Wu, Shaohua; Qin, Yukun

2018-02-01

The performance of cathode on H 2 O 2 electrogeneration is a critical factor that limits the practical application of electro-Fenton (EF) process. Herein, we report a simple but effective electrochemical modification of reticulated vitreous carbon foam (RVC foam) electrode for enhanced H 2 O 2 electrogeneration. Cyclic voltammetry, chronoamperometry, and X-ray photoelectron spectrum were used to characterize the modified electrode. Oxygen-containing groups (72.5-184.0 μmol/g) were introduced to RVC foam surface, thus resulting in a 59.8-258.2% higher H 2 O 2 yield. The modified electrodes showed much higher electrocatalytic activity toward O 2 reduction and good stability. Moreover, aimed at weakening the extent of electroreduction of H 2 O 2 in porous RVC foam, the strategy of pulsed current was proposed. H 2 O 2 concentration was 582.3 and 114.0% higher than the unmodified and modified electrodes, respectively. To test the feasibility of modification, as well as pulsed current, EF process was operated for removal of Reactive Blue 19 (RB19). The fluorescence intensity of hydroxybenzoic acid in EF with modified electrode is 3.2 times higher than EF with unmodified electrode, illustrating more hydroxyl radicals were generated. The removal efficiency of RB 19 in EF with unmodified electrode, modified electrode, and unmodified electrode assisted by pulsed current was 53.9, 68.9, and 81.1%, respectively, demonstrating that the green modification approach, as well as pulsed current, is applicable in EF system for pollutant removal. Graphical abstract ᅟ.

Voltammetric Sensor Based on Fe-doped ZnO and TiO2 Nanostructures-modified Carbon-paste Electrode for Determination of Levodopa

NASA Astrophysics Data System (ADS)

Anaraki Firooz, Azam; Hosseini Nia, Bahram; Beheshtian, Javad; Ghalkhani, Masoumeh

2017-10-01

In this study, undoped and 1 wt.% Fe-doped with ZnO, and TiO2 nanostructures were synthesized by a simple hydrothermal method without using templates. The influence of the Fe dopant on structural, optical and electrochemical response was studied by x-ray diffraction, scanning electron microscopy, UV-Vis spectra, photoluminescence spectra and electrochemical characterization system. The electrochemical response of the carbon paste electrode modified with synthesized nanostructures (undoped ZnO and TiO2 as well as doped with Fe ions) toward levodopa (L-Dopa) was studied. Cyclic voltammetry using provided modified electrodes showed electro-catalytic properties for electro-oxidation of L-Dopa and a significant reduction was observed in the anodic overvoltage compared to the bare electrode. The results indicated the presence of the sufficient dopants. The best response was obtained in terms of the current enhancement, overvoltage reduction, and reversibility improvement of the L-Dopa oxidation reaction under experimental conditions by the modified electrode with TiO2 nanoparticles doped with Fe ions.

Influence of water vapor on the formation of pinning centers in YBa2Cu3O y upon low-temperature annealing

NASA Astrophysics Data System (ADS)

Bobylev, I. B.; Gerasimov, E. G.; Zyuzeva, N. A.

2017-08-01

The influence of the double heat treatment ( T = 300 and 930°C) on the critical parameters of highly textured YBa2Cu3O6.96 and YBa2Cu3O6.8 ceramics has been investigated. It has been shown that, upon low-temperature annealing in humid air, planar stacking faults are formed in these ceramics. These defects are partly retained after reduction annealing (at T = 930°C) and are efficient pinning centers in magnetic fields applied parallel and perpendicular to the c axis. Due to the absorption of water, the oxygen content is increased in the ceramics, which is accompanied by an increase in the critical temperature of superconducting transition up to 94 K for YBa2Cu3O6.96 and up to 90 K for YBa2Cu3O6.8. Optimal conditions of the double annealing have been established, after which the critical-current density increased to j c ≥ 104 A/cm2 in an external magnetic field of up to 6 T. The low-temperature treatment in the neutral atmosphere saturated by water vapors deteriorates the current-carrying capacity of the highly textured ceramics, which is connected with the disappearance of texture due to the copper reduction and the precipitation of impurity phases.

Electrochemical reduction of CO2 to CO over Zn in propylene carbonate/tetrabutylammonium perchlorate

NASA Astrophysics Data System (ADS)

Shen, Feng-xia; Shi, Jin; Chen, Tian-you; Shi, Feng; Li, Qing-yuan; Zhen, Jian-zheng; Li, Yun-fei; Dai, Yong-nian; Yang, Bin; Qu, Tao

2018-02-01

Developing low cost and high efficient electrode for carbon dioxide (CO2) reduction in organic media is essential for practical application. Zn is a cheap metal and has high catalytic effects on CO2 reduction to carbon monoxide (CO) in aqueous solution. However, little attention has been given to investigate the performance of Zn in organic media for CO2 reduction. In present work, we have conducted CO2 reduction in propylene carbonate/tetrabutylammonium perchlorate on Zn due to that propylene carbonate is a widely used industrial absorber, and tetrabutylammonium perchlorate is a commonly used organic supporting electrolyte. In addition, because electrochemical reduction of CO2 to CO naturally produces H2O, we have discussed water effects on CO2 reduction in propylene carbonate/tetrabutylammonium perchlorate+6.8 wt % H2O. Our experiment results reveal that the faradaic efficiency for CO formation reaches to 83%, and the current density remains stable at 6.72 mA/cm2 at voltage -2.3 V for 4 h. Interestingly, Zn presents higher catalytic activity than Ag, and slightly lower than Au. X-ray photoelectron spectroscopy results confirm that no poisonous species is formed and absorbed on the cathode, which is an important advantage in practical application.

Promoting formation of noncrystalline Li2O2 in the Li-O2 battery with RuO2 nanoparticles.

PubMed

Yilmaz, Eda; Yogi, Chihiro; Yamanaka, Keisuke; Ohta, Toshiaki; Byon, Hye Ryung

2013-10-09

Low electrical efficiency for the lithium-oxygen (Li-O2) electrochemical reaction is one of the most significant challenges in current nonaqueous Li-O2 batteries. Here we present ruthenium oxide nanoparticles (RuO2 NPs) dispersed on multiwalled carbon nanotubes (CNTs) as a cathode, which dramatically increase the electrical efficiency up to 73%. We demonstrate that the RuO2 NPs contribute to the formation of poorly crystalline lithium peroxide (Li2O2) that is coated over the CNT with large contact area during oxygen reduction reaction (ORR). This unique Li2O2 structure can be smoothly decomposed at low potential upon oxygen evolution reaction (OER) by avoiding the energy loss associated with the decomposition of the more typical Li2O2 structure with a large size, small CNT contact area, and insulating crystals.

Electrochemical performance of potassium-doped wüstite nanoparticles supported on graphene as an anode material for lithium ion batteries

NASA Astrophysics Data System (ADS)

Jung, Dong-Won; Jeong, Jae-Hoon; Han, Sang-Wook; Oh, Eun-Suok

2016-05-01

A graphene composite with potassium-doped FeO nanoparticles (K-FeO/graphene) is synthesized by the thermal diffusion of potassium into Fe2O3/graphene using polyol reduction. This is applied as anode material in lithium ion batteries in order to enhance the electrochemical performance of conventional iron oxides (hematite or magnetite). Rhombohedral Fe2O3 crystals are transformed into face-centered cubic FeO crystals, which show a broad d-spacing (5.2 Å) between their (111) crystal planes, by the calcination of potassium-added Fe2O3/graphene. Because of its structural characteristics, the K-FeO/graphene composite demonstrates an excellent discharge capacity of 1776 mA h g-1 at the 50th cycle at a current of 100 mA h g-1 with stable capacity retention. Even with the very high current density of 18.56 A g-1, its capacity remains at 851 mA h g-1 after 800 cycles.

N-type Cu2O doped activated carbon as catalyst for improving power generation of air cathode microbial fuel cells.

PubMed

Zhang, Xi; Li, Kexun; Yan, Pengyu; Liu, Ziqi; Pu, Liangtao

2015-01-01

A novel n-type Cu2O doped activated carbon (AC) air cathode (Cu/AC) was developed as an alternative to Pt electrode for oxygen reduction in microbial fuel cells (MFCs). The maximum power density of MFCs using this novel air cathode was as high as 1390±76mWm(-2), almost 59% higher than the bare AC air cathode. Specifically, the resistance including total resistance and charge transfer resistance significantly decreased comparing to the control. Tafel curve also showed the faster electro-transfer kinetics of Cu/AC with exchange current density of 1.03×10(-3)Acm(-2), which was 69% higher than the control. Ribbon-like Cu2O was deposited on the surface of AC with the mesopore surface area increasing. Cubic Cu2O crystals exclusively expose (111) planes with the interplanar crystal spacing of 2.48Å, which was the dominate active sites for oxygen reduction reaction (ORR). N-type Cu2O with oxygen vacancies played crucial roles in electrochemical catalytic activity. Copyright © 2015 Elsevier Ltd. All rights reserved.

Enhancement of activity of RuSex electrocatalyst by modification with nanostructured iridium towards more efficient reduction of oxygen

NASA Astrophysics Data System (ADS)

Dembinska, Beata; Kiliszek, Malgorzata; Elzanowska, Hanna; Pisarek, Marcin; Kulesza, Pawel J.

2013-12-01

Electrocatalytic activity of carbon (Vulcan XC-72) supported selenium-modified ruthenium, RuSex/C, nanoparticles for reduction of oxygen was enhanced through intentional decoration with iridium nanostructures (dimensions, 2-3 nm). The catalytic materials were characterized in oxygenated 0.5 mol dm-3 H2SO4 using cyclic and rotating ring disk voltammetric techniques as well as using transmission electron microscopy and scanning electron microscopy equipped with X-ray dispersive analyzer. Experiments utilizing gas diffusion electrode aimed at mimicking conditions existing in the low-temperature fuel cell. Upon application of our composite catalytic system, the reduction of oxygen proceeded at more positive potentials, and higher current densities were observed when compared to the behavior of the simple iridium-free system (RuSex/C) investigated under the analogous conditions. The enhancement effect was more pronounced than that one would expect from simple superposition of voltammetric responses for the oxygen reduction at RuSex/C and iridium nanostructures studied separately. Nanostructured iridium acted here as an example of a powerful catalyst for the reduction of H2O2 (rather than O2) and, when combined with such a moderate catalyst as ruthenium-selenium (for O2 reduction), it produced an integrated system of increased electrocatalytic activity in the oxygen reduction process. The proposed system retained its activity in the presence of methanol that could appear in a cathode compartment of alcohol fuel cell.

[Advanced treatment of coking wastewater with a novel heterogeneous electro-Fenton technology].

PubMed

Li, Hai-Tao; Li, Yu-Ping; Zhang, An-Yang; Cao, Hong-Bin; Li, Xin-Gang; Zhang, Yi

2011-01-01

A novel electro-catalytic reactor, with oxygen-reduction cathode (PAQ/GF), dimensionally stable anode (IrO2-RuO2 -TiO2/ Ti) and heterogeneous catalysts, is developed for advanced treatment of coking wastewater after biological process, integrating cathodic and anodic simultaneous oxidation processes. A PAQ/GF electrode was synthesized by the electro-polymerization of 2-ethyl anthraquinone on graphite felt, which was characterized with cyclic voltametry measurements; the results indicated that the PAQ/GF electrode showed high reversibility for oxidation-reduction reaction of anthraquinone and catalytic activity for O2 reduction to H2O2; 13.5 mmol/L H2O2 was obtained after electrolysis for 6 h at -0.7 V (vs. SCE) and pH 6 with a current efficiency of 50% in a membrane reactor. Fe-Cu/Y350 catalysts, prepared by impregnation method, could catalyze the production of hydroxyl radicals (*OH) from H2O2, which was confirmed both by fading reaction of crystal violet and oxidation of *OH-probe compound (p-chlorobenzoic acid); Fe-Cu/Y350 also showed high catalytic-activity for the oxidation of organics by hypochlorous sodium, because COD removal of coking wastewater reached 26% in the catalytic process while only 11% of COD removal was obtained in the absence of Fe-Cu/Y350. COD removal of coking wastewater reached 49.4% (26.0% and 23.4% in cathodic system and anodic system, respectively) in the developed electrolytic-reactor, which was higher than that of conventional cathodic-anodic-oxidation process (29.8%). At optimal reaction condition of initial COD = 192 mg/L, I = 10A x m(-2) and pH 4-5, more than 50% COD were removed after electrolysis for 1 h. The mechanism might be as follows: in cathodic system, H2O2 is generated from reduction of O2 on PAQ/GF cathode, and catalyzed by Fe-Cu/Y350 for production of *OH, which causes mineralization and degradation of organic pollutants; in anodic system, Cl2 and HClO are generated from Cl- oxidation on IrO2-RuO2-TiO2/Ti anode and the organic pollutants are oxidized by Cl2, and HClO with Fe-Cu/Y350 catalysts or by direct anodic oxidation.

Reduction of FeO contents in sinter under high bed operation

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

Fujii, K.; Hazama, K.; Hoshikuma, Y.

1996-12-31

High-bed operation (bed height more than 700 mm) is currently being carried out at the Kure No. 1 sintering plant. Before initiating this high-bed operation, the authors conducted sinter pot tests at various bed heights to investigate the effect of bed height on sintering. The following results were obtained from these pot tests: Heightening of the sinter bed increased yield at the upper layer, but at the lower layer, the yield reached a maximum value at a certain bed height. From observation of the sinter cakes, the reduction in yield is attributed to uneven burn caused by surplus heat atmore » the lower layers. Therefore, when high-bed operation is carried out, reduction of the burning energy (reduction of the FeO content in the sinter) is required. This high-bed operation with lower FeO content has enabled the company to reduce fuel consumption and SiO{sub 2} content, while maintaining high yield and high sinter quality.« less

Effect of UV lamp irradiation during oxidation of Zr/Pt/Si structure on electrical properties of Pt/ZrO 2/Pt/Si structure

NASA Astrophysics Data System (ADS)

Bae, Joon Woo; Lim, Jae-Won; Mimura, Kouji; Uchikoshi, Masahito; Miyazaki, Takamichi; Isshiki, Minoru

2010-03-01

Metal-insulator-metal (MIM) capacitors were fabricated using ZrO 2 films and the effects of structural and native defects of the ZrO 2 films on the electrical and dielectric properties were investigated. For preparing ZrO 2 films, Zr films were deposited on Pt/Si substrates by ion beam deposition (IBD) system with/without substrate bias voltages and oxidized at 200 °C for 60 min under 0.1 MPa O 2 atmosphere with/without UV light irradiation ( λ = 193 nm, Deep UV lamp). The ZrO 2(˜12 nm) films on Pt(˜100 nm)/Si were characterized by X-ray diffraction pattern (XRD), field emission scanning electron microscopy (FE-SEM) and high-resolution transmission electron microscopy (HRTEM), capacitance-voltage ( C- V) and current-voltage ( I- V) measurements were carried out on MIM structures. ZrO 2 films, fabricated by oxidizing the Zr film deposited with substrate bias voltage under UV light irradiation, show the highest capacitance (784 pF) and the lowest leakage current density. The active oxygen species formed by UV irradiation are considered to play an important role in the reduction of the leakage current density, because they can reduce the density of oxygen vacancies.

Ionic currents in the guinea-pig taenia coli.

PubMed Central

Inomata, H; Kao, C Y

1976-01-01

Short segments of portions of taenia coli of the guinea-pig averaging 54 mum X 219 mum X ca. 200 mum have been studied by a double sucrose-gap voltage-clamp technique. 2. The average total capacitance was 0-4 muF, corresponding to approximately 10(4) cells, if a specific membrane capacitance of 3 muF/cm2 were assumed. 3. A significant resistance, averaging 11-4omega, was in series with the membrane, and seriously limited the accuracy of the voltage control possible. 4. On depolarization, an early transient inward current was followed by a late maintained outwary current. 5. The late current was carried mainly by K+, because its direction could be reversed if the preparation were first depolarized in isotonic K2SO4 and held back to the original resting potential. 6. After appropriate corrections for residual capacitative and leakage currents, a reversal potential for the late current (Eb) was determined to be 15-20 mV more negative than the natural resting potential. It was not affected by the amplitude or the duration of the activating voltage step, but could be changed by prolonged applications of holding current. 7. At rest, the ratio of PNa:PK was 0-16:1; for Eb it was 0-05:1. 8. The reversal potential for the transient early inward current (Ea) averaged 22 mV in Krebs-bicarbonate solution, but was shifted to about 35 mV when the late current was first suppressed with tetraethylammonium ion. The shift suggested that there was some overlap of the early and late currents. 9. Reduction of [Na+]o to 50% of normal, or replacement of all Na+ with dimethyldiethanol ammonium ion and choline ion, failed to cause any significant shifts in the reversal potential of the early current or reduce the magnitude of the early current. 10. Reduction of [Ca2+]o to 0-25 or 0-1 of the normal caused shifts of the Ea toward the negative and reductions in the early current. These changes can occur without changes in the maximum chord conductance of the early current, such as might happen in ordinary Krebs-bicarbonate solution, or in preparations which had been depolarized by prior treatment with isotonic K2SO4 and then held back to the original membrane voltage. 11. Increase of [Ca2+]o to 5 times normal increased the early inward current, and the maximum chord conductances of the early and late currents, but did not shift the Ea. 12. In preparations pretreated with TEA, increasing [Ca2+]o to 5 times normal shifted Ea toward 45 mV. 13. The various observations are interpreted to mean that the early current in the taenia coli is carried principally by influx of Ca2+, and not by Na+. PMID:1255524

Electrodeposition of germanium from supercritical fluids.

PubMed

Ke, Jie; Bartlett, Philip N; Cook, David; Easun, Timothy L; George, Michael W; Levason, William; Reid, Gillian; Smith, David; Su, Wenta; Zhang, Wenjian

2012-01-28

Several Ge(II) and Ge(IV) compounds were investigated as possible reagents for the electrodeposition of Ge from liquid CH(3)CN and CH(2)F(2) and supercritical CO(2) containing as a co-solvent CH(3)CN (scCO(2)) and supercritical CH(2)F(2) (scCH(2)F(2)). For Ge(II) reagents the most promising results were obtained using [NBu(n)(4)][GeCl(3)]. However the reproducibility was poor and the reduction currents were significantly less than the estimated mass transport limited values. Deposition of Ge containing films was possible at high cathodic potential from [NBu(n)(4)][GeCl(3)] in liquid CH(3)CN and supercritical CO(2) containing CH(3)CN but in all cases they were heavily contaminated by C, O, F and Cl. Much more promising results were obtained using GeCl(4) in liquid CH(2)F(2) and supercritical CH(2)F(2). In this case the reduction currents were consistent with mass transport limited reduction and bulk electrodeposition produced amorphous films of Ge. Characterisation by XPS showed the presence of low levels of O, F and C, XPS confirmed the presence of Ge together with germanium oxides, and Raman spectroscopy showed that the as deposited amorphous Ge could be crystallised by the laser used in obtaining the Raman measurements.

Metabolic pathways for photobiological hydrogen production by nitrogenase- and hydrogenase-containing unicellular cyanobacteria Cyanothece.

PubMed

Skizim, Nicholas J; Ananyev, Gennady M; Krishnan, Anagha; Dismukes, G Charles

2012-01-20

Current biotechnological interest in nitrogen-fixing cyanobacteria stems from their robust respiration and capacity to produce hydrogen. Here we quantify both dark- and light-induced H(2) effluxes by Cyanothece sp. Miami BG 043511 and establish their respective origins. Dark, anoxic H(2) production occurs via hydrogenase utilizing reductant from glycolytic catabolism of carbohydrates (autofermentation). Photo-H(2) is shown to occur via nitrogenase and requires illumination of PSI, whereas production of O(2) by co-illumination of PSII is inhibitory to nitrogenase above a threshold pO(2). Carbohydrate also serves as the major source of reductant for the PSI pathway mediated via nonphotochemical reduction of the plastoquinone pool by NADH dehydrogenases type-1 and type-2 (NDH-1 and NDH-2). Redirection of this reductant flux exclusively through the proton-coupled NDH-1 by inhibition of NDH-2 with flavone increases the photo-H(2) production rate by 2-fold (at the expense of the dark-H(2) rate), due to production of additional ATP (via the proton gradient). Comparison of photobiological hydrogen rates, yields, and energy conversion efficiencies reveals opportunities for improvement.

Possibility of material cost reduction toward development of low-cost second-generation superconducting wires

NASA Astrophysics Data System (ADS)

Ichinose, Ataru; Horii, Shigeru; Doi, Toshiya

2017-10-01

Two approaches to reducing the material cost of second-generation superconducting wires are proposed in this paper: (1) instead of the electrical stabilizing layers of silver and copper presently used on the superconducting layer, a Nb-doped SrTiO3 conductive buffer layer and cube-textured Cu are proposed as an advanced architecture, and (2) the use of an electromagnetic (EM) steel tape as a metal substrate of coated conductors in a conventional architecture. In structures fabricated without using electrical stabilizing layers on the superconducting layer, the critical current density achieved at 77 K in a self-field was approximately 2.6 MA/cm2. On the other hand, in the case of using EM steel tapes, although the critical current density was far from practical at the current stage, the biaxial alignment of YBa2Cu3O y (YBCO) and buffer layers was realized without oxidation on the metal surface. In this study, the possibility of material cost reduction has been strongly indicated toward the development of low-cost second-generation superconducting wires in the near future.

Effect of TiO2 Addition on Grain Growth, Anodic Bubble Evolution and Anodic Overvoltage of NiFe2O4-Based Composite Inert Anodes

NASA Astrophysics Data System (ADS)

Wang, Bin; Du, Jinjing; Liu, Yihan; Fang, Zhao; Hu, Ping

2017-11-01

A two-step powder compaction and sintering process was employed to fabricate TiO2-doped NiFe2O4 ceramic-based inert anodes. Grain growth during isothermal sintering was analyzed using Brook grain growth model. The bubble behavior of NiFe2O4 ceramic-based inert anodes was investigated in a two-compartment see-through quartz cell for aluminum electrolysis process. Anodic overvoltage and potential decay curves of the inert anodes were measured by using the steady state and current interruption technique. The results showed that the kinetic index of grain growth decreased with an increase in temperature. The average activation energy of grain growth for 1.0 wt.% TiO2-doped NiFe2O4 ceramic samples with a sintering temperature range from 1373 to 1673 K dropped from 675.30 to 183.47 kJ/mol. The diameter size of bubbles before releasing from the bottom surface of the anodes was reduced with increasing the current density, and the larger average releasing bubble size for carbon anode at the same current density could be obtained, which was compared to the NiFe2O4 inert anodes. Besides, the cell voltage of carbon anodes fluctuated much more violently under the same experimental conditions. After adding small amount of TiO2, a minor reduction in anodic overvoltage of NiFe2O4-based anodes can be observed.

Fe2O3/Reduced Graphene Oxide/Fe3O4 Composite in Situ Grown on Fe Foil for High-Performance Supercapacitors.

PubMed

Zhao, Chongjun; Shao, Xiaoxiao; Zhang, Yuxiao; Qian, Xiuzhen

2016-11-09

A Fe 2 O 3 /reduced graphene oxide (RGO)/Fe 3 O 4 nanocomposite in situ grown on Fe foil was synthesized via a simple one-step hydrothermal growth process, where the iron foil served as support, reductant of graphene oxide, Fe source of Fe 3 O 4 , and also the current collector of the electrode. When it directly acted as the electrode of a supercapacitor, as-synthesized Fe 2 O 3 /RGO/Fe 3 O 4 @Fe exhibited excellent electrochemical performance with a high capability of 337.5 mF/cm 2 at 20 mA/cm 2 and a superior cyclability with 2.3% capacity loss from the 600th to the 2000th cycle.

Comparison of eggshell surface sanitization technologies and impacts on consumer acceptability.

PubMed

Al-Ajeeli, Morouj N; Taylor, T Matthew; Alvarado, Christine Z; Coufal, Craig D

2016-05-01

Shell eggs can be contaminated with many types of microorganisms, including bacterial pathogens, and thus present a risk for the transmission of foodborne disease to consumers. Currently, most United States egg processors utilize egg washing and sanitization systems to decontaminate surfaces of shell eggs prior to packaging. However, previous research has indicated that current shell egg sanitization technologies employed in the commercial egg industry may not completely eliminate bacteria from the surface of eggshells, and thus alternative egg sanitization technologies with the potential for increased microbial reductions on eggshells should be investigated. The objectives of this study were to compare the antimicrobial efficacy and consumer sensory attributes of industry-available eggshell sanitization methods (chlorine and quaternary ammonium compounds (QAC) applied via spray) to various alternative egg sanitization technologies. Eggs (White Leghorn hens; n=195) were obtained for evaluation of sanitizer-induced reduction in mesophilic aerobic bacteria (n=90) or inoculated Salmonella Enteritidis (SE) reduction (n=105). Sanitizing treatments evaluated in this experiment were: chlorine spray (100 ppm available chlorine), QAC spray (200 ppm), peracetic acid spray (PAA; 135 ppm) alone or in combination with ultraviolet light (UV; 254 nm), and hydrogen peroxide (H2O2; 3.5% solution) spray in combination with UV (H2O2+UV). For enumeration of aerobic bacteria, eggs were sampled at 0, 7, and 14 days of storage at 4°C; surviving SE cells from inoculated eggs were enumerated by differential plating. Sensory trials were conducted to determine consumer liking of scrambled eggs made from eggs sanitized with chlorine, QAC, H2O2+UV, or no treatment (control). The H2O2 and UV treatment resulted in the greatest reductions in eggshell aerobic plate counts compared to other treatments throughout egg storage (P<0.05). All treatments utilized reduced SE below the limit of detection by eggshell rinse. There were no differences in consumers' liking of overall flavor between the 4 treatments evaluated. The application of H2O2+UV treatment to shell eggs represents a novel technology that could have important implications for egg quality and safety preservation. © 2016 Poultry Science Association Inc.

Electrical characterization of 4H-SiC metal-oxide-semiconductor structure with Al2O3 stacking layers as dielectric

NASA Astrophysics Data System (ADS)

Chang, P. K.; Hwu, J. G.

2018-02-01

Interface defects and oxide bulk traps conventionally play important roles in the electrical performance of SiC MOS device. Introducing the Al2O3 stack grown by repeated anodization of Al films can notably lower the leakage current in comparison to the SiO2 structure, and enhance the minority carrier response at low frequency when the number of Al2O3 layers increase. In addition, the interface quality is not deteriorated by the stacking of Al2O3 layers because the stacked Al2O3 structure grown by anodization possesses good uniformity. In this work, the capacitance equivalent thickness (CET) of stacking Al2O3 will be up to 19.5 nm and the oxidation process can be carried out at room temperature. For the Al2O3 gate stack with CET 19.5 nm on n-SiC substrate, the leakage current at 2 V is 2.76 × 10-10 A/cm2, the interface trap density at the flatband voltage is 3.01 × 1011 eV-1 cm-2, and the effective breakdown field is 11.8 MV/cm. Frequency dispersion and breakdown characteristics may thus be improved as a result of the reduction in trap density. The Al2O3 stacking layers are capable of maintaining the leakage current as low as possible even after constant voltage stress test, which will further ameliorate reliability characteristics.

Study of Sn and Mg doping effects on TiO2/Ge stack structure by combinatorial synthesis

NASA Astrophysics Data System (ADS)

Nagata, Takahiro; Suzuki, Yoshihisa; Yamashita, Yoshiyuki; Ogura, Atsushi; Chikyow, Toyohiro

2018-04-01

The effects of Sn and Mg doping of a TiO2 film on a Ge substrate were investigated to improve leakage current properties and Ge diffusion into the TiO2 film. For systematic analysis, dopant-composition-spread TiO2 samples with dopant concentrations of up to 20.0 at. % were fabricated by RF sputtering and a combinatorial method. X-ray photoelectron spectroscopy revealed that the instability of Mg doping of TiO2 at dopant concentrations above 10.5 at. %. Both Sn and Mg dopants reduced Ge diffusion into TiO2. Sn doping enhanced the crystallization of the rutile phase, which is a high-dielectric-constant phase, although the Mg-doped TiO2 film indicated an amorphous structure. Sn-doping indicated systematic leakage current reduction with increasing dopant concentration. Doping at Sn concentrations higher than 16.8 at. % improved the leakage properties (˜10-7 A/cm2 at -3.0 V) and capacitance-voltage properties of metal-insulator-semiconductor (MIS) operation. The Sn doping of TiO2 may be useful for interface control and as a dielectric material for Ge-based MIS capacitors.

Influence of vanadium doping on the electrochemical performance of nickel oxide in supercapacitors.

PubMed

Park, Hae Woong; Na, Byung-Ki; Cho, Byung Won; Park, Sun-Min; Roh, Kwang Chul

2013-10-28

In this study, V-doped NiO materials were prepared by simple coprecipitation and thermal decomposition, and the effect of the vanadium content on the morphology, structural properties, electrochemical behavior, and cycling stability of NiO upon oxidation and reduction was analyzed for supercapacitor applications. The results show an improvement in the capacitive characteristics of the V-doped NiO, including increases in the specific capacitance after the addition of just 1.0, 2.0, and 4.0 at% V. All VxNi1-xO electrodes (x = 0.01, 0.02, 0.04) exhibited higher specific capacitances of 371.2, 365.7, and 386.2 F g(-1) than that of pure NiO (303.2 F g(-1)) at a current density of 2 A g(-1) after 500 cycles, respectively. The V0.01Ni0.99O electrode showed good capacitance retention of 73.5% at a current density of 2 A g(-1) for more than 500 cycles in a cycling test. Importantly, the rate capability of the V0.01Ni0.99O electrode was maintained at about 84.7% as discharge current density was increased from 0.5 A g(-1) to 4 A g(-1).

120 MeV Ag ion induced effects in Au/HfO2/Si MOSCAPs

NASA Astrophysics Data System (ADS)

Manikanthababu, N.; Prajna, K.; Pathak, A. P.; Rao, S. V. S. Nageswara

2018-05-01

HfO2/Si thinfilms were deposited by RF sputtering technique. 120 MeV Ag ion irradiation has been used to study the electrical properties of Au/HfO2/Si MOSCAPs. SHI (120 MeV Ag) induced annealing, defects creation and intermixing effects on the electrical properties of these systems have been studied. Here, we have observed that the high electronic excitation can cause a significant reduction of leakage currents in these MOSCAP devices. Various quantum mechanical tunneling phenomenon has been observed from the I-V characteristics.

Measuring Greenhouse Gas Emissions and Sinks Across California Land Cover

NASA Astrophysics Data System (ADS)

Fischer, M. L.

2017-12-01

Significant reductions in greenhouse gas (GHG) emissions are needed to limit rising planetary temperatures that will otherwise limit Earth's capacity to support life, introducing geopolitical instability. To help mitigate this threat, California has legislated landmark reductions in state-level greenhouse gas (GHG) emissions that set an example for broader action. Beginning with relatively assured reduction of current emissions to 1990 levels by 2020, future goals are much more challenging with 40% and 80% reductions below 1990 emissions by 2030 and 2050, respectively. While the majority of the reductions must focus on fossil fuels, inventory estimates of non-CO2 GHG emissions (i.e., CH4, N2O, and industrial compounds) constitute 15% of the total, suggesting reductions are required across multiple land use sectors. However, recent atmospheric inversion studies show methane and nitrous oxide (CH4 & N2O) emissions exceed current inventory estimates by factors of 1.2-1.8 and 1.6-2.6 (at 95% confidence), respectively, perhaps constituting up to 30% of State total emissions. The discrepancy is likely because current bottom-up models used for inventories do not accurately capture important management or biophysical factors. In the near term, process level experiments and sector-specific inversions are being planned to quantify the factors controlling non-CO2 GHG emissions for several of the dominant emission sectors. For biosphere carbon, California forests lands, which also depend on the combination of management, climate, and weather, lost above ground carbon from 2001-2010, and may be expected to lose soil and root carbon as a longer-term result. Here, it is important to identify and apply the best principles in forestry and agriculture to increase carbon stocks in depleted forest and agricultural areas, focusing on approaches that provide resilience to future climate and weather variations. Taken together, improved atmospheric, plant, and soil observations, together with empirical and/or process-level models should be developed to quantify current trajectories of both biological CO2 exchange and non-CO2 GHG emissions, identify knowledge gaps, and guide mitigation policies.

C3N4-H5PMo10V2O40: a dual-catalysis system for reductant-free aerobic oxidation of benzene to phenol

NASA Astrophysics Data System (ADS)

Long, Zhouyang; Zhou, Yu; Chen, Guojian; Ge, Weilin; Wang, Jun

2014-01-01

Hydroxylation of benzene is a widely studied atom economical and environmental benign reaction for producing phenol, aiming to replace the existing three-step cumene process. Aerobic oxidation of benzene with O2 is an ideal and dream process, but benzene and O2 are so inert that current systems either require expensive noble metal catalysts or wasteful sacrificial reducing agents; otherwise, phenol yields are extremely low. Here we report a dual-catalysis non-noble metal system by simultaneously using graphitic carbon nitride (C3N4) and Keggin-type polyoxometalate H5PMo10V2O40 (PMoV2) as catalysts, showing an exceptional activity for reductant-free aerobic oxidation of benzene to phenol. The dual-catalysis mechanism results in an unusual route to create phenol, in which benzene is activated on the melem unit of C3N4 and O2 by the V-O-V structure of PMoV2. This system is simple, highly efficient and thus may lead the one-step production of phenol from benzene to a more practical pathway.

C3N4-H5PMo10V2O40: a dual-catalysis system for reductant-free aerobic oxidation of benzene to phenol

PubMed Central

Long, Zhouyang; Zhou, Yu; Chen, Guojian; Ge, Weilin; Wang, Jun

2014-01-01

Hydroxylation of benzene is a widely studied atom economical and environmental benign reaction for producing phenol, aiming to replace the existing three-step cumene process. Aerobic oxidation of benzene with O2 is an ideal and dream process, but benzene and O2 are so inert that current systems either require expensive noble metal catalysts or wasteful sacrificial reducing agents; otherwise, phenol yields are extremely low. Here we report a dual-catalysis non-noble metal system by simultaneously using graphitic carbon nitride (C3N4) and Keggin-type polyoxometalate H5PMo10V2O40 (PMoV2) as catalysts, showing an exceptional activity for reductant-free aerobic oxidation of benzene to phenol. The dual-catalysis mechanism results in an unusual route to create phenol, in which benzene is activated on the melem unit of C3N4 and O2 by the V-O-V structure of PMoV2. This system is simple, highly efficient and thus may lead the one-step production of phenol from benzene to a more practical pathway. PMID:24413448

Oxidation and reduction behaviors of a prototypic MgO-PuO2-x inert matrix fuel

NASA Astrophysics Data System (ADS)

Miwa, Shuhei; Osaka, Masahiko

2017-04-01

Oxidation and reduction behaviors of prototypic MgO-based inert matrix fuels (IMFs) containing PuO2-x were experimentally investigated by means of thermogravimetry. The oxidation and reduction kinetics of the MgO-PuO2-x specimen were determined. The oxidation and reduction rates of the MgO-PuO2-x were found to be low compared with those of PuO2-x. It is note that the changes in O/Pu ratios of MgO-PuO2-x from stoichiometry were smaller than those of PuO2-x at high oxygen partial pressure.

A highly sensitive electrochemical biosensor for catechol using conducting polymer reduced graphene oxide-metal oxide enzyme modified electrode.

PubMed

Sethuraman, V; Muthuraja, P; Anandha Raj, J; Manisankar, P

2016-10-15

The fabrication, characterization and analytical performances were investigated for a catechol biosensor, based on the PEDOT-rGO-Fe2O3-PPO composite modified glassy carbon (GC) electrode. The graphene oxide (GO) doped conducting polymer poly (3,4-ethylenedioxythiophene) (PEDOT) was prepared through electrochemical polymerization by potential cycling. Reduction of PEDOT-GO was carried out by amperometric method. Fe2O3 nanoparticles were synthesized in ethanol by hydrothermal method. The mixture of Fe2O3, PPO and glutaraldehyde was casted on the PEDOT-rGO electrode. The surface morphology of the modified electrodes was studied by FE-SEM and AFM. Cyclic voltammetric studies of catechol on the enzyme modified electrode revealed higher reduction peak current. Determination of catechol was carried out successfully by Differential Pulse Voltammetry (DPV) technique. The fabricated biosensor investigated shows a maximum current response at pH 6.5. The catechol biosensor exhibited wide sensing linear range from 4×10(-8) to 6.20×10(-5)M, lower detection limit of 7×10(-9)M, current maxima (Imax) of 92.55µA and Michaelis-Menten (Km) constant of 30.48µM. The activation energy (Ea) of enzyme electrode is 35.93KJmol(-1) at 50°C. There is no interference from d-glucose and l-glutamic acid, ascorbic acid and o-nitrophenol. The PEDOT-rGO-Fe2O3-PPO biosensor was stable for at least 75 days when stored in a buffer at about 4°C. Copyright © 2015 Elsevier B.V. All rights reserved.

Kinetics of abiotic nitrous oxide production via oxidation of hydroxylamine by particulate metals in seawater

NASA Astrophysics Data System (ADS)

Cavazos, A. R.; Taillefert, M.; Glass, J. B.

2016-12-01

The oceans are a significant of nitrous oxide (N2O) to the atmosphere. Current models of global oceanic N2­O flux focus on microbial N2O cycling and often ignore abiotic reactions, such as the thermodynamically favorable oxidation of the nitrification intermediate hydroxylamine (NH2OH) by Mn(IV) or Fe(III). At circumneutral pH, NH2OH oxidation is more thermodynamically favorable via Mn(IV) than Fe(III) reduction. We characterized the kinetics of NH2OH oxidation in synthetic ocean water at pH 5.1-8.8 using microsensor electrodes to measure real-time N2O production. N2O production rates and yield were greater when NH2OH was oxidized by Mn(IV) than Fe(III). Accordingly, the reduction of Mn(IV) was first order with respect to NH2OH whereas the reduction of Fe(III) was zero order with respect to NH2OH. Interestingly, the order of the reaction with respect to Mn(IV) appears to be negative whereas the reaction is second order with respect to Fe(III). The inverse order with respect to Mn(IV) may be due to the aggregation of particles in seawater, which decreases their surface area and changes their reactivity. Finally, the reaction is first order with respect to protons with Fe(III) as the oxidant but zero order with Mn(IV). The stronger effect of the pH on the reaction with Fe(III) as the oxidant compared to Mn(IV) reflects the stoichiometry of these two reactions, as each mole of N2O produced by Fe(III) reduction consumes eight protons while each mole of N2O produced with Mn(IV) as the oxidant requires only four protons. Our data show that abiotic NH2OH oxidation by Mn(IV) or Fe(III) particles may represent a significant source of N2O in seawater. These findings suggest that abiotic N2O production in marine waters may be significant in areas of the oceans where particulate metals originating from aerosols, dust, or rivers may react with NH2OH released from ammonia-oxidizing microorganisms.

Effect of Substrates on the Photoelectrochemical Reduction of Water over Cathodically Electrodeposited p-Type Cu2O Thin Films.

PubMed

Shyamal, Sanjib; Hajra, Paramita; Mandal, Harahari; Singh, Jitendra Kumar; Satpati, Ashis Kumar; Pande, Surojit; Bhattacharya, Chinmoy

2015-08-26

In this study, we demonstrate development of p-Cu2O thin films through cathodic electrodeposition technique at constant current of 0.1 mA/cm(2) on Cu, Al, and indium tin oxide (ITO) substrates from basic CuSO4 solution containing Triton X-100 as the surfactant at 30-35 °C. The optical and morphological characterizations of the semiconductors have been carried out using UV-vis spectroscopy, X-ray diffraction (XRD), scanning electron microscopy (SEM), and Raman spectroscopy. The band gap energy of ∼2.1 eV is recorded, whereas SEM reveals that the surface morphology is covered with Cu2O semiconductors. XRD analyses confirm that with change in substrate, the size of Cu2O "cubic" crystallites decreases from ITO to Al to Cu substrates. Photoelectrochemical characterizations under dark and illuminated conditions have been carried out through linear sweep voltammetry, chronoamperometry and electrochemical impedance spectroscopic analysis. The photoelectrochemical reduction of water (H2O → H2) in pH 4.9 aqueous solutions over the different substrates vary in the order of Cu > Al > ITO. The highest current of 4.6 mA/cm(2) has been recorded over the Cu substrate even at a low illumination of 35 mW/cm(2), which is significantly higher than the values (2.4 mA/cm(2) on Au coated FTO or 4.07 mA/cm(2) on Cu foil substrate at an illumination of 100 mW/cm(2)) reported in literature.

Induced polarized state in intentionally grown oxygen deficient KTaO{sub 3} thin films

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

Mota, D. A.; Romaguera-Barcelay, Y.; Tkach, A.

2013-07-21

Deliberately oxygen deficient potassium tantalate thin films were grown by RF magnetron sputtering on Si/SiO{sub 2}/Ti/Pt substrates. Once they were structurally characterized, the effect of oxygen vacancies on their electric properties was addressed by measuring leakage currents, dielectric constant, electric polarization, and thermally stimulated depolarization currents. By using K{sub 2}O rich KTaO{sub 3} targets and specific deposition conditions, KTaO{sub 3-{delta}} oxygen deficient thin films with a K/Ta = 1 ratio were obtained. Room temperature X-ray diffraction patterns show that KTaO{sub 3-{delta}} thin films are under a compressive strain of 2.3% relative to KTaO{sub 3} crystals. Leakage current results reveal themore » presence of a conductive mechanism, following the Poole-Frenkel formalism. Furthermore, dielectric, polarization, and depolarization current measurements yield the existence of a polarized state below T{sub pol} {approx} 367 Degree-Sign C. A Cole-Cole dipolar relaxation was also ascertained apparently due to oxygen vacancies induced dipoles. After thermal annealing the films in an oxygen atmosphere at a temperature above T{sub pol}, the aforementioned polarized state is suppressed, associated with a drastic oxygen vacancies reduction emerging from annealing process.« less

Interrogating heterobimetallic co-catalytic responses for the electrocatalytic reduction of CO2 using supramolecular assembly.

PubMed

Machan, Charles W; Kubiak, Clifford P

2016-10-12

The use of hydrogen-bonding interactions to direct the non-covalent assembly of a heterobimetallic supramolecular system with Re and Mn bipyridine-based electrocatalysts is reported. Under catalytic conditions, the formation of hydrogen bonds generates a catalyst system which passes ∼10% more current than the individual current responses of the respective Re and Mn complexes for the reduction of CO 2 to CO and H 2 O. Infrared spectroelectrochemical studies indicate that the Re and Mn metal centers interact during the reduction mechanism, even forming heterobimetallic bonds under reducing conditions in the absence of substrate. These findings demonstrate that non-covalent assembly is a powerful method for generating new co-catalyst systems with greater reactivity and efficiency for transformations of interest.

Water reduction by a p-GaInP2 photoelectrode stabilized by an amorphous TiO2 coating and a molecular cobalt catalyst

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

Gu, Jing; Yan, Yong; Young, James L.

2015-12-21

Producing hydrogen through solar water splitting requires the coverage of large land areas. Abundant metal-based molecular catalysts offer scalability, but only if they match noble metal activities. We report on a highly active p-GaInP2 photocathode protected through a 35-nm TiO2 layer functionalized by a cobaloxime molecular catalyst (GaInP2-TiO2-cobaloxime). This photoelectrode mediates H2 production with a current density of ~9"0mA"0cm-2 at a potential of 0"0V versus RHE under 1-sun illumination at pH"013. The calculated turnover number for the catalyst during a 20-h period is 139,000, with an average turnover frequency of 1.9"0s-1. Bare GaInP2 shows a rapid current decay, whereas themore » GaInP2-TiO2-cobaloxime electrode shows« less

The electrochemical generation of useful chemical species from lunar materials

NASA Technical Reports Server (NTRS)

Tsai, Kan J.; Kuchynka, Daniel J.; Sammells, Anthony F.

1989-01-01

The current status of work on an electrochemical technology for the simultaneous generation of oxygen and lithium from a Li2O containing molten salt (Li2O-LiCl-LiF) is discussed. The electrochemical cell utilizes an oxygen vacancy conducting solid electrolyte, yttria-stabilized zirconia, to effect separation between the oxygen evolving and lithium reduction half-cell reactions. The cell, which operates at 700 to 800 C, possesses rapid electrode kinetics at the lithium-alloy electrode with exchange current density values being greater than 60 mA/sq cm, showing high reversibility for this reaction. When used in the electrolytic mode, lithium produced at the negative electrode would be continuously removed from the cell for later use (under lunar conditions) as an easily storable reducting agent (compared to H2) for the chemical refining of lunar ores via the general reaction: 2Li + MO yields Li2O + M where MO represents a lunar ore. Emphasis to this time has been on the simulated lunar ore ilmenite (FeTiO3), which we have found becomes chemically reduced by Li at 432 C. Furthermore, both Fe2O3 and TiO2 have been reduced by Li to give the corresponding metal. This electrochemical approach provides a convenient route for producing metals under lunar conditions and oxygen for the continuous maintenance of human habitats on the Moon's surface. Because of the high reversibility of this electrochemical system, it has also formed the basis for the lithium-oxygen secondary battery. This secondary lithium-oxygen battery system posses the highest theoretical energy density yet investigated.

The electrochemical generation of useful chemical species from lunar materials

NASA Astrophysics Data System (ADS)

Tsai, Kan J.; Kuchynka, Daniel J.; Sammells, Anthony F.

1989-03-01

The current status of work on an electrochemical technology for the simultaneous generation of oxygen and lithium from a Li2O containing molten salt (Li2O-LiCl-LiF) is discussed. The electrochemical cell utilizes an oxygen vacancy conducting solid electrolyte, yttria-stabilized zirconia, to effect separation between the oxygen evolving and lithium reduction half-cell reactions. The cell, which operates at 700 to 800 C, possesses rapid electrode kinetics at the lithium-alloy electrode with exchange current density values being greater than 60 mA/sq cm, showing high reversibility for this reaction. When used in the electrolytic mode, lithium produced at the negative electrode would be continuously removed from the cell for later use (under lunar conditions) as an easily storable reducting agent (compared to H2) for the chemical refining of lunar ores via the general reaction: 2Li + MO yields Li2O + M where MO represents a lunar ore. Emphasis to this time has been on the simulated lunar ore ilmenite (FeTiO3), which we have found becomes chemically reduced by Li at 432 C. Furthermore, both Fe2O3 and TiO2 have been reduced by Li to give the corresponding metal. This electrochemical approach provides a convenient route for producing metals under lunar conditions and oxygen for the continuous maintenance of human habitats on the Moon's surface. Because of the high reversibility of this electrochemical system, it has also formed the basis for the lithium-oxygen secondary battery. This secondary lithium-oxygen battery system posses the highest theoretical energy density yet investigated.

Vertically-aligned sandwich nanowires enhance the photoelectrochemical reduction of hydrogen peroxide: hierarchical formation on carbon nanotubes of cadmium sulfide quantum dots and Prussian blue nanocoatings.

PubMed

Gong, Kuanping

2015-07-01

We describe a vertically-aligned array of sandwiched nanowires comprising Prussian blue (PB) nanocoating-carbon nanotube (CNT) core-shell structures with CdS particles positioning at the core/shell interface, viz. PB/CdS/CNT. The PB/CdS/CNT electrode thus constructed are noticeable in synchronically harvesting photon-, ionic-, and chemical-energies, respectively, from visible light radiation, K(+) uptaking and releasing, and the reduction of H2O2. In 0.2 M K2SO4 aqueous solution, the photoelectrocatalytic reduction of 1.5 mM H2O2 at PB/CdS/CNT delivered the current density as high as 1.91 mA/cm(2) at reduced overpotential, that is, three times that at the Pt/C. This superb performance is causally linked to the judicious choice of materials and their assembly into defining sandwich nanostructures wherein the three components closely cooperate with each other in the photoelectrocatalytic reduction of H2O2, including photo-induced charge separation in CdS, spontaneous electron injection into PB due to its relatively low Fermi level, and the electrocatalytic reduction of H2O2 by PB via an electrochemical-chemical-electrochemical reaction mechanism. The structural alignment of PB/CdS/CNT ensures the simplest pathway for the mass diffusion and electron shuttle, and a high surface area accessible to the chemical and electrochemical reactions, so as to minimize the concentration- and electrochemical-polarization and thus ensure the fast overall kinetics of the electrode reaction. Copyright © 2014 Elsevier Inc. All rights reserved.

Physical understanding of trends in current collapse with atomic layer deposited dielectrics in AlGaN/GaN MOS heterojunction FETs

NASA Astrophysics Data System (ADS)

Ramanan, Narayanan; Lee, Bongmook; Misra, Veena

2016-03-01

Many passivation dielectrics are pursued for suppressing current collapse due to trapping/detrapping of access-region surface traps in AlGaN/GaN based metal oxide semiconductor heterojuction field effect transistors (MOS-HFETs). The suppression of current collapse can potentially be achieved either by reducing the interaction of surface traps with the gate via surface leakage current reduction, or by eliminating surface traps that can interact with the gate. But, the latter is undesirable since a high density of surface donor traps is required to sustain a high 2D electron gas density at the AlGaN/GaN heterointerface and provide a low ON-resistance. This presents a practical trade-off wherein a passivation dielectric with the optimal surface trap characteristics and minimal surface leakage is to be chosen. In this work, we compare MOS-HFETs fabricated with popular ALD gate/passivation dielectrics like SiO2, Al2O3, HfO2 and HfAlO along with an additional thick plasma-enhanced chemical vapor deposition SiO2 passivation. It is found that after annealing in N2 at 700 °C, the stack containing ALD HfAlO provides a combination of low surface leakage and a high density of shallow donor traps. Physics-based TCAD simulations confirm that this combination of properties helps quick de-trapping and minimal current collapse along with a low ON resistance.

Electrochemical quartz crystal microbalance analysis of the oxygen reduction reaction on Pt-based electrodes. Part 2: adsorption of oxygen species and ClO4(-) anions on Pt and Pt-Co alloy in HClO4 solutions.

PubMed

Omura, J; Yano, H; Tryk, D A; Watanabe, M; Uchida, H

2014-01-14

To gain deeper insight into the role of adsorbed oxygenated species in the O2 reduction reaction (ORR) kinetics on platinum and platinum-cobalt alloys for fuel cells, we carried out a series of measurements with the electrochemical quartz crystal microbalance (EQCM) and the rotating disk electrode (RDE) in acid solution. The effects of anion adsorption on the activities for the ORR were first assessed in HClO4 and HF electrolyte solutions at various concentrations. In our previous work (Part 1), we reported that the perchlorate anion adsorbs specifically on bulk-Pt, with a Frumkin-Temkin isotherm, that is, a linear relationship between Δm and log[HClO4]. Here, we find that the specific adsorption on the Pt-skin/Pt3Co alloy was significantly stronger than that on bulk-Pt, in line with its modified electronic properties. The kinetically controlled current density j(k) for the O2 reduction at the Pt-skin/Pt3Co-RDE was about 9 times larger than that of the bulk-Pt-RDE in 0.01 M HClO4 saturated with air, but the j(k) values on Pt-skin/Pt3Co decreased with increasing [HClO4] more steeply than in the case of Pt, due to the blocking of the active sites by the specifically adsorbed ClO4(-). We have detected reversible mass changes for one or more adsorbed oxygen-containing species (Ox = O2, O, OH, H2O) on the Pt-skin/Pt3Co-EQCM and Pt-EQCM in O2-saturated and He-purged 0.01 M HClO4 solutions, in which the specific adsorption of ClO4(-) anions was negligible. The coverages of oxygen species θ(Ox) on the Pt-skin/Pt3Co in the potential range from 0.86 to 0.96 V in the O2-saturated solution were found to be larger than those on pure Pt, providing strong evidence that the higher O2 reduction activity on the Pt3Co is correlated with higher θ(Ox), contrary to the conventional view.

Rate Dependent Multi-Mechanism Discharge of Ag 0.50VOP 4·1.8H 2O: Insights from In Situ Energy Dispersive X-ray Diffraction

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

Huie, Matthew M.; Bock, David C.; Zhong, Zhong

Ag 0.50VOPO 4·1.8H 2O (silver vanadium phosphate, SVOP) demonstrates a counterintuitive higher initial loaded voltage under higher discharge current. Energy dispersive X-ray diffraction (EDXRD) from synchrotron radiation was used to create tomographic profiles of cathodes at various depths of discharge for two discharge rates. SVOP displays two reduction mechanisms, reduction of a vanadium center accompanied by lithiation of the structure, or reduction-displacement of a silver cation to form silver metal. In-situ EDXRD provides the opportunity to observe spatially resolved changes to the parent SVOP crystal and formation of Ag 0 during reduction. At a C/170 discharge rate V 5+ reductionmore » is the preferred initial reaction resulting in higher initial loaded voltage. At a discharge rate of C/400 reduction of Ag + with formation of conductive Ag 0 occurs earlier during discharge. Discharge rate also affects the spatial location of reduction products. The faster discharge rate initiates reduction close to the current collector with non-uniform distribution of silver metal resulting in isolated cathode areas. The slower rate develops a more homogenous distribution of reduced SVOP and silver metal. This study illuminates the roles of electronic and ionic conductivity limitations within a cathode at the mesoscale and how they impact the course of reduction processes and loaded voltage.« less

Rate Dependent Multi-Mechanism Discharge of Ag 0.50VOP 4·1.8H 2O: Insights from In Situ Energy Dispersive X-ray Diffraction

DOE PAGES

Huie, Matthew M.; Bock, David C.; Zhong, Zhong; ...

2016-09-01

Ag 0.50VOPO 4·1.8H 2O (silver vanadium phosphate, SVOP) demonstrates a counterintuitive higher initial loaded voltage under higher discharge current. Energy dispersive X-ray diffraction (EDXRD) from synchrotron radiation was used to create tomographic profiles of cathodes at various depths of discharge for two discharge rates. SVOP displays two reduction mechanisms, reduction of a vanadium center accompanied by lithiation of the structure, or reduction-displacement of a silver cation to form silver metal. In-situ EDXRD provides the opportunity to observe spatially resolved changes to the parent SVOP crystal and formation of Ag 0 during reduction. At a C/170 discharge rate V 5+ reductionmore » is the preferred initial reaction resulting in higher initial loaded voltage. At a discharge rate of C/400 reduction of Ag + with formation of conductive Ag 0 occurs earlier during discharge. Discharge rate also affects the spatial location of reduction products. The faster discharge rate initiates reduction close to the current collector with non-uniform distribution of silver metal resulting in isolated cathode areas. The slower rate develops a more homogenous distribution of reduced SVOP and silver metal. This study illuminates the roles of electronic and ionic conductivity limitations within a cathode at the mesoscale and how they impact the course of reduction processes and loaded voltage.« less

Photo-reduction of bromate in drinking water by metallic Ag and reduced graphene oxide (RGO) jointly modified BiVO4 under visible light irradiation.

PubMed

Chen, Fei; Yang, Qi; Zhong, Yu; An, Hongxue; Zhao, Jianwei; Xie, Ting; Xu, Qiuxiang; Li, Xiaoming; Wang, Dongbo; Zeng, Guangming

2016-09-15

Bromate (BrO3(-)), an oxyhalide disinfection by-product (DBP) in drinking water, has been demonstrated to be carcinogenic and genotoxic. In the current work, metallic Ag and reduced graphene oxide (RGO) co-modified BiVO4 was successfully synthesized by a stepwise chemical method coupling with a photo-deposition process and applied in the photo-reduction of BrO3(-) under visible light irradiation. In this composite, metallic Ag acted as an electron donor or mediator and RGO enhanced the BrO3(-) adsorption onto the surface of catalysts as well as an electron acceptor to restrict the recombination of photo-generated electron-hole pairs. The Ag@BiVO4@RGO composite exhibited greater photo-reduction BrO3(-) performance than pure BiVO4, Ag@BiVO4 and RGO@BiVO4 under identical experimental conditions: initial BrO3(-) concentration 150 μg/L, catalyst dosage 0.5 g/L, pH 7.0 and visible light (λ > 420 nm). The photoluminescence spectra (PL), electron-spin resonance (ESR), photocurrent density (PC) and electrochemical impedance spectroscopy (EIS) measurements indicated that the modified BiVO4 enhanced the photo-generated electrons and separated the electron-hole pairs. The photocatalytic reduction efficiency for BrO3(-) removal decreased with the addition of electron quencher K2S2O8, suggesting that electrons were the primary factor in this photo-reduction process. The declining photo-reduction efficiency of BrO3(-) in tap water should attribute to the consumption of photo-generated electrons by coexisting anions and the adsorption of dissolved organic matter (DOM) on graphene surface. The overall results indicate a promising application potential for photo-reduction in the DBPs removal from drinking water. Copyright © 2016 Elsevier Ltd. All rights reserved.

Nitrous Oxide Reduction by an Obligate Aerobic Bacterium, Gemmatimonas aurantiaca Strain T-27

PubMed Central

Park, Doyoung; Kim, Hayeon

2017-01-01

ABSTRACT N2O-reducing organisms with nitrous oxide reductases (NosZ) are known as the only biological sink of N2O in the environment. Among the most abundant nosZ genes found in the environment are nosZ genes affiliated with the understudied Gemmatimonadetes phylum. In this study, a unique regulatory mechanism of N2O reduction in Gemmatimonas aurantiaca strain T-27, an isolate affiliated with the Gemmatimonadetes phylum, was examined. Strain T-27 was incubated with N2O and/or O2 as the electron acceptor. Significant N2O reduction was observed only when O2 was initially present. When batch cultures of strain T-27 were amended with O2 and N2O, N2O reduction commenced after O2 was depleted. In a long-term incubation with the addition of N2O upon depletion, the N2O reduction rate decreased over time and came to an eventual stop. Spiking of the culture with O2 resulted in the resuscitation of N2O reduction activity, supporting the hypothesis that N2O reduction by strain T-27 required the transient presence of O2. The highest level of nosZ transcription (8.97 nosZ transcripts/recA transcript) was observed immediately after O2 depletion, and transcription decreased ∼25-fold within 85 h, supporting the observed phenotype. The observed difference between responses of strain T-27 cultures amended with and without N2O to O2 starvation suggested that N2O helped sustain the viability of strain T-27 during temporary anoxia, although N2O reduction was not coupled to growth. The findings in this study suggest that obligate aerobic microorganisms with nosZ genes may utilize N2O as a temporary surrogate for O2 to survive periodic anoxia. IMPORTANCE Emission of N2O, a potent greenhouse gas and ozone depletion agent, from the soil environment is largely determined by microbial sources and sinks. N2O reduction by organisms with N2O reductases (NosZ) is the only known biological sink of N2O at environmentally relevant concentrations (up to ∼1,000 parts per million by volume [ppmv]). Although a large fraction of nosZ genes recovered from soil is affiliated with nosZ found in the genomes of the obligate aerobic phylum Gemmatimonadetes, N2O reduction has not yet been confirmed in any of these organisms. This study demonstrates that N2O is reduced by an obligate aerobic bacterium, Gemmatimonas aurantiaca strain T-27, and suggests a novel regulation mechanism for N2O reduction in this organism, which may also be applicable to other obligate aerobic organisms possessing nosZ genes. We expect that these findings will significantly advance the understanding of N2O dynamics in environments with frequent transitions between oxic and anoxic conditions. PMID:28389533

Nitrous Oxide Reduction by an Obligate Aerobic Bacterium, Gemmatimonas aurantiaca Strain T-27.

PubMed

Park, Doyoung; Kim, Hayeon; Yoon, Sukhwan

2017-06-15

N 2 O-reducing organisms with nitrous oxide reductases (NosZ) are known as the only biological sink of N 2 O in the environment. Among the most abundant nosZ genes found in the environment are nosZ genes affiliated with the understudied Gemmatimonadetes phylum. In this study, a unique regulatory mechanism of N 2 O reduction in Gemmatimonas aurantiaca strain T-27, an isolate affiliated with the Gemmatimonadetes phylum, was examined. Strain T-27 was incubated with N 2 O and/or O 2 as the electron acceptor. Significant N 2 O reduction was observed only when O 2 was initially present. When batch cultures of strain T-27 were amended with O 2 and N 2 O, N 2 O reduction commenced after O 2 was depleted. In a long-term incubation with the addition of N 2 O upon depletion, the N 2 O reduction rate decreased over time and came to an eventual stop. Spiking of the culture with O 2 resulted in the resuscitation of N 2 O reduction activity, supporting the hypothesis that N 2 O reduction by strain T-27 required the transient presence of O 2 The highest level of nosZ transcription (8.97 nosZ transcripts/ recA transcript) was observed immediately after O 2 depletion, and transcription decreased ∼25-fold within 85 h, supporting the observed phenotype. The observed difference between responses of strain T-27 cultures amended with and without N 2 O to O 2 starvation suggested that N 2 O helped sustain the viability of strain T-27 during temporary anoxia, although N 2 O reduction was not coupled to growth. The findings in this study suggest that obligate aerobic microorganisms with nosZ genes may utilize N 2 O as a temporary surrogate for O 2 to survive periodic anoxia. IMPORTANCE Emission of N 2 O, a potent greenhouse gas and ozone depletion agent, from the soil environment is largely determined by microbial sources and sinks. N 2 O reduction by organisms with N 2 O reductases (NosZ) is the only known biological sink of N 2 O at environmentally relevant concentrations (up to ∼1,000 parts per million by volume [ppmv]). Although a large fraction of nosZ genes recovered from soil is affiliated with nosZ found in the genomes of the obligate aerobic phylum Gemmatimonadetes , N 2 O reduction has not yet been confirmed in any of these organisms. This study demonstrates that N 2 O is reduced by an obligate aerobic bacterium, Gemmatimonas aurantiaca strain T-27, and suggests a novel regulation mechanism for N 2 O reduction in this organism, which may also be applicable to other obligate aerobic organisms possessing nosZ genes. We expect that these findings will significantly advance the understanding of N 2 O dynamics in environments with frequent transitions between oxic and anoxic conditions. Copyright © 2017 American Society for Microbiology.

Rapid nitrous oxide cycling in the suboxic ocean

NASA Astrophysics Data System (ADS)

Babbin, Andrew R.; Bianchi, Daniele; Jayakumar, Amal; Ward, Bess B.

2015-06-01

Nitrous oxide (N2O) is a powerful greenhouse gas and a major cause of stratospheric ozone depletion, yet its sources and sinks remain poorly quantified in the oceans. We used isotope tracers to directly measure N2O reduction rates in the eastern tropical North Pacific. Because of incomplete denitrification, N2O cycling rates are an order of magnitude higher than predicted by current models in suboxic regions, and the spatial distribution suggests strong dependence on both organic carbon and dissolved oxygen concentrations. Furthermore, N2O turnover is 20 times higher than the net atmospheric efflux. The rapid rate of this cycling coupled to an expected expansion of suboxic ocean waters implies future increases in N2O emissions.

Effect of La substitution on structural and electrical properties of BiFeO3 thin film

NASA Astrophysics Data System (ADS)

Das, S. R.; Bhattacharya, P.; Choudhary, R. N. P.; Katiyar, R. S.

2006-03-01

The effect of La substitution on the structural and electrical properties of multiferroic BiFeO3 thin films grown on Pt/TiO2/SiO2/Si substrates by pulsed laser deposition has been reported. X-ray diffraction data confirmed the substitutions of La into the Bi site with the elimination of all of the secondary phases. The dielectric constant of the films was systematically increased from 165 to ~350 and the films showed excellent dielectric loss behavior. We observed a gradual increase in the remnant polarization (2Pr) with lanthanum substitution obtaining a maximum value of ~42 μC/cm2 at 20 mol % La incorporation. The leakage current behavior at room temperature of the films was studied and it was found that the leakage current decreased from 10-4 to 10-7 A/cm2 for La-substituted films at a field strength of 50 kV/cm. The reduction of dc leakage current of La-substituted films is explained on the basis of relative phase stability and improved microstructure of the material.

SnO2, IrO2, Ta2O5, Bi2O3, and TiO2 nanoparticle anodes: electrochemical oxidation coupled with the cathodic reduction of water to yield molecular H2

NASA Astrophysics Data System (ADS)

Choi, Jina; Qu, Yan; Hoffmann, Michael R.

2012-08-01

In recent years, the search for environmentally friendly alternative energy sources with reduced carbon footprints has increased. The coupling of photovoltaic power sources with advanced electrolysis systems for hydrogen production via water splitting using organic contaminants as sacrificial electron donors has been considered to a be viable alternative. In this report, we demonstrated the feasibility of a scaled-up rooftop prototype of the proposed hybrid photovoltaic-electrolysis system, which utilizes semiconductor nanoparticles coated on to metal substrates as electrodes for the generation of hydrogen coupled with the oxidation of wastewater. Application of an anodic bias of >2.0 V to bismuth-doped TiO2 (BiO x -TiO2) on Ti metal anodes with a sequential under-coatings of nanoparticulate SnO2, IrO2, Ta2O5, and Bi2O3 results in the electrochemical degradation of a variety of organic chemical contaminants in water (i.e., rhodamine B (Rh.B), methylene blue (MB), salicylic acid, triclosan, and phenol) and actual wastewater from a chemical manufacturing plant, while at the same time, molecular hydrogen is produced at stainless steel (SS) cathodes. The kinetics of the anodic substrates oxidation is investigated as a function of the cell current ( I cell), substrate concentration, and background electrolyte composition (e.g., NaCl, Na2SO4, or seawater). Average current efficiencies were found to be in the range of 4-22 %, while the cathodic current and energy efficiencies for hydrogen production were found to be in the range of 50-70 % and 20-40 %, respectively.

Novel strategy to mitigate cathode catalyst degradation during air/air startup cycling via the atmospheric resistive switching mechanism of a hydrogen anode with a platinum catalyst supported on tantalum-doped titanium dioxide

NASA Astrophysics Data System (ADS)

Shintani, Haruhiko; Kojima, Yuya; Kakinuma, Katsuyoshi; Watanabe, Masahiro; Uchida, Makoto

2015-10-01

We propose a new strategy for alleviating the reverse current phenomenon using a unique ;atmospheric resistive switching mechanism; (ARSM) of a metal oxide semiconductor support, such that the electrical resistivity changes depending on the gas atmosphere. The membrane-electrode assembly (MEA) using Ta-doped TiO2-supported platinum (Pt/Ta-TiO2) as the anode catalyst showed approximately one order of magnitude greater resistance in air than in hydrogen. The overpotential of the hydrogen oxidation reaction was negligible up to at least 1.5 A cm-2. The losses of electrochemically active surface area and carbon corrosion of the cathode catalyst during air/air startup cycling were significantly suppressed by the use of the Pt/Ta-TiO2 anode. The decrease in the degradation is attributed to a reduction of the reverse current due to a low oxygen reduction reaction rate at the anode, which showed high resistivity in air. These results demonstrate the effectiveness of the ARSM in mitigating cathode catalyst degradation during air/air startup cycling.

High-performance thin-film transistors with solution-processed ScInO channel layer based on environmental friendly precursor

NASA Astrophysics Data System (ADS)

Song, Wei; Lan, Linfeng; Li, Meiling; Wang, Lei; Lin, Zhenguo; Sun, Sheng; Li, Yuzhi; Song, Erlong; Gao, Peixiong; Li, Yan; Peng, Junbiao

2017-09-01

Thin-film transistors (TFTs) with solution-processed scandium (Sc) substituted indium oxide (Sc x In1-x O3, ScInO) thin films based on environmental friendly water-induced precursor were fabricated. As the Sc concentration increases from 0% to 10%, the mobility decreases from 23.7 cm2 V-1 s-1 to 6.4 cm2 V-1 s-1, which is attributed to the non-overlapping of the Sc3+ electron orbit. However, the off current decreases and the turn-ON voltage (V ON) shifts towards the positive direction as the Sc content increases, which indicates lower carrier density after incorporation of Sc into In2O3. More interestingly, the incorporation of Sc into In2O3 can effectively improve the electrical stability of the TFT devices under gate bias stress, which is attributed to the reduction of the number of oxygen vacancies due to the relatively low standard electrode potential (-2.36) of Sc and strong bonding strength of Sc-O (680 kJ mol-1). The reduction of oxygen vacancies is confirmed by the x-ray photoelectron spectroscopy (XPS) experiments.

Formation and reduction behaviors of zirconium oxide compounds in LiCl-Li2O melt at 923 K

NASA Astrophysics Data System (ADS)

Sakamura, Yoshiharu; Iizuka, Masatoshi; Kitawaki, Shinichi; Nakayoshi, Akira; Kofuji, Hirohide

2015-11-01

The reduction behaviors of ZrO2, Li2ZrO3 and (U,Pu,Zr)O2 in a LiCl-Li2O salt bath at 923 K were investigated. This study was conducted as part of a feasibility study on the pyrochemical treatment of damaged fuel debris generated by severe accidents at light water reactors. It was demonstrated in electrolytic reduction tests that the uranium in synthetic corium specimens of (U,Pu,Zr)O2 with various ZrO2 contents could be reduced to the metallic form and that part of the zirconium was converted to Li2ZrO3. Zirconium metal and Li2ZrO3 were obtained by the reduction of ZrO2. The reduction of Li2ZrO3 did not proceed even in LiCl containing no Li2O. Moreover, the stable chemical forms of the ZrO2-Li2O complex oxide were investigated as a function of the Li2O concentration in LiCl. ZrO2 was converted to Li2ZrO3 at a Li2O concentration of 0.018 wt%. As the Li2O concentration was increased, Li2ZrO3 was converted to Li6Zr2O7 and then to Li8ZrO6. It is suggested that the removal of Li2ZrO3 from the reduction product is a key point in the pyrochemical treatment of corium.

Isothermal reduction kinetics and mineral phase of chromium-bearing vanadium-titanium sinter reduced with CO gas at 873-1273 K

NASA Astrophysics Data System (ADS)

Yang, Song-tao; Zhou, Mi; Jiang, Tao; Xue, Xiang-xin

2018-02-01

Reduction of chromium-bearing vanadium-titanium sinter (CVTS) was studied under simulated conditions of a blast furnace, and thermodynamics and kinetics were theoretically analyzed. Reduction kinetics of CVTS at different temperatures was evaluated using a shrinking unreacted core model. The microstructure, mineral phase, and variation of the sinter during reduction were observed by X-ray diffraction, scanning electron microscopy, and metallographic microscopy. Results indicate that porosity of CVTS increased with temperature. Meanwhile, the reduction degree of the sinter improved with the reduction rate. Reduction of the sinter was controlled by a chemical reaction at the initial stage and inner diffusion at the final stage. Activation energies measured 29.22-99.69 kJ/mol. Phase transformations in CVTS reduction are as follows: Fe2O3→Fe3O4→FeO→Fe; Fe2TiO5→Fe2TiO4→FeTiO3; FeO·V2O3→V2O3; FeO·Cr2O3→Cr2O3.

Recent progress and perspectives in the photocatalytic CO2 reduction of Ti-oxide-based nanomaterials

NASA Astrophysics Data System (ADS)

Sohn, Youngku; Huang, Weixin; Taghipour, Fariborz

2017-02-01

The conversion of CO2 with H2O to valuable chemicals and fuels is a new solution to current environmental and energy problems, and the high energy barrier of these reactions can be overcome by the input of solar and electrical energy. However, the reduction efficiencies and selectivities of these reactions are insufficient for practical use, and significant effort and strategy are required to overcome the many obstacles preventing the large-scale application of photocatalytic CO2 reduction. This article reviews recent progress in CO2 reduction using titanium oxide-based materials and various strategic factors for increasing photocatalytic efficiency. This article also highlights non-titanium-oxide catalysts, the photoelectrocatalytic reduction of CO2, and other recent review articles concerning the recycling of CO2 to value-added carbon compounds.

The influence of foreign vs. North American emissions on surface ozone in the US

NASA Astrophysics Data System (ADS)

Reidmiller, D. R.; Fiore, A. M.; Jaffe, D. A.; Bergmann, D.; Cuvelier, C.; Dentener, F. J.; Duncan, B. N.; Folberth, G.; Gauss, M.; Gong, S.; Hess, P.; Jonson, J. E.; Keating, T.; Lupu, A.; Marmer, E.; Park, R.; Schultz, M. G.; Shindell, D. T.; Szopa, S.; Vivanco, M. G.; Wild, O.; Zuber, A.

2009-03-01

As part of the Hemispheric Transport of Air Pollution (HTAP; http://www.htap.org/) project, we analyze results from 16 global and hemispheric chemical transport models and compare these to Clean Air Status and Trends Network (CASTNet) observations in the United States (US) for 2001. Using the policy-relevant maximum daily 8-h ozone (MDA8 O3) statistic, the multi-model ensemble represents the observations well (mean r2=0.57, ensemble bias=+4.1 ppbv for all regions and all seasons) despite a wide range in the individual model results. Correlations are strongest in the NorthEastern US during spring and fall (r2=0.68); and weakest in the Midwestern US in summer (r2=0.46). However, large positive mean biases exist during summer for all Eastern US regions, ranging from 10-20 ppbv, and a smaller negative bias is present in the Western US during spring (~3 ppbv). In most all other regions and seasons, the biases of the model ensemble simulations are ≤5 ppbv. Sensitivity simulations in which anthropogenic O3-precursor emissions (NOx+NMVOC+CO+aerosols) were decreased by 20% in each of four source regions: East Asia (EA), South Asia (SA), Europe (EU) and North America (NA) show that the greatest response of MDA8 O3 to the summed foreign emissions reductions occurs during spring in the West (0.9 ppbv reduction due to 20% reductions from EA+SA+EU). East Asia is the largest contributor to MDA8 O3 at all ranges of the O3 distribution for most regions (typically ~0.45 ppbv). The exception is in the NorthEastern US where European emissions reductions had the greatest impact on MDA8 O3, particularly in the middle of the MDA8 O3 distribution (response of ~0.35 ppbv between 35-55 ppbv). In all regions and seasons, however, O3-precursor emissions reductions of 20% in the NA source region decrease MDA8 O3 the most - by a factor of 2 to nearly 10 relative to foreign emissions reductions. The O3 response to anthropogenic NA emissions is greatest in the Eastern US during summer at the high end of the O3 distribution (5-6 ppbv for 20% reductions). While the impact of foreign emissions on surface O3 in the US is not negligible - and is of increasing concern given the growth in emissions upwind of the US - domestic emissions reductions remain a far more effective means of decreasing MDA8 O3 values, particularly those above 75 ppb (the current US standard).

Catalysts for ultrahigh current density oxygen cathodes for space fuel cell applications

NASA Technical Reports Server (NTRS)

Tryk, D.; Yeager, E.; Shingler, M.; Aldred, W.; Wang, C.

1990-01-01

The objective of this research was to identify promising electrocatalyst/support systems for the oxygen cathode in alkaline fuel cells operating at relatively high temperatures, O2 pressures and current densities. A number of materials were prepared, including Pb-Ru and Pb-Ir pyrochlores, RuO2 and Pt-doped RuO2, and lithiated NiO. Several of these were prepared using techniques that had not been previously used to prepare them. Particularly interesting is the use of the alkaline solution technique to prepare the Pt-doped Pb-Ru pyrochlore in high area form. Well-crystallized Pb(2)Ru(2)O(7-y) was used to fabricate high performance O2 cathodes with relatively good stability in room temperature KOH. This material was also found to be stable over a useful potential range at approximately 140 C in concentrated KOH. Other pyrochlores were found to be either unstable (amorphous samples) or the fabrication of the gas-fed electrodes could not be fully optimized during this project period. Future work may be directed at this problem. High area platinum supported on conductive metal oxide supports produced mixed results: small improvements in O2 reduction performance for Pb(2)Ru(2)O(7-y) but a large improvement for Li-doped NiO at room temperature. Nearly reversible behavior was observed for the O2/OH couple for Li-doped NiO at approximately 200 C.

Nitrous oxide emissions from agricultural landscapes: quantification tools, policy development, and opportunities for improved management

NASA Astrophysics Data System (ADS)

Tonitto, C.; Gurwick, N. P.

2012-12-01

Policy initiatives to reduce greenhouse gas emissions (GHG) have promoted the development of agricultural management protocols to increase SOC storage and reduce GHG emissions. We review approaches for quantifying N2O flux from agricultural landscapes. We summarize the temporal and spatial extent of observations across representative soil classes, climate zones, cropping systems, and management scenarios. We review applications of simulation and empirical modeling approaches and compare validation outcomes across modeling tools. Subsequently, we review current model application in agricultural management protocols. In particular, we compare approaches adapted for compliance with the California Global Warming Solutions Act, the Alberta Climate Change and Emissions Management Act, and by the American Carbon Registry. In the absence of regional data to drive model development, policies that require GHG quantification often use simple empirical models based on highly aggregated data of N2O flux as a function of applied N - Tier 1 models according to IPCC categorization. As participants in development of protocols that could be used in carbon offset markets, we observed that stakeholders outside of the biogeochemistry community favored outcomes from simulation modeling (Tier 3) rather than empirical modeling (Tier 2). In contrast, scientific advisors were more accepting of outcomes based on statistical approaches that rely on local observations, and their views sometimes swayed policy practitioners over the course of policy development. Both Tier 2 and Tier 3 approaches have been implemented in current policy development, and it is important that the strengths and limitations of both approaches, in the face of available data, be well-understood by those drafting and adopting policies and protocols. The reliability of all models is contingent on sufficient observations for model development and validation. Simulation models applied without site-calibration generally result in poor validation results, and this point particularly needs to be emphasized during policy development. For cases where sufficient calibration data are available, simulation models have demonstrated the ability to capture seasonal patterns of N2O flux. The reliability of statistical models likewise depends on data availability. Because soil moisture is a significant driver of N2O flux, the best outcomes occur when empirical models are applied to systems with relevant soil classification and climate. The structure of current carbon offset protocols is not well-aligned with a budgetary approach to GHG accounting. Current protocols credit field-scale reduction in N2O flux as a result of reduced fertilizer use. Protocols do not award farmers credit for reductions in CO2 emissions resulting from reduced production of synthetic N fertilizer. To achieve the greatest GHG emission reductions through reduced synthetic N production and reduced landscape N saturation requires a re-envisioning of the agricultural landscape to include cropping systems with legume and manure N sources. The current focus on on-farm GHG sources focuses credits on simple reductions of N applied in conventional systems rather than on developing cropping systems which promote higher recycling and retention of N.

Enhanced electrical properties of dual-layer channel ZnO thin film transistors prepared by atomic layer deposition

NASA Astrophysics Data System (ADS)

Li, Huijin; Han, Dedong; Dong, Junchen; Yu, Wen; Liang, Yi; Luo, Zhen; Zhang, Shengdong; Zhang, Xing; Wang, Yi

2018-05-01

The thin film transistors (TFTs) with a dual-layer channel structure combing ZnO thin layer grown at 200 °C and ZnO film grown at 120 °C by atomic layer deposition are fabricated. The dual-layer channel TFT exhibits a low leakage current of 2.8 × 10-13 A, Ion/Ioff ratio of 3.4 × 109, saturation mobility μsat of 12 cm2 V-1 s-1, subthreshold swing (SS) of 0.25 V/decade. The SS value decreases to 0.18 V/decade after the annealing treatment in O2 due to the reduction of the trap states at the channel/dielectric interface and in the bulk channel layer. The enhanced performance obtained from the dual-layer channel TFTs is due to the ability of maintaining high mobility and suppressing the increase in the off-current at the same time.

Water reduction by a p-GaInP2 photoelectrode stabilized by an amorphous TiO2 coating and a molecular cobalt catalyst.

PubMed

Gu, Jing; Yan, Yong; Young, James L; Steirer, K Xerxes; Neale, Nathan R; Turner, John A

2016-04-01

Producing hydrogen through solar water splitting requires the coverage of large land areas. Abundant metal-based molecular catalysts offer scalability, but only if they match noble metal activities. We report on a highly active p-GaInP2 photocathode protected through a 35-nm TiO2 layer functionalized by a cobaloxime molecular catalyst (GaInP2-TiO2-cobaloxime). This photoelectrode mediates H2 production with a current density of ∼9 mA cm(-2) at a potential of 0 V versus RHE under 1-sun illumination at pH 13. The calculated turnover number for the catalyst during a 20-h period is 139,000, with an average turnover frequency of 1.9 s(-1). Bare GaInP2 shows a rapid current decay, whereas the GaInP2-TiO2-cobaloxime electrode shows ≤5% loss over 20 min, comparable to a GaInP2-TiO2-Pt catalyst particle-modified interface. The activity and corrosion resistance of the GaInP2-TiO2-cobaloxime photocathode in basic solution is made possible by an atomic layer-deposited TiO2 and an attached cobaloxime catalyst.

Facing-target mid-frequency magnetron reactive sputtered hafnium oxide film: Morphology and electrical properties

NASA Astrophysics Data System (ADS)

Zhang, Yu; Xu, Jun; Wang, You-Nian; Choi, Chi Kyu; Zhou, Da-Yu

2016-03-01

Amorphous hafnium dioxide (HfO2) film was prepared on Si (100) by facing-target mid-frequency reactive magnetron sputtering under different oxygen/argon gas ratio at room temperature with high purity Hf target. 3D surface profiler results showed that the deposition rates of HfO2 thin film under different O2/Ar gas ratio remain unchanged, indicating that the facing target midfrequency magnetron sputtering system provides effective approach to eliminate target poisoning phenomenon which is generally occurred in reactive sputtering procedure. X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR) demonstrated that the gradual reduction of oxygen vacancy concentration and the densification of deposited film structure with the increase of oxygen/argon (O2/Ar) gas flow ratio. Atomic force microscopy (AFM) analysis suggested that the surface of the as-deposited HfO2 thin film tends to be smoother, the root-meansquare roughness (RMS) reduced from 0.876 nm to 0.333 nm while O2/Ar gas flow ratio increased from 1/4 to 1/1. Current-Voltage measurements of MOS capacitor based on Au/HfO2/Si structure indicated that the leakage current density of HfO2 thin films decreased by increasing of oxygen partial pressure, which resulted in the variations of pore size and oxygen vacancy concentration in deposited thin films. Based on the above characterization results the leakage current mechanism for all samples was discussed systematically.

Degradation of (La(0.8)Sr(0.2))(0.98)MnO(3-δ)-Zr(0.84)Y(0.16)O(2-γ) composite electrodes during reversing current operation.

PubMed

Hughes, Gareth A; Railsback, Justin G; Yakal-Kremski, Kyle J; Butts, Danielle M; Barnett, Scott A

2015-01-01

Reversing-current operation of solid oxide cell (La(0.8)Sr(0.2))(0.98)MnO(3-δ)-Zr(0.84)Y(0.16)O(2-γ) (LSM-YSZ) oxygen electrodes is described. Degradation was characterized by impedance spectroscopy in symmetric cells tested at 800 °C in air with a symmetric current cycle with a period of 12 hours. No change in cell resistance could be detected, in 1000 h tests with a sensitivity of ∼1% per kh, at a current density of 0.5 A cm(-2) corresponding to an overpotential of 0.18 V. At a current density to 0.6 A cm(-2) (0.33 V overpotential) measurable resistance degradation at a rate of 3% per kh was observed, while higher current/overpotential values led to faster degradation. Degradation was observed mainly in the ohmic resistance for current densities of 0.6, 0.8 and 0.9 A cm(-2), with little change in the polarization resistance. Polarization degradation, mainly observed at higher current density, was present as an increase in an impedance response at ∼30 kHz, apparently associated with the resistance of YSZ grain boundaries within the electrode. Microstructural and chemical analysis showed significant changes in electrode structure after the current cycling, including an increase in LSM particle size and a reduction in the amount of YSZ and LSM at the electrode/electrolyte interface - the latter presumably a precursor to delamination.

Effect of substrate nature on the electrochemical deposition of calcium-deficient hydroxyapatites

NASA Astrophysics Data System (ADS)

Gualdrón-Reyes, A. F.; Domínguez-Vélez, V.; Morales-Morales, J. A.; Cabanzo, R.; Meléndez, A. M.

2017-01-01

Calcium phosphates were obtained by reducing nitrate ions to produce hydroxide ions on TiO2/stainless steel and TiO2/titanium electrodes. TiO2 coatings on metallic substrates were prepared by sol-gel dip-coating method. The morphology of deposits was observed by FESEM. Chemical nature of calcium phosphate deposits was identified by Raman micro-spectroscopy and FESEM/EDS microanalysis. Electrochemical behavior of nitrate and nitrite reduction on stainless steel and titanium electrodes was studied by linear sweep voltammetry. In addition, voltammetric study of the calcium phosphate electrodeposition on both electrodes was performed. From these measurements was selected the potential to form a calcium phosphate. A catalytic current associated to nitrate reduction reaction was obtained for stainless steel electrode, leading to significant deposition of calcium phosphate. Ca/P ratio for both substrates was less than 1.67. The formation of calcium deficient hydroxyapatite was confirmed by Raman spectroscopy.

Selective photocatalytic reduction of CO2 by H2O/H2 to CH4 and CH3OH over Cu-promoted In2O3/TiO2 nanocatalyst

NASA Astrophysics Data System (ADS)

Tahir, Muhammad; Tahir, Beenish; Saidina Amin, Nor Aishah; Alias, Hajar

2016-12-01

Photocatalytic CO2 reduction by H2O and/or H2 reductant to selective fuels over Cu-promoted In2O3/TiO2 photocatalyst has been investigated. The samples, prepared via a simple and direct sol-gel method, were characterized by XRD, SEM, TEM, XPS, N2 adsorption-desorption, UV-vis diffuse reflectance, Raman and PL spectroscopy. Cu and In loaded into TiO2, oxidized as Cu2+ and In3+, promoted efficient separation of photo-generated electron/hole pairs (e-/h+). The results indicate that the reduction rate of CO2 by H2O to CH4 approached to 181 μmol g-1 h-1 using 0.5% Cu-3% In2O3/TiO2 catalyst, a 1.53 fold higher than the production rate over the 3% In2O3/TiO2 and 5 times the amount produced over the pure TiO2. In addition, Cu was found to promote efficient production of CH3OH and yield rate reached to 68 μmol g-1 h-1 over 1% Cu-3% In2O3/TiO2 catalyst. This improvement was attributed to charge transfer property and suppressed recombination rate by Cu-metal. More importantly, H2 reductant was less favorable for CH4 production, yet a significant amount of CH4 and CH3OH were obtained using a mixture of H2O/H2 reductant. Therefore, Cu-loaded In2O3/TiO2 catalyst has shown to be capable for methanol production, whereas product selectivity was greatly depending on the amount of Cu-loading and the type of reductant. A photocatalytic reaction mechanism was proposed to understand the experimental results over the Cu-loaded In2O3/TiO2 catalyst.

Microsized Porous SiOx@C Composites Synthesized through Aluminothermic Reduction from Rice Husks and Used as Anode for Lithium-Ion Batteries.

PubMed

Cui, Jinlong; Cui, Yongfu; Li, Shaohui; Sun, Hongliang; Wen, Zhongsheng; Sun, Juncai

2016-11-09

Microsized porous SiO x @C composites used as anode for lithium-ion batteries (LIBs) are synthesized from rice husks (RHs) through low-temperature (700 °C) aluminothermic reduction. The resulting SiO x @C composite shows mesoporous irregular particle morphology with a high specific surface area of 597.06 m 2 /g under the optimized reduction time. This porous SiO x @C composite is constructed by SiO x nanoparticles uniformly dispersed in the C matrix. When tested as anode material for LIBs, it displays considerable specific capacity (1230 mAh/g at a current density of 0.1 A/g) and excellent cyclic stability with capacity fading of less than 0.5% after 200 cycles at 0.8 A/g. The dramatic volume change for the Si anode during lithium-ion (Li + ) insertion and extraction can be successfully buffered because of the formation of Li 2 O and Li 4 SiO 4 during initial lithiation process and carbon coating layer on the surface of SiO x . The porous structure could also mitigate the volume change and mechanical strains and shorten the Li + diffusion path length. These characteristics improve the cyclic stability of the electrode. This low-cost and environment-friendly SiO x @C composite anode material exhibits great potential as an alternative for traditional graphite anodes.

Initial Reduction of CO2 on Pd-, Ru-, and Cu-Doped CeO2(111) Surfaces: Effects of Surface Modification on Catalytic Activity and Selectivity.

PubMed

Guo, Chen; Wei, Shuxian; Zhou, Sainan; Zhang, Tian; Wang, Zhaojie; Ng, Siu-Pang; Lu, Xiaoqing; Wu, Chi-Man Lawrence; Guo, Wenyue

2017-08-09

Surface modification by metal doping is an effective treatment technique for improving surface properties for CO 2 reduction. Herein, the effects of doped Pd, Ru, and Cu on the adsorption, activation, and reduction selectivity of CO 2 on CeO 2 (111) were investigated by periodic density functional theory. The doped metals distorted the configuration of a perfect CeO 2 (111) by weakening the adjacent Ce-O bond strength, and Pd doping was beneficial for generating a highly active O vacancy. The analyses of adsorption energy, charge density difference, and density of states confirmed that the doped metals were conducive for enhancing CO 2 adsorption, especially for Cu/CeO 2 (111). The initial reductive dissociation CO 2 → CO* + O* on metal-doped CeO 2 (111) followed the sequence of Cu- > perfect > Pd- > Ru-doped CeO 2 (111); the reductive hydrogenation CO 2 + H → COOH* followed the sequence of Cu- > perfect > Ru- > Pd-doped CeO 2 (111), in which the most competitive route on Cu/CeO 2 (111) was exothermic by 0.52 eV with an energy barrier of 0.16 eV; the reductive hydrogenation CO 2 + H → HCOO* followed the sequence of Ru- > perfect > Pd-doped CeO 2 (111). Energy barrier decomposition analyses were performed to identify the governing factors of bond activation and scission along the initial CO 2 reduction routes. Results of this study provided deep insights into the effect of surface modification on the initial reduction mechanisms of CO 2 on metal-doped CeO 2 (111) surfaces.

Production and reduction of nitrous oxide in agricultural and forest soils.

PubMed

Yu, K; Chen, G; Struwe, S; Kjøller, A

2000-06-01

A soil-water slurry experiment was conducted to study the potentials of N2O production and reduction in denitrification of agricultural and beech forest soils in Denmark. The effects of nitrate and ammonium additions on denitrification were also investigated. The forest soil showed a higher denitrification potential than the agricultural soil. However, N2O reduction potential of the agricultural soil was higher than the beech forest soil, shown by the ratio of N2O/N2 approximately 0.11 and 3.65 in the agricultural and the beech forest soils, respectively. Both nitrate and ammonium additions stimulated the N2O production in the two soils, but reduced the N2O reduction rates in the agricultural soil slurries. In contrast to the effect on the agricultural soil, nitrate reduced the N2O reduction rate in the beech forest soil, while ammonium showed a stimulating effect on the N2O reduction activity. After one week incubation, all of the N2O produced was reduced to N2 in the agricultural soil when nitrate was still present. Nitrous oxide reduction in the beech forest soil occurred only when nitrate almost disappeared. The different nitrate inhibitory effect on the N2O reduction activity in the two soils was due to the difference in soil pH. Inhibition of nitrate on N2O reduction was significant under acidic condition. Consequently, soil could serve as a sink of atmospheric N2O under the conditions of anaerobic, pH near neutral and low nitrate content.

Investigations of surface coatings to reduce memory effect in plastic scintillator detectors used for radioxenon detection

NASA Astrophysics Data System (ADS)

Bläckberg, L.; Fay, A.; Jõgi, I.; Biegalski, S.; Boman, M.; Elmgren, K.; Fritioff, T.; Johansson, A.; Mårtensson, L.; Nielsen, F.; Ringbom, A.; Rooth, M.; Sjöstrand, H.; Klintenberg, M.

2011-11-01

In this work Al2O3 and SiO2 coatings are tested as Xe diffusion barriers on plastic scintillator substrates. The motivation is improved beta-gamma coincidence detection systems, used to measure atmospheric radioxenon within the verification regime of the Comprehensive Nuclear-Test-Ban Treaty. One major drawback with the current setup of these systems is that the radioxenon tends to diffuse into the plastic scintillator material responsible for the beta detection, resulting in an unwanted memory effect. Here, coatings with thicknesses between 20 and 900 nm have been deposited onto plastic scintillators, and investigated using two different experimental techniques. The results show that all tested coatings reduce the Xe diffusion into the plastic. The reduction is observed to increase with coating thickness for both coating materials. The 425 nm Al2O3 coating is the most successful one, presenting a diffusion reduction of a factor 100, compared to uncoated plastic. In terms of memory effect reduction this coating is thus a viable solution to the problem in question.

NiCo2O4/N-doped graphene as an advanced electrocatalyst for oxygen reduction reaction

NASA Astrophysics Data System (ADS)

Zhang, Hui; Li, Huiyong; Wang, Haiyan; He, Kejian; Wang, Shuangyin; Tang, Yougen; Chen, Jiajie

2015-04-01

Developing low-cost catalyst for high-performance oxygen reduction reaction (ORR) is highly desirable. Herein, NiCo2O4/N-doped reduced graphene oxide (NiCo2O4/N-rGO) hybrid is proposed as a high-performance catalyst for ORR for the first time. The well-formed NiCo2O4/N-rGO hybrid is studied by cyclic voltammetry (CV) curves and linear-sweep voltammetry (LSV) performed on the rotating-ring-disk-electrode (RDE) in comparison with N-rGO-free NiCo2O4 and the bare N-rGO. Due to the synergistic effect, the NiCo2O4/N-rGO hybrid exhibits significant improvement of catalytic performance with an onset potential of -0.12 V, which mainly favors a direct four electron pathway in ORR process, close to the behavior of commercial carbon-supported Pt. Also, the benefits of N-incorporation are investigated by comparing NiCo2O4/N-rGO with NiCo2O4/rGO, where higher cathodic currents, much more positive half-wave potential and more electron transfer numbers are observed for the N-doping one, which should be ascribed to the new highly efficient active sites created by N incorporation into graphene. The NiCo2O4/N-rGO hybrid could be used as a promising catalyst for high power metal/air battery.

Efficient electrolyzer for CO2 splitting in neutral water using earth-abundant materials.

PubMed

Tatin, Arnaud; Comminges, Clément; Kokoh, Boniface; Costentin, Cyrille; Robert, Marc; Savéant, Jean-Michel

2016-05-17

Low-cost, efficient CO2-to-CO+O2 electrochemical splitting is a key step for liquid-fuel production for renewable energy storage and use of CO2 as a feedstock for chemicals. Heterogeneous catalysts for cathodic CO2-to-CO associated with an O2-evolving anodic reaction in high-energy-efficiency cells are not yet available. An iron porphyrin immobilized into a conductive Nafion/carbon powder layer is a stable cathode producing CO in pH neutral water with 90% faradaic efficiency. It is coupled with a water oxidation phosphate cobalt oxide anode in a home-made electrolyzer by means of a Nafion membrane. Current densities of approximately 1 mA/cm(2) over 30-h electrolysis are achieved at a 2.5-V cell voltage, splitting CO2 and H2O into CO and O2 with a 50% energy efficiency. Remarkably, CO2 reduction outweighs the concurrent water reduction. The setup does not prevent high-efficiency proton transport through the Nafion membrane separator: The ohmic drop loss is only 0.1 V and the pH remains stable. These results demonstrate the possibility to set up an efficient, low-voltage, electrochemical cell that converts CO2 into CO and O2 by associating a cathodic-supported molecular catalyst based on an abundant transition metal with a cheap, easy-to-prepare anodic catalyst oxidizing water into O2.

Electrochemical reduction of hexahydro-1,3,5-trinitro-1,3,5-triazine in aqueous solutions.

PubMed

Bonin, Pascale M L; Bejan, Dorin; Schutt, Leah; Hawari, Jalal; Bunce, Nigel J

2004-03-01

Electrochemical reduction of RDX, hexahydro-1,3,5-trinitro-1,3,5-triazine, a commercial and military explosive, was examined as a possible remediation technology for treating RDX-contaminated groundwater. A cascade of divided flow-through cells was used, with reticulated vitreous carbon cathodes and IrO2/Ti dimensionally stable anodes, initially using acetonitrile/water solutions to increase the solubility of RDX. The major degradation pathway involved reduction of RDX to the corresponding mononitroso compound, followed by ring cleavage to yield formaldehyde and methylenedinitramine. The reaction intermediates underwent further reduction and/or hydrolysis, the net result being the complete transformation of RDX to small molecules. The rate of degradation increased with current density, but the current efficiency was highest at low current densities. The technique was extended successfully both to 100% aqueous solutions of RDX and to an undivided electrochemical cell.

Molecular Cobalt Catalysts for O 2 Reduction: Low-Overpotential Production of H 2 O 2 and Comparison with Iron-Based Catalysts

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

Wang, Yu-Heng; Pegis, Michael L.; Mayer, James M.

A series of mononuclear pseudo-macrocyclic cobalt complexes have been investigated as catalysts for O2 reduction. Each of these complexes, with CoIII/II reduction potentials that span nearly 400 mV, mediate highly selective two- electron reduction of O2 to H2O2 (93–99%) using decamethylferrocene (Fc*) as the reductant and acetic acid as the proton source. Kinetic studies reveal that the rate exhibits a first- order dependence on [Co] and [AcOH], but no dependence on [O2] or [Fc*]. A linear correlation is observed between log(TOF) vs. E1/2(CoIII/II) for the different cobalt complexes (TOF = turnover frequency). The thermodynamic potential for+ O2 reduction to H2O2more » was estimated by measuring the H /H2 open-circuit potential under the reaction conditions. This value provides the basis for direct assessment of the thermodynamic efficiency of the different catalysts and shows that H2O2 is formed with overpotentials as low as 90 mV. These results are compared with a recently reported series of Fe-porphyrin complexes, which catalyze four-electron reduction of O2 to H2O. The data show that the TOFs of the Co complexes exhibit a shallower dependence on E1/2(MIII/II) than the Fe complexes. This behavior, which underlies the low overpotential, is rationalized on the basis of the catalytic rate law.« less

Effect of Dielectric Interface on the Performance of MoS2 Transistors.

PubMed

Li, Xuefei; Xiong, Xiong; Li, Tiaoyang; Li, Sichao; Zhang, Zhenfeng; Wu, Yanqing

2017-12-27

Because of their wide bandgap and ultrathin body properties, two-dimensional materials are currently being pursued for next-generation electronic and optoelectronic applications. Although there have been increasing numbers of studies on improving the performance of MoS 2 field-effect transistors (FETs) using various methods, the dielectric interface, which plays a decisive role in determining the mobility, interface traps, and thermal transport of MoS 2 FETs, has not been well explored and understood. In this article, we present a comprehensive experimental study on the effect of high-k dielectrics on the performance of few-layer MoS 2 FETs from 300 to 4.3 K. Results show that Al 2 O 3 /HfO 2 could boost the mobility and drain current. Meanwhile, MoS 2 transistors with Al 2 O 3 /HfO 2 demonstrate a 2× reduction in oxide trap density compared to that of the devices with the conventional SiO 2 substrate. Also, we observe a negative differential resistance effect on the device with 1 μm-channel length when using conventional SiO 2 as the gate dielectric due to self-heating, and this is effectively eliminated by using the Al 2 O 3 /HfO 2 gate dielectric. This dielectric engineering provides a highly viable route to realizing high-performance transition metal dichalcogenide-based FETs.

Necessary and sufficient conditions for the successful three-phase photocatalytic reduction of CO2 by H2O over heterogeneous photocatalysts.

PubMed

Teramura, Kentaro; Tanaka, Tsunehiro

2018-03-28

Artificial photosynthesis has recently drawn an increasing amount of attention due to the fact that it allows for direct solar-to-chemical energy conversion. However, one of the basic steps of this process, namely the reduction of CO2 by H2O to afford O2 and CO2 reduction products (CO2RPs) such as HCOOH, CO, HCHO, CH3OH, and CH4, is very difficult to achieve. In contrast to the CO2 reduction in plants and homogenous systems, the reduction of CO2 to CO2RPs over heterogeneous photocatalysts was challenged by the competing reduction of H+ to H2. Unfortunately, most of the research performed so far has focused only on the reduction of CO2, rather than the characterization of the H2O oxidation and H2 production. Moreover, the fact that the heterogeneous photocatalytic reduction of CO2 into CO2RPs by H2O should satisfy several selectivity criteria has often been ignored. Herein, we propose three such evaluation criteria, namely (1) the origin of carbon in CO2RPs (determined using isotopically labeled CO2 (13CO2)), (2) the relative amount of H2 and CO2RPs produced, and (3) the amount of O2 produced by the oxidation of H2O. If all these criteria are satisfied, i.e., the carbons of CO2RPs originate from CO2, the amount of H2 produced is negligible, and a stoichiometric amount of O2 is produced by the oxidation of H2O, then CO2 introduced into the gas phase is believed to be reduced by H2O to CO2RPs in the aqueous phase.

Pd nanoparticle assemblies--as the substitute of HRP, in their biosensing applications for H2O2 and glucose.

PubMed

Han, Min; Liu, Suli; Bao, Jianchun; Dai, Zhihui

2012-01-15

The spherical porous Pd nanoparticle assemblies (NPAs) have been successfully synthesized by starch-assisted chemical reduction of Pd(II) species at room temperature. Such Pd NPAs are not simply used to enlarge the surface area and to promote the electron transfer. They also catalyze the reduction of H(2)O(2) which are regarded as horseradish peroxidase (HRP) substitutes in electron transfer process. By using them as electrocatalysts, as low as 6.8×10(-7) M H(2)O(2) can be detected with a linear range from 1.0×10(-6) to 8.2×10(-4) M. Moreover, through co-immobilization of such Pd NPAs and glucose oxidase (GOx), a sensitive and selective glucose biosensor is developed. The detection principle lies on measuring the increase of cathodic current by co-reduction of dissolved oxygen and the in situ generated H(2)O(2) during the enzymatic reaction. Under optimal conditions, the detection limit is down to 6.1×10(-6) M with a very wide linear range from 4.0×10(-5) to 2.2×10(-2) M. The proposed biosensor shows a fast response, good stability, high selectivity and reproducibility of serum glucose level. It provides a promising strategy to construct fast, sensitive, stable and anti-interferential amperometric biosensors for early diagnosis and prevention of diabetes. Copyright © 2011 Elsevier B.V. All rights reserved.

Investigating the Effect of Titanium Dioxide (TiO2) Pollution on the Performance of the Mono-crystalline Solar Module

NASA Astrophysics Data System (ADS)

Ahmed Darwish, Zeki; Sopian, K.; Kazem, Hussein A.; Alghoul, M. A.; Alawadhi, Hussain

2017-11-01

This paper presents a study of titanium oxide TiO2 as one of the components of dust pollution affecting the PV performance. This pollutant can be found in various quantities in different locations around the world. The production of energy by different types of photovoltaic systems is very sensitive and depends on various environmental factors. Dust is one of the main contributing factors, yet the type of the dust is often neglected when studying the behaviour of the solar panel. In this experimental work we have studied the performance of the monocrystalline solar module as affected by the density of TiO2. The reduction of the PV module power caused by titanium dioxide under various mass densities was investigated. The results showed that the TiO2 has a significant effect on the PV output power. The dust density varied between 0-125 g.m-2. The corresponding reduction of the PV output power increased from 0 to 86.7%. This is based on various influencing parameters such as: short circuit current (Isc), maximum current (Im), open circuit voltage (Voc), maximum voltage (Vm), maximum power (Pm) and efficiency (E). Two functions are proposed as a mathematical model in order to explain this behaviour, namely the exponential and Fourier functions. The coefficients of all general models are valid for this type of dust with a density value ranging from 0-125 g.m-2.

Structural and electrical characteristics of high-κ Er2O3 and Er2TiO5 gate dielectrics for a-IGZO thin-film transistors

PubMed Central

2013-01-01

In this letter, we investigated the structural and electrical characteristics of high-κ Er2O3 and Er2TiO5 gate dielectrics on the amorphous indium-gallium-zinc-oxide (a-IGZO) thin-film transistor (TFT) devices. Compared with the Er2O3 dielectric, the a-IGZO TFT device incorporating an Er2TiO5 gate dielectric exhibited a low threshold voltage of 0.39 V, a high field-effect mobility of 8.8 cm2/Vs, a small subthreshold swing of 143 mV/decade, and a high Ion/Ioff current ratio of 4.23 × 107, presumably because of the reduction in the oxygen vacancies and the formation of the smooth surface roughness as a result of the incorporation of Ti into the Er2TiO5 film. Furthermore, the reliability of voltage stress can be improved using an Er2TiO5 gate dielectric. PMID:23294730

Structural and electrical characteristics of high-κ Er2O3 and Er2TiO5 gate dielectrics for a-IGZO thin-film transistors.

PubMed

Chen, Fa-Hsyang; Her, Jim-Long; Shao, Yu-Hsuan; Matsuda, Yasuhiro H; Pan, Tung-Ming

2013-01-08

In this letter, we investigated the structural and electrical characteristics of high-κ Er2O3 and Er2TiO5 gate dielectrics on the amorphous indium-gallium-zinc-oxide (a-IGZO) thin-film transistor (TFT) devices. Compared with the Er2O3 dielectric, the a-IGZO TFT device incorporating an Er2TiO5 gate dielectric exhibited a low threshold voltage of 0.39 V, a high field-effect mobility of 8.8 cm2/Vs, a small subthreshold swing of 143 mV/decade, and a high Ion/Ioff current ratio of 4.23 × 107, presumably because of the reduction in the oxygen vacancies and the formation of the smooth surface roughness as a result of the incorporation of Ti into the Er2TiO5 film. Furthermore, the reliability of voltage stress can be improved using an Er2TiO5 gate dielectric.

Biogenic selenium nanoparticles: current status and future prospects.

PubMed

Wadhwani, Sweety A; Shedbalkar, Utkarsha U; Singh, Richa; Chopade, Balu A

2016-03-01

Selenium nanoparticles (SeNPs) are gaining importance in the field of medicine owing to their antibacterial and anticancer properties. SeNPs are biocompatible and non-toxic compared to the counterparts, selenite (SeO3 (-2)) and selenate (SeO4 (-2)). They can be synthesized by physical, chemical, and biological methods and have distinct bright orange-red color. Biogenic SeNPs are stable and do not aggregate owing to natural coating of the biomolecules. Various hypotheses have been proposed to describe the mechanism of microbial synthesis of SeNPs. It is primarily a two-step reduction process from SeO4 (-2) to SeO3 (-2) to insoluble elemental selenium (Se(0)) catalyzed by selenate and selenite reductases. Phenazine-1-carboxylic acid and glutathione are involved in selenite reduction. Se factor A (SefA) and metalloid reductase Rar A present on the surface of SeNPs confer stability to the nanoparticles. SeNPs act as potent chemopreventive and chemotherapeutic agents. Conjugation with antibiotics enhances their anticancer efficacy. These also have applications in nanobiosensors and environmental remediation.

Kinetic Investigations of SiMn Slags From Different Mn Sources

NASA Astrophysics Data System (ADS)

Kim, Pyunghwa Peace; Tangstad, Merete

2018-06-01

The kinetics of MnO and SiO2 reduction were investigated for Silicomanganese (SiMn) slags using a Thermogravimetric analysis (TGA) between 1773 K and 1923 K (1500 °C and 1650 °C) under CO atmospheric pressure. The charge materials were based on Assmang ore and HC FeMn Slag. Rate models for MnO and SiO2 reduction were applied to describe the metal-producing rates, as shown by the following equations: r_{MnO} = k_{MnO} × A × ( {a_{MnO} - {a_{Mn} }/{K_{T }}} ) r_{{{SiO}2 }} = k_{SiO2} × A × ( {a_{{{SiO}2 }} - {a_{Si} }/{K_{T }}} ). The results show that the choice of raw materials in the charge considerably affected the reduction rate of MnO and SiO2. The highest reduction rate was found to be from charges using HC FeMn slag. The difference in the driving forces was insignificant among the SiMn slags, and the similar slag viscosities could not explain the different reduction rates. Instead, the difference is attributed to small amounts of sulfur and the amount of iron in the charge. In addition, the rate models were applicable to describe the reduction of MnO and SiO2 in SiMn slags.

Understanding the Magnesiothermic Reduction Mechanism of TiO2 to Produce Ti

NASA Astrophysics Data System (ADS)

Choi, Kyunsuk; Choi, Hanshin; Sohn, Il

2017-04-01

Titanium dioxide (TiO2) powders in the mineral form of rutile were reduced to metallic and an intermediate phase via a magnesiothermic reaction in molten Mg at temperatures between 973 K and 1173 K (700 °C and 900 °C) under high-purity Ar atmosphere. The reaction behavior and pathway indicated intermediate phase formation during the magnesiothermic reduction of TiO2 using XRD (X-ray diffraction), SEM (scanning electron microscope), and TEM (transmission electron microscope). Mg/TiO2 = 2 resulted in various intermediate phases of oxygen containing titanium, including Ti6O, Ti3O, and Ti2O, with metallic Ti present. MgTi2O4 ternary intermediate phases could also be observed, but they were dependent on the excess Mg present in the sample. Nevertheless, even with excessive amounts of Mg at Mg/TiO2 = 10, complete reduction to metallic Ti could not be obtained and some Ti6O intermediate phases were present. Although thermodynamics do not predict the formation of the MgTi2O4 spinel phase, detailed phase identification through XRD, SEM, and TEM showed significant amounts of this intermediate ternary phase even at excess Mg additions. Considering the stepwise reduction of TiO2 by Mg and the pronounced amounts of MgTi2O4 phase observed, the rate-limiting reaction is likely the reduction of MgTi2O4 to the TitO phase. Thus, an additional reduction step beyond thermodynamic predictions was developed.

Carbon Felt-Based Bioelectrocatalytic Flow-Through Detectors: 2,6-Dichlorophenol Indophenol and Peroxidase Coadsorbed Carbon-Felt for Flow-Amperometric Determination of Hydrogen Peroxide

PubMed Central

Wang, Yue; Hasebe, Yasushi

2014-01-01

2,6-dichlorophenol indophenol (DCIP) and horseradish peroxidase (HRP) were coadsorbed on a porous carbon felt (CF) from their mixed aqueous solution under ultrasound irradiation for 5 min. The resulting DCIP and HRP-coadsorbed CF (DCIP/HRP-CF) showed an excellent bioelectrocatalytic activity for the reduction of H2O2. The coadsorption of DCIP together with HRP was essential to obtain larger bioelectrocatalytic current to H2O2. The DCIP/HRP-CF was successfully used as a working electrode unit of a bioelectrocatalytic flow-through detector for highly sensitive and continuous amperometric determination of H2O2. Under the optimized operational conditions (i.e., applied potential, +0.2 V versus Ag/AgCl; carrier pH 5.0, and carrier flow rate, 1.9 mL/min), the cathodic peak current of H2O2 linearly increased over the concentration range from 0.1 to 30 μM (the sensitivity, 0.88 μA/μM (slope of linear part); the limit of detection, 0.1 μM (S/N = 3) current noise level, 30 nA) with a sample through-put of ca. 40–90 samples/h. PMID:28788505

Optimization of the lithium/thionyl chloride battery

NASA Technical Reports Server (NTRS)

White, Ralph E.

1989-01-01

A 1-D math model for the lithium/thionyl chloride primary cell is used in conjunction with a parameter estimation technique in order to estimate the electro-kinetic parameters of this electrochemical system. The electro-kinetic parameters include the anodic transfer coefficient and exchange current density of the lithium oxidation, alpha sub a,1 and i sub o,i,ref, the cathodic transfer coefficient and the effective exchange current density of the thionyl chloride reduction, alpha sub c,2 and a sup o i sub o,2,ref, and a morphology parameter, Xi. The parameter estimation is performed on simulated data first in order to gain confidence in the method. Data, reported in the literature, for a high rate discharge of an experimental lithium/thionyl chloride cell is used for an analysis.

Mechanism of Nitrogenase H 2 Formation by Metal-Hydride Protonation Probed by Mediated Electrocatalysis and H/D Isotope Effects

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

Khadka, Nimesh; Milton, Ross D.; Shaw, Sudipta

Nitrogenase catalyzes the reduction of dinitrogen (N2) to ammonia (NH3) with obligatory reduction of protons (H+) to dihydrogen (H2) through a mechanism involving reductive elimination of two [Fe-H-Fe] bridging hydrides at its active site FeMo-cofactor. The overall rate-limiting step is associated with ATP-driven electron delivery from Fe protein, precluding isotope effect measurements on substrate reduction steps. Here, we use mediated bioelectrocatalysis to drive electron delivery to MoFe protein without Fe protein and ATP hydrolysis, thereby eliminating the normal rate-limiting step. The ratio of catalytic current in mixtures of H2O and D2O, the proton inventory, changes linearly with the D2O/H2O ratio,more » revealing that a single H/D is involved in the rate limiting step. Kinetic models, along with measurements that vary the electron/proton delivery rate and use different substrates, reveal that the rate-limiting step under these conditions is the H2 formation reaction. Altering the chemical environment around the active site FeMo-cofactor in the MoFe protein either by substituting nearby amino acids or transferring the isolated FeMo-cofactor into a different peptide matrix, changes the net isotope effect, but the proton inventory plot remains linear, consistent with an unchanging rate-limiting step. Density functional theory predicts a transition state for H2 formation where the proton from S-H+ moves to the hydride in Fe-H-, predicting the number and magnitude of the observed H/D isotope effect. This study not only reveals the mechanism of H2 formation, but also illustrates a strategy for mechanistic study that can be applied to other enzymes and to biomimetic complexes.« less

Cubic PdNP-based air-breathing cathodes integrated in glucose hybrid biofuel cells

NASA Astrophysics Data System (ADS)

Faggion Junior, D.; Haddad, R.; Giroud, F.; Holzinger, M.; Maduro de Campos, C. E.; Acuña, J. J. S.; Domingos, J. B.; Cosnier, S.

2016-05-01

Cubic Pd nanoparticles (PdNPs) were synthesized using ascorbic acid as a reducing agent and were evaluated for the catalytic oxygen reduction reaction. PdNPs were confined with multiwalled carbon nanotube (MWCNT) dispersions to form black suspensions and these inks were dropcast onto glassy carbon electrodes. Different nanoparticle sizes were synthesized and investigated upon oxygen reduction capacities (onset potential and electrocatalytic current densities) under O2 saturated conditions at varying pH values. Strong evidence of O2 diffusion limitation was demonstrated. In order to overcome oxygen concentration and diffusion limitations in solution, we used a gas diffusion layer to create a PdNP-based air-breathing cathode, which delivered -1.5 mA cm-2 at 0.0 V with an onset potential of 0.4 V. This air-breathing cathode was combined with a specially designed phenanthrolinequinone/glucose dehydrogenase-based anode to form a complete glucose/O2 hybrid bio-fuel cell providing an open circuit voltage of 0.554 V and delivering a maximal power output of 184 +/- 21 μW cm-2 at 0.19 V and pH 7.0.Cubic Pd nanoparticles (PdNPs) were synthesized using ascorbic acid as a reducing agent and were evaluated for the catalytic oxygen reduction reaction. PdNPs were confined with multiwalled carbon nanotube (MWCNT) dispersions to form black suspensions and these inks were dropcast onto glassy carbon electrodes. Different nanoparticle sizes were synthesized and investigated upon oxygen reduction capacities (onset potential and electrocatalytic current densities) under O2 saturated conditions at varying pH values. Strong evidence of O2 diffusion limitation was demonstrated. In order to overcome oxygen concentration and diffusion limitations in solution, we used a gas diffusion layer to create a PdNP-based air-breathing cathode, which delivered -1.5 mA cm-2 at 0.0 V with an onset potential of 0.4 V. This air-breathing cathode was combined with a specially designed phenanthrolinequinone/glucose dehydrogenase-based anode to form a complete glucose/O2 hybrid bio-fuel cell providing an open circuit voltage of 0.554 V and delivering a maximal power output of 184 +/- 21 μW cm-2 at 0.19 V and pH 7.0. Electronic supplementary information (ESI) available: Physical characterization, Fig. S1-S4 electrochemical experiments Fig. S5-S11. See DOI: 10.1039/c6nr01245k

Electrical properties and interfacial issues of high-k/Si MIS capacitors characterized by the thickness of Al{sub 2}O{sub 3} interlayer

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

Wang, Xing; Liu, Hongxia, E-mail: hxliu@mail.xidian.edu.cn; Fei, Chenxi

2016-06-15

A thin Al{sub 2}O{sub 3} interlayer deposited between La{sub 2}O{sub 3} layer and Si substrate was used to scavenge the interfacial layer (IL) by blocking the out-diffusion of substrate Si. Some advantages and disadvantages of this method were discussed in detail. Evident IL reduction corroborated by the transmission electron microscopy results suggested the feasibility of this method in IL scavenging. Significant improvements in oxygen vacancy and leakage current characteristics were achieved as the thickness of Al{sub 2}O{sub 3} interlayer increase. Meanwhile, some disadvantages such as the degradations in interface trap and oxide trapped charge characteristics were also observed.

Multishelled Si@Cu Microparticles Supported on 3D Cu Current Collectors for Stable and Binder-free Anodes of Lithium-Ion Batteries.

PubMed

Zhang, Zailei; Wang, Zhong Lin; Lu, Xianmao

2018-04-24

Silicon has proved to be a promising anode material of high-specific capacity for the next-generation lithium ion batteries (LIBs). However, during repeated discharge/charge cycles, Si-based electrodes, especially those in microscale size, pulverize and lose electrical contact with the current collectors due to large volume expansion. Here, we introduce a general method to synthesize Cu@M (M = Si, Al, C, SiO 2 , Si 3 N 4 , Ag, Ti, Ta, SnIn 2 O 5 , Au, V, Nb, W, Mg, Fe, Ni, Sn, ZnO, TiN, Al 2 O 3 , HfO 2 , and TiO 2 ) core-shell nanowire arrays on Cu substrates. The resulting Cu@Si nanowire arrays were employed as LIB anodes that can be reused via HCl etching and H 2 -reduction. Multishelled Cu@Si@Cu microparticles supported on 3D Cu current collectors were further prepared as stable and binder-free LIB anodes. This 3D Cu@Si@Cu structure allows the interior conductive Cu network to effectively accommodate the volume expansion of the electrode and facilitates the contact between the Cu@Si@Cu particles and the current collectors during the repeated insertion/extraction of lithium ions. As a result, the 3D Cu@Si@Cu microparticles at a high Si-loading of 1.08 mg/cm 2 showed a capacity retention of 81% after 200 cycles. In addition, charging tests of 3D Cu@Si@Cu-LiFePO 4 full cells by a triboelectric nanogenerator with a pulsed current demonstrated that LIBs with silicon anodes can effectively store energy delivered by mechanical energy harvesters.

New understanding on separation of Mn and Fe from ferruginous manganese ores by the magnetic reduction roasting process

NASA Astrophysics Data System (ADS)

Liu, Bingbing; Zhang, Yuanbo; Wang, Juan; Wang, Jia; Su, Zijian; Li, Guanghui; Jiang, Tao

2018-06-01

Magnetic reduction roasting followed by magnetic separation process is reported as a simple route to realize separation of Mn and Fe from ferruginous manganese ores (Fe-Mn ores). However, the separation and recovery of Mn and Fe oxides are not very effective. This work clarified the underlying reason for the poor separation and also proposed some suggestions for the magnetic reduction process. In this work, the effect of temperature on the magnetic reduction roasting - magnetic separation of Fe-Mn ore was investigated firstly. Then the reduction behaviors of MnO2-Fe2O3 system and MnO2-Fe2O3-10 wt.%SiO2 system under 10 vol.% CO-90 vol.% CO2 at 600-1000 °C were investigated by XRD, XPS, SEM-EDS, VSM, DSC and thermodynamics analyses. Reduction and separation tests showed that higher reduction temperature was beneficial to the recovery of iron while it's not in favor of the recovery of manganese when the temperature was over 800 °C. The formation of composite oxide MnxFe3-xO4 with strong magnetism between the interface of the MnO2 and Fe2O3 particles leaded to the poor separation of iron and manganese. In addition, the formation mechanism of MnxFe3-xO4 from MnO2 and Fe2O3 as well as the interface reaction reduced under 10 vol.% CO was discussed in this study. Finally, some suggestions were recommended for the magnetic reduction roasting for utilizing the Fe-Mn ores effectively.

Pt/SnO2-based CO-oxidation catalysts for long-life closed-cycle CO2 lasers

NASA Technical Reports Server (NTRS)

Schryer, David R.; Upchurch, Billy T.; Hess, Robert V.; Wood, George M.; Sidney, Barry D.; Miller, Irvin M.; Brown, Kenneth G.; Vannorman, John D.; Schryer, Jacqueline; Brown, David R.

1990-01-01

Noble-metal/tin-oxide based catalysts such as Pt/SnO2 have been shown to be good catalysts for the efficient oxidation of CO at or near room temperature. These catalysts require a reductive pretreatment and traces of hydrogen or water to exhibit their full activity. Addition of Palladium enhances the activity of these catalysts with about 15 to 20 percent Pt, 4 percent Pd, and the balance SnO2 being an optimum composition. Unfortunately, these catalysts presently exhibit significant decay due in part to CO2 retention, probably as a bicarbonate. Research on minimizing the decay in activity of these catalysts is currently in progress. A proposed mechanism of CO oxidation on Pt/SnO2-based catalysts has been developed and is discussed.

Nanocrystalline Fe-Fe2O3 particle-deposited N-doped graphene as an activity-modulated Pt-free electrocatalyst for oxygen reduction reaction

NASA Astrophysics Data System (ADS)

Dhavale, Vishal M.; Singh, Santosh K.; Nadeema, Ayasha; Gaikwad, Sachin S.; Kurungot, Sreekumar

2015-11-01

The size-controlled growth of nanocrystalline Fe-Fe2O3 particles (2-3 nm) and their concomitant dispersion on N-doped graphene (Fe-Fe2O3/NGr) could be attained when the mutually assisted redox reaction between NGr and Fe3+ ions could be controlled within the aqueous droplets of a water-in-oil emulsion. The synergistic interaction existing between Fe-Fe2O3 and NGr helped the system to narrow down the overpotential for the oxygen reduction reaction (ORR) by bringing a significant positive shift to the reduction onset potential, which is just 15 mV higher than its Pt-counterpart. In addition, the half-wave potential (E1/2) of Fe-Fe2O3/NGr is found to be improved by a considerable amount of 135 mV in comparison to the system formed by dispersing Fe-Fe2O3 nanoparticles on reduced graphene oxide (Fe-Fe2O3/RGO), which indicates the presence of a higher number of active sites in Fe-Fe2O3/NGr. Despite this, the ORR kinetics of Fe-Fe2O3/NGr are found to be shifted significantly to the preferred 4-electron-transfer pathway compared to NGr and Fe-Fe2O3/RGO. Consequently, the H2O2% was found to be reduced by 78.3% for Fe-Fe2O3/NGr (13.0%) in comparison to Fe-Fe2O3/RGO (51.2%) and NGr (41.0%) at -0.30 V (vs. Hg/HgO). This difference in the yield of H2O2 formed between the systems along with the improvements observed in terms of the oxygen reduction onset and E1/2 in the case of Fe-Fe2O3/NGr reveals the activity modulation achieved for the latter is due to the coexistence of factors such as the presence of the mixed valancies of iron nanoparticles, small size and homogeneous distribution of Fe-Fe2O3 nanoparticles and the electronic modifications induced by the doped nitrogen in NGr. A controlled interplay of these factors looks like worked favorably in the case of Fe-Fe2O3/NGr. As a realistic system level validation, Fe-Fe2O3/NGr was employed as the cathode electrode of a single cell in a solid alkaline electrolyte membrane fuel cell (AEMFC). The system could display an open circuit voltage (OCV) of 0.73 V and maximum power and current densities of 54.40 mW cm-2 and 200 mA cm-2, respectively, which are comparable to the performance characteristics of a similar system derived by using 40 wt% Pt/C as the cathode electrode.The size-controlled growth of nanocrystalline Fe-Fe2O3 particles (2-3 nm) and their concomitant dispersion on N-doped graphene (Fe-Fe2O3/NGr) could be attained when the mutually assisted redox reaction between NGr and Fe3+ ions could be controlled within the aqueous droplets of a water-in-oil emulsion. The synergistic interaction existing between Fe-Fe2O3 and NGr helped the system to narrow down the overpotential for the oxygen reduction reaction (ORR) by bringing a significant positive shift to the reduction onset potential, which is just 15 mV higher than its Pt-counterpart. In addition, the half-wave potential (E1/2) of Fe-Fe2O3/NGr is found to be improved by a considerable amount of 135 mV in comparison to the system formed by dispersing Fe-Fe2O3 nanoparticles on reduced graphene oxide (Fe-Fe2O3/RGO), which indicates the presence of a higher number of active sites in Fe-Fe2O3/NGr. Despite this, the ORR kinetics of Fe-Fe2O3/NGr are found to be shifted significantly to the preferred 4-electron-transfer pathway compared to NGr and Fe-Fe2O3/RGO. Consequently, the H2O2% was found to be reduced by 78.3% for Fe-Fe2O3/NGr (13.0%) in comparison to Fe-Fe2O3/RGO (51.2%) and NGr (41.0%) at -0.30 V (vs. Hg/HgO). This difference in the yield of H2O2 formed between the systems along with the improvements observed in terms of the oxygen reduction onset and E1/2 in the case of Fe-Fe2O3/NGr reveals the activity modulation achieved for the latter is due to the coexistence of factors such as the presence of the mixed valancies of iron nanoparticles, small size and homogeneous distribution of Fe-Fe2O3 nanoparticles and the electronic modifications induced by the doped nitrogen in NGr. A controlled interplay of these factors looks like worked favorably in the case of Fe-Fe2O3/NGr. As a realistic system level validation, Fe-Fe2O3/NGr was employed as the cathode electrode of a single cell in a solid alkaline electrolyte membrane fuel cell (AEMFC). The system could display an open circuit voltage (OCV) of 0.73 V and maximum power and current densities of 54.40 mW cm-2 and 200 mA cm-2, respectively, which are comparable to the performance characteristics of a similar system derived by using 40 wt% Pt/C as the cathode electrode. Electronic supplementary information (ESI) available: Experimental, deconvulated XPS of C 1s, and O 1s of Fe-Fe2O3/RGO, Fe-Fe2O3/NGr, RGO and NGr. Deconvoluted N 1s of Fe-Fe2O3/NGr and NGr, formulae, CV, LSV at different rpm, and K-L plots. See DOI: 10.1039/c5nr04929f

Enhanced deodorization and sludge reduction in situ by a humus soil cooperated anaerobic/anoxic/oxic (A2O) wastewater treatment system.

PubMed

Yan, Xing; Li, Biqing; Lei, Fang; Feng, Xin; Pang, Bo

2016-08-01

Simultaneous sludge reduction and malodor abatement in humus soil cooperated an anaerobic/anoxic/oxic (A2O) wastewater treatment were investigated in this study. The HSR-A2O was composed of a humus soil reactor (HSR) and a conventional A2O (designated as C-A2O).The results showed that adding HSR did not deteriorate the chemical oxygen demand (COD) removal, while total phosphorus (TP) removal efficiency in HSR-A2O was improved by 18 % in comparison with that in the C-A2O. Both processes had good performance on total nitrogen (TN) removal, and there was no significant difference between them (76.8 and 77.1 %, respectively). However, NH4 (+)-N and NO3 (-)-N were reduced to 0.3 and 6.7 mg/L in HSR-A2O compared to 1.5 and 4.5 mg/L. Moreover, adding HSR induced the sludge reduction, and the sludge production rate was lower than that in the C-A2O. The observed sludge yield was estimated to be 0.32 kg MLSS/day in HSR-A2O, which represent a 33.5 % reduction compared to a C-A2O process. Activated sludge underwent humification and produced more humic acid in HSR-A2O, which is beneficial to sludge reduction. Odor abatement was achieved in HSR-A2O, ammonium (NH3), and sulfuretted hydrogen (H2S) emission decreased from 1.34 and 1.33 to 0.06 mg/m(3), 0.025 mg/m(3) in anaerobic area, with the corresponding reduction efficiency of 95.5 and 98.1 %. Microbial community analysis revealed that the relevant microorganism enrichment explained the reduction effect of humus soil on NH3 and H2S emission. The whole study demonstrated that humus soil enhanced odor abatement and sludge reduction in situ.

Corrosion of Pipeline and Wellbore Steel by Liquid CO2 Containing Trace Amounts of Water and SO2

NASA Astrophysics Data System (ADS)

McGrail, P.; Schaef, H. T.; Owen, A. T.

2009-12-01

Carbon dioxide capture and storage in deep saline formations is currently considered the most attractive option to reduce greenhouse gas emissions with continued use of fossil fuels for energy production. Transporting captured CO2 and injection into suitable formations for storage will necessarily involve pipeline systems and wellbores constructed of carbon steels. Industry standards currently require nearly complete dehydration of liquid CO2 to reduce corrosion in the pipeline transport system. However, it may be possible to establish a corrosion threshold based on H2O content in the CO2 that could allow for minor amounts of H2O to remain in the liquid CO2 and thereby eliminate a costly dehydration step. Similarly, trace amounts of sulfur and nitrogen compounds common in flue gas streams are currently removed through expensive desulfurization and catalytic reduction processes. Provided these contaminants could be safely and permanently transported and stored in the geologic reservoir, retrofits of existing fossil-fuel plants could address comprehensive emissions reductions, including CO2 at perhaps nearly the same capital and operating cost. Because CO2-SO2 mixtures have never been commercially transported or injected, both experimental and theoretical work is needed to understand corrosion mechanisms of various steels in these gas mixtures containing varying amounts of water. Experiments were conducted with common tool steel (AISI-01) and pipeline steel (X65) immersed in liquid CO2 at room temperature containing ~1% SO2 and varying amounts of H2O (0 to 2500 ppmw). A threshold concentration of H2O in the liquid CO2-SO2 mixture was established based on the absence of visible surface corrosion. For example, experiments exposing steel to liquid CO2-SO2 containing ~300 ppmw H2O showed a delay in onset of visible corrosion products and minimal surface corrosion was visible after five days of testing. However increasing the water content to 760 ppmw produced extensive surface corrosion after 48 hours at room temperature. Surface characterization by SEM showed one type of morphology that included large circular features radiating outward from a central structure. Chemical analyses obtained by SEM-EDX indicate the phases contained mostly Fe and S with minor amounts of Mn. Corrosion products completely covering the metal coupon surface were identified by XRD as iron sulfite hydrate (FeSO3●3H2O), with lesser amounts of gravegliaite (MnSO3●3H2O), and rozenite (Fe(SO4)●(H2O)4).

Decreased N2O reduction by low soil pH causes high N2O emissions in a riparian ecosystem.

PubMed

Van den Heuvel, R N; Bakker, S E; Jetten, M S M; Hefting, M M

2011-05-01

Quantification of harmful nitrous oxide (N(2)O) emissions from soils is essential for mitigation measures. An important N(2)O producing and reducing process in soils is denitrification, which shows deceased rates at low pH. No clear relationship between N(2)O emissions and soil pH has yet been established because also the relative contribution of N(2)O as the denitrification end product decreases with pH. Our aim was to show the net effect of soil pH on N(2)O production and emission. Therefore, experiments were designed to investigate the effects of pH on NO(3)(-) reduction, N(2)O production and reduction and N(2) production in incubations with pH values set between 4 and 7. Furthermore, field measurements of soil pH and N(2)O emissions were carried out. In incubations, NO(3)(-) reduction and N(2) production rates increased with pH and net N(2)O production rate was highest at pH 5. N(2)O reduction to N(2) was halted until NO(3)(-) was depleted at low pH values, resulting in a built up of N(2)O. As a consequence, N(2)O:N(2) production ratio decreased exponentially with pH. N(2)O reduction appeared therefore more important than N(2)O production in explaining net N(2)O production rates. In the field, a negative exponential relationship for soil pH against N(2)O emissions was observed. Soil pH could therefore be used as a predictive tool for average N(2)O emissions in the studied ecosystem. The occurrence of low pH spots may explain N(2)O emission hotspot occurrence. Future studies should focus on the mechanism behind small scale soil pH variability and the effect of manipulating the pH of soils. © 2011 Blackwell Publishing Ltd.

The substrate oxidation mechanism of pyranose 2-oxidase and other related enzymes in the glucose-methanol-choline superfamily.

PubMed

Wongnate, Thanyaporn; Chaiyen, Pimchai

2013-07-01

Enzymes in the glucose-methanol-choline (GMC) oxidoreductase superfamily catalyze the oxidation of an alcohol moiety to the corresponding aldehyde. In this review, the current understanding of the sugar oxidation mechanism in the reaction of pyranose 2-oxidase (P2O) is highlighted and compared with that of other enzymes in the GMC family for which structural and mechanistic information is available, including glucose oxidase, choline oxidase, cholesterol oxidase, cellobiose dehydrogenase, aryl-alcohol oxidase, and pyridoxine 4-oxidase. Other enzymes in the family that have been newly discovered or for which less information is available are also discussed. A large primary kinetic isotope effect was observed for the flavin reduction when 2-d-D-glucose was used as a substrate, but no solvent kinetic isotope effect was detected for the flavin reduction step. The reaction of P2O is consistent with a hydride transfer mechanism in which there is stepwise formation of d-glucose alkoxide prior to the hydride transfer. Site-directed mutagenesis of P2O and pH-dependence studies indicated that His548 is a catalytic base that facilitates the deprotonation of C2-OH in D-glucose. This finding agrees with the current mechanistic model for aryl-alcohol oxidase, glucose oxidase, cellobiose dehydrogenase, methanol oxidase, and pyridoxine 4-oxidase, but is different from that of cholesterol oxidase and choline oxidase. Although all of the GMC enzymes share similar structural folding and use the hydride transfer mechanism for flavin reduction, they appear to have subtle differences in the fine-tuned details of how they catalyze substrate oxidation. © 2013 The Authors Journal compilation © 2013 FEBS.

Templated assembly of BiFeO3 nanocrystals into 3D mesoporous networks for catalytic applications

NASA Astrophysics Data System (ADS)

Papadas, I. T.; Subrahmanyam, K. S.; Kanatzidis, M. G.; Armatas, G. S.

2015-03-01

The self-assembly of uniform nanocrystals into large porous architectures is currently of immense interest for nanochemistry and nanotechnology. These materials combine the respective advantages of discrete nanoparticles and mesoporous structures. In this article, we demonstrate a facile nanoparticle templating process to synthesize a three-dimensional mesoporous BiFeO3 material. This approach involves the polymer-assisted aggregating assembly of 3-aminopropanoic acid-stabilized bismuth ferrite (BiFeO3) nanocrystals followed by thermal decomposition of the surfactant. The resulting material consists of a network of tightly connected BiFeO3 nanoparticles (~6-7 nm in diameter) and has a moderately high surface area (62 m2 g-1) and uniform pores (ca. 6.3 nm). As a result of the unique mesostructure, the porous assemblies of BiFeO3 nanoparticles show an excellent catalytic activity and chemical stability for the reduction of p-nitrophenol to p-aminophenol with NaBH4.The self-assembly of uniform nanocrystals into large porous architectures is currently of immense interest for nanochemistry and nanotechnology. These materials combine the respective advantages of discrete nanoparticles and mesoporous structures. In this article, we demonstrate a facile nanoparticle templating process to synthesize a three-dimensional mesoporous BiFeO3 material. This approach involves the polymer-assisted aggregating assembly of 3-aminopropanoic acid-stabilized bismuth ferrite (BiFeO3) nanocrystals followed by thermal decomposition of the surfactant. The resulting material consists of a network of tightly connected BiFeO3 nanoparticles (~6-7 nm in diameter) and has a moderately high surface area (62 m2 g-1) and uniform pores (ca. 6.3 nm). As a result of the unique mesostructure, the porous assemblies of BiFeO3 nanoparticles show an excellent catalytic activity and chemical stability for the reduction of p-nitrophenol to p-aminophenol with NaBH4. Electronic supplementary information (ESI) available: IR spectra and TG profiles of as-made BiFeO3 NPs and MBFA samples, TEM images of 3-APA-capped BiFeO3 NPs, EDS spectrum of MBFAs, N2 adsorption-desorption isotherms of randomly aggregated BiFeO3 NPs and catalytic data for 4-NP reduction by MBFAs and other nanostructured catalysts. See DOI: 10.1039/c5nr00185d

Epitaxial ZnO gate dielectrics deposited by RF sputter for AlGaN/GaN metal-oxide-semiconductor high-electron-mobility transistors

NASA Astrophysics Data System (ADS)

Yoon, Seonno; Lee, Seungmin; Kim, Hyun-Seop; Cha, Ho-Young; Lee, Hi-Deok; Oh, Jungwoo

2018-01-01

Radio frequency (RF)-sputtered ZnO gate dielectrics for AlGaN/GaN metal-oxide-semiconductor high-electron-mobility transistors (MOS-HEMTs) were investigated with varying O2/Ar ratios. The ZnO deposited with a low oxygen content of 4.5% showed a high dielectric constant and low interface trap density due to the compensation of oxygen vacancies during the sputtering process. The good capacitance-voltage characteristics of ZnO-on-AlGaN/GaN capacitors resulted from the high crystallinity of oxide at the interface, as investigated by x-ray diffraction and high-resolution transmission electron microscopy. The MOS-HEMTs demonstrated comparable output electrical characteristics with conventional Ni/Au HEMTs but a lower gate leakage current. At a gate voltage of -20 V, the typical gate leakage current for a MOS-HEMT with a gate length of 6 μm and width of 100 μm was found to be as low as 8.2 × 10-7 mA mm-1, which was three orders lower than that of the Ni/Au Schottky gate HEMT. The reduction of the gate leakage current improved the on/off current ratio by three orders of magnitude. These results indicate that RF-sputtered ZnO with a low O2/Ar ratio is a good gate dielectric for high-performance AlGaN/GaN MOS-HEMTs.

Pyroprocessing of oxidized sodium-bonded fast reactor fuel - An experimental study of treatment options for degraded EBR-II fuel

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

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

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

The influence of foreign vs. North American emissions on surface ozone in the US

NASA Astrophysics Data System (ADS)

Reidmiller, D. R.; Fiore, A. M.; Jaffe, D. A.; Bergmann, D.; Cuvelier, C.; Dentener, F. J.; Duncan, B. N.; Folberth, G.; Gauss, M.; Gong, S.; Hess, P.; Jonson, J. E.; Keating, T.; Lupu, A.; Marmer, E.; Park, R.; Schultz, M. G.; Shindell, D. T.; Szopa, S.; Vivanco, M. G.; Wild, O.; Zuber, A.

2009-07-01

As part of the Hemispheric Transport of Air Pollution (HTAP; http:// www.htap.org) project, we analyze results from 15 global and 1 hemispheric chemical transport models and compare these to Clean Air Status and Trends Network (CASTNet) observations in the United States (US) for 2001. Using the policy-relevant maximum daily 8-h average ozone (MDA8 O3) statistic, the multi-model ensemble represents the observations well (mean r2=0.57, ensemble bias = +4.1 ppbv for all US regions and all seasons) despite a wide range in the individual model results. Correlations are strongest in the northeastern US during spring and fall (r2=0.68); and weakest in the midwestern US in summer (r2=0.46). However, large positive mean biases exist during summer for all eastern US regions, ranging from 10-20 ppbv, and a smaller negative bias is present in the western US during spring (~3 ppbv). In nearly all other regions and seasons, the biases of the model ensemble simulations are ≤5 ppbv. Sensitivity simulations in which anthropogenic O3-precursor emissions (NOx + NMVOC + CO + aerosols) were decreased by 20% in four source regions: East Asia (EA), South Asia (SA), Europe (EU) and North America (NA) show that the greatest response of MDA8 O3 to the summed foreign emissions reductions occurs during spring in the West (0.9 ppbv reduction due to 20% emissions reductions from EA + SA + EU). East Asia is the largest contributor to MDA8 O3 at all ranges of the O3 distribution for most regions (typically ~0.45 ppbv) followed closely by Europe. The exception is in the northeastern US where emissions reductions in EU had a slightly greater influence than EA emissions, particularly in the middle of the MDA8 O3 distribution (response of ~0.35 ppbv between 35-55 ppbv). EA and EU influences are both far greater (about 4x) than that from SA in all regions and seasons. In all regions and seasons O3-precursor emissions reductions of 20% in the NA source region decrease MDA8 O3 the most - by a factor of 2 to nearly 10 relative to foreign emissions reductions. The O3 response to anthropogenic NA emissions is greatest in the eastern US during summer at the high end of the O3 distribution (5-6 ppbv for 20% reductions). While the impact of foreign emissions on surface O3 in the US is not negligible - and is of increasing concern given the recent growth in Asian emissions - domestic emissions reductions remain a far more effective means of decreasing MDA8 O3 values, particularly those above 75 ppb (the current US standard).

Improved electron density through hetero-junction binary sensitized TiO2/ CdTe / D719 system as photoanode for dye sensitized solar cell

NASA Astrophysics Data System (ADS)

Pandey, A. K.; Ahmad, Muhammad Shakeel; Alizadeh, Mahdi; Rahim, Nasrudin Abd

2018-07-01

The combined effect of dual sensitization and hetero-junction symmetry has been investigated on the performance of TiO2 based dye sensitized solar cell. CdTe nanoparticles have been introduced in TiO2 matrix to function as sensitizer as well as act as hetero-junction between D719 dye and TiO2 nanoarchitecture. Four concentrations of CdTe i.e. 0.5 wt%, 2 wt%, 5 wt% and 8 wt% have been investigated. Morphological and compositional studies have been conducted using scanning electron microscope (SEM) and X-ray diffraction (XRD) respectively. Light absorption characteristics have been investigated by employing Uv-vis spectroscopy and the overall performance has been studied using solar simulator and electrochemical impedance spectroscopy (EIS). Performance has been found to be increased with the addition of CdTe due to high electron density and reduction in recombination reactions. An increase of 41.73% in incident photo conversion efficiency (IPCE) and 75.57% in short circuit current density (Jsc) have been recorded for the specimens containing 5 wt% CdTe compared to bare TiO2 based DSSCs. Further addition of CdTe leads to reduction in overall performance of DSSCs.

Hollow mesoporous silica nanotubes modified with palladium nanoparticles for environmental catalytic applications.

PubMed

Tian, Meng; Long, Yu; Xu, Dan; Wei, Shuoyun; Dong, Zhengping

2018-07-01

Nowadays, chemical catalytic methods for the treatment of organic wastes are attracting more and more research attention. In the current research, novel catalysts with palladium nanoparticles (Pd NPs) supported on the hollow mesoporous silica nanotubes (h-mSiO 2 ) were synthesized for the catalytic reduction of 4-nitrophenol (4-NP) and hydrodechlorination (HDC) of 4-chlorophenol (4-CP). The key point for the fabrication of the catalysts is that a certain thickness of the silica shell was wrapped on the multiwalled carbon nanotubes (MWNTs) or Pd/MWNTs through biphase stratification approach, and then the samples were calcined to remove the MWNTs. Thereby, h-mSiO 2 and Pd@h-mSiO 2 samples were obtained. The prepared materials have excellent pore structure and exhibit high specific surface areas. The reduction of 4-NP by the Pd/h-mSiO 2 and Pd@h-mSiO 2 catalysts showed higher TOF values than many other catalysts, and the yield of HDC of 4-CP to phenol reached 100% with a low loading of Pd in water solvent. The excellent catalytic activities of the Pd/h-mSiO 2 and Pd@h-mSiO 2 catalysts should attribute to the excellent connectivity of the h-mSiO 2 which not only can increase the accessibility of the Pd active sites but also enhance the mass transfer of the reactants. It is worth mention that, there is almost no Pd NPs aggregation or losing during the reaction process, and the prepared catalysts still showed good catalytic activity and physical stability after recycling. Moreover, the catalyst shows potential for catalytic reduction of nitroarenes in a fixed bed reactor, thus could be used for continuously treat nitroarenes polluted water. Copyright © 2018 Elsevier Inc. All rights reserved.

A non-enzymatic amperometric hydrogen peroxide sensor based on iron nanoparticles decorated reduced graphene oxide nanocomposite.

PubMed

Amanulla, Baishnisha; Palanisamy, Selvakumar; Chen, Shen-Ming; Velusamy, Vijayalakshmi; Chiu, Te-Wei; Chen, Tse-Wei; Ramaraj, Sayee Kannan

2017-02-01

A simple and facile green process was used for the synthesis of iron nanoparticles (FeNPs) decorated reduced graphene oxide (rGO) nanocomposite by using Ipomoea pes-tigridis leaf extract as a reducing and stabilizing agent. The as-prepared rGO/FeNPs nanocomposite was characterized by transmission electron microscopy, X-ray spectroscopy and Fourier transform infrared spectroscopy. The nanocomposite was further modified on the glassy carbon electrode and used for non-enzymatic sensing of hydrogen peroxide (H 2 O 2 ). Cyclic voltammetry results reveal that rGO/FeNPs nanocomposite has excellent electro-reduction behavior to H 2 O 2 when compared to the response of FeNPs and rGO modified electrodes. Furthermore, the nanocomposite modified electrode shows 9 and 6 folds enhanced reduction current response to H 2 O 2 than that of rGO and FeNPs modified electrodes. Amperometric method was further used to quantify the H 2 O 2 using rGO/FeNPs nanocomposite, and the response was linear over the concentration ranging from 0.1μM to 2.15mM. The detection limit and sensitivity of the sensor were estimated as 0.056μM and 0.2085μAμM -1 cm -2 , respectively. The fabricated sensor also utilized for detection of H 2 O 2 in the presence of potentially active interfering species, and found high selectivity towards H 2 O 2 . Copyright © 2016 Elsevier Inc. All rights reserved.

Kinetics of NiO and NiCl2 Hydrogen Reduction as Precursors and Properties of Produced Ni/Al2O3 and Ni-Pd/Al2O3 Catalysts

PubMed Central

Sokić, Miroslav; Kamberović, Željko; Nikolić, Vesna; Marković, Branislav; Korać, Marija; Anđić, Zoran; Gavrilovski, Milorad

2015-01-01

The objects of this investigation were the comparative kinetic analysis of the NiO and NiCl2 reduction by hydrogen during an induction period and elimination of the calcination during the synthesis of Ni/Al2O3 catalysts. The effect of temperature and time on NiO and NiCl2 reduction degrees was studied. Avrami I equation was selected as the most favorable kinetic model and used to determine activation energy of the NiO and NiCl2 reduction for the investigated temperature range (623–923 K) and time intervals (1–5 minutes). The investigation enabled reaching conclusions about the reaction ability and rate of the reduction processes. Afterward, Ni/Al2O3 catalysts were obtained by using oxide and chloride precursor for Ni. The catalysts were supported on alumina-based foam and prepared via aerosol route. Properties of the samples before and after low-temperature hydrogen reduction (633 K) were compared. Obtained results indicated that the synthesis of Ni/Al2O3 catalysts can be more efficient if chloride precursor for Ni is directly reduced by hydrogen during the synthesis process, without the calcination step. In addition, Ni-Pd/Al2O3 catalysts with different metal content were prepared by using chloride precursors. Lower reduction temperature was utilized and the chlorides were almost completely reduced at 533 K. PMID:25789335

Arsenic Trioxide – An Old Drug Rediscovered

PubMed Central

Emadi, Ashkan; Gore, Steven D.

2010-01-01

Over the last 17 years, clinical trials conducted worldwide have demonstrated the efficacy of arsenic trioxide (As2O3) in the treatment of relapsed acute promyelocytic leukemia (APL). Currently, the role of As2O3 in front-line therapy is under investigation. Recent trials in the US have demonstrated that the addition of As2O3 to standard treatment regimens improves survival outcomes in patients with APL and may allow a reduction in cytotoxic chemotherapy exposure. As2O3 has also shown efficacy in other malignancies, particularly multiple myeloma and myelodysplastic syndromes. Therapeutic doses of As2O3 are well tolerated, with no evidence of long-term toxicity. Adverse events include APL differentiation syndrome, electrocardiographic abnormalities, and mild elevations in liver enzymes. This review highlights trials investigating the role of As2O3 in induction and consolidation for newly diagnosed APL, as well as its role in other hematologic malignancies. The chemistry, mechanisms of action, and clinical side effects of As2O3 are also discussed. PMID:20471733

ZrO2 Layer Thickness Dependent Electrical and Dielectric Properties of BST/ZrO2/BST Multilayer Thin Films

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

Sahoo, S. K.; Misra, D.; Agrawal, D. C.

2011-01-01

Recently, high K materials play an important role in microelectronic devices such as capacitors, memory devices, and microwave devices. Now a days ferroelectric barium strontium titanate [Ba{sub x}Sr{sub 1-x}TiO{sub 3}, (BST)] thin film is being actively investigated for applications in dynamic random access memories (DRAM), field effect transistor (FET), and tunable devices because of its properties such as high dielectric constant, low leakage current, low dielectric loss, and high dielectric breakdown strength. Several approaches have been used to optimize the dielectric and electrical properties of BST thin films such as doping, graded compositions, and multilayer structures. We have found thatmore » inserting a ZrO{sub 2} layer in between two BST layers results in a significant reduction in dielectric constant, loss tangent, and leakage current in the multilayer thin films. Also it is shown that the properties of multilayer structure are found to depend strongly on the sublayer thicknesses. In this work the effect of ZrO{sub 2} layer thickness on the dielectric, ferroelectric as well as electrical properties of BST/ZrO{sub 2}/BST multilayer structure is studied. The multilayer Ba{sub 0.8}Sr{sub 0.2}TiO{sub 3}/ZrO{sub 2}/Ba{sub 0.8}Sr{sub 0.2}TiO{sub 3} film is deposited by a sol-gel process on the platinized Si substrate. The thickness of the middle ZrO{sub 2} layer is varied while keeping the top and bottom BST layer thickness as fixed. It is observed that the dielectric constant, dielectric loss tangent, and leakage current of the multilayer films reduce with the increase of ZrO{sub 2} layer thickness and hence suitable for memory device applications. The ferroelectric properties of the multilayer film also decrease with the ZrO{sub 2} layer thickness.« less

Demonstration of β-(Al x Ga1- x )2O3/β-Ga2O3 modulation doped field-effect transistors with Ge as dopant grown via plasma-assisted molecular beam epitaxy

NASA Astrophysics Data System (ADS)

Ahmadi, Elaheh; Koksaldi, Onur S.; Zheng, Xun; Mates, Tom; Oshima, Yuichi; Mishra, Umesh K.; Speck, James S.

2017-07-01

β-(Al x Ga1- x )2O3/β-Ga2O3 heterostructures were grown via plasma-assisted molecular beam epitaxy. The β-(Al x Ga1- x )2O3 barrier was partially doped by Ge to achieve a two-dimensional electron gas (2DEG) in Ga2O3. The formation of the 2DEG was confirmed by capacitance-voltage measurements. The impact of Ga-polishing on both the surface morphology and the reduction of the unintentionally incorporated Si at the growth interface was investigated using atomic force microscopy and secondary-ion mass spectrometry. Modulation doped field-effect transistors were fabricated. A maximum current density of 20 mA/mm with a pinch-off voltage of -6 V was achieved on a sample with a 2DEG sheet charge density of 1.2 × 1013 cm-2.

Operando Synchrotron XRD Investigation of Silver Metal Formation upon Electrochemical Reduction of Silver Iron Pyrophosphate (Ag 7Fe 3(P 2O 7) 4)

DOE PAGES

Zhang, Yiman; Kirshenbaum, Kevin C.; Marschilok, Amy C.; ...

2017-05-11

The formation of conductive metallic silver upon electrochemical reduction and lithiation of Ag 7Fe 3(P 2O 7) 4 is investigated. Alternating current impedance spectroscopy measurements show a 34% decrease in charge transfer resistance upon one electron equivalent (ee) of reduction, which is coincident with the formation of a Ag metal conductive network evidenced by both ex situ and operando X-ray diffraction. Quantitative assessment of Ag metal formation derived from operando XRD shows that only Ag + ions are reduced during the first 3ee, followed by simultaneous reduction of Ag + and Fe 3+ reduction for the next 5ee (3ee tomore » 8ee), culminating in reduction of the remaining Ag +. Scanning electron microscopy images show smaller Ag metal crystallite size and shorter nearest neighbor distance between and among Ag particles with higher depth of discharge. A high rate intermittent pulsatile discharge test is conducted where the cell delivers 12 total pulses during full discharge to probe the effect of Ag metal formation on the Li/Ag 7Fe 3(P 2O 7) 4 cell electrochemistry. The Ohmic resistance is derived from the voltage drop of each pulse. The resistance is 65 Ω initially, reaches its minimum of 26 Ω at 4.5 ee discharge, and levels off at 35 Ω after 7.0 ee reduction. In conclusion, the initial Ag reduction is more significant for the conductive network formation indicated by the decrease of both R ct and Ohmic resistance, which facilitates the high power output of the cell.« less

Operando Synchrotron XRD Investigation of Silver Metal Formation upon Electrochemical Reduction of Silver Iron Pyrophosphate (Ag 7Fe 3(P 2O 7) 4)

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

Zhang, Yiman; Kirshenbaum, Kevin C.; Marschilok, Amy C.

The formation of conductive metallic silver upon electrochemical reduction and lithiation of Ag 7Fe 3(P 2O 7) 4 is investigated. Alternating current impedance spectroscopy measurements show a 34% decrease in charge transfer resistance upon one electron equivalent (ee) of reduction, which is coincident with the formation of a Ag metal conductive network evidenced by both ex situ and operando X-ray diffraction. Quantitative assessment of Ag metal formation derived from operando XRD shows that only Ag + ions are reduced during the first 3ee, followed by simultaneous reduction of Ag + and Fe 3+ reduction for the next 5ee (3ee tomore » 8ee), culminating in reduction of the remaining Ag +. Scanning electron microscopy images show smaller Ag metal crystallite size and shorter nearest neighbor distance between and among Ag particles with higher depth of discharge. A high rate intermittent pulsatile discharge test is conducted where the cell delivers 12 total pulses during full discharge to probe the effect of Ag metal formation on the Li/Ag 7Fe 3(P 2O 7) 4 cell electrochemistry. The Ohmic resistance is derived from the voltage drop of each pulse. The resistance is 65 Ω initially, reaches its minimum of 26 Ω at 4.5 ee discharge, and levels off at 35 Ω after 7.0 ee reduction. In conclusion, the initial Ag reduction is more significant for the conductive network formation indicated by the decrease of both R ct and Ohmic resistance, which facilitates the high power output of the cell.« less

Synthesis of Hierarchical Nanoporous Microstructures via the Kirkendall Effect in Chemical Reduction Process

NASA Astrophysics Data System (ADS)

Gao, Ling; Pang, Chao; He, Dafang; Shen, Liming; Gupta, Arunava; Bao, Ningzhong

2015-11-01

A series of novel hierarchical nanoporous microstructures have been synthesized through one-step chemical reduction of micron size Cu2O and Co3O4 particles. By controlling the reduction time, non-porous Cu2O microcubes sequentially transform to nanoporous Cu/Cu2O/Cu dented cubic composites and hollow eightling-like Cu microparticles. The mechanism involved in the complex structural evolution is explained based on oxygen diffusion and Kirkendall effect. The nanoporous Cu/Cu2O/Cu dented cubic composites exhibit superior electrochemical performance as compared to solid Cu2O microcubes. The reduction of nonporous Co3O4 also exhibits a uniform sequential reduction process from nonporous Co3O4 to porous Co3O4/CoO composites, porous CoO, porous CoO/Co composites, and porous foam-like Co particles. Nanoscale channels originate from the particle surface and eventually develop inside the entire product, resulting in porous foam-like Co microparticles. The Kirkendall effect is believed to facilitate the formation of porous structures in both processes.

Pulmonary Cerium Dioxide Nanoparticles Exposure Differentially Impairs Coronary and Mesenteric Arteriolar Reactivity

PubMed Central

Minarchick, Valerie C; Stapleton, Phoebe A; Porter, Dale W; Wolfarth, Michael G; Çiftyürek, Engin; Barger, Mark; Sabolsky, Edward M.; Nurkiewicz, Timothy R

2013-01-01

Cerium dioxide nanoparticles (CeO2 NPs) are an engineered nanomaterial that possesses unique catalytic, oxidative and reductive properties. Currently, CeO2 NPs are being used as a fuel catalyst but these properties are also utilized in the development of potential drug treatments for radiation and stroke protection. These uses of CeO2 NPs present a risk for human exposure; however, to date no studies have investigated the effects of CeO2 NPs on the microcirculation following pulmonary exposure. Previous studies in our laboratory with other nanomaterials have shown impairments in normal microvascular function after pulmonary exposures. Therefore, we predicted that CeO2 NP exposure would cause microvascular dysfunction that is dependent on the tissue bed and dose. Twenty-four hour post exposure to CeO2 NPs (0–400 μg), mesenteric and coronary arterioles were isolated and microvascular function was assessed. Our results provided evidence that pulmonary CeO2 NP exposure impairs endothelium-dependent and -independent arteriolar dilation in a dose-dependent manner. The CeO2 NP exposure dose which causes a 50% impairment in arteriolar function (EC50) was calculated and ranged from 15 – 100 μg depending on the chemical agonist and microvascular bed. Microvascular assessments with acetylcholine revealed a 33–75% reduction in function following exposure. Additionally, there was a greater sensitivity to CeO2 NP exposure in the mesenteric microvasculature due to the 40% decrease in the calculated EC50 compared to the coronary microvasculature EC50. CeO2 NP exposure increased mean arterial pressure in some groups. Taken together these observed microvascular changes may likely have detrimental effects on local blood flow regulation and contribute to cardiovascular dysfunction associated with particle exposure. PMID:23645470

Preparation and characterization of maghemite nanoparticles from mild steel for magnetically guided drug therapy.

PubMed

Kumar, Nitesh; Kulkarni, Kaustubh; Behera, Laxmidhar; Verma, Vivek

2017-08-01

Maghemite (γ-Fe 2 O 3 ) nanoparticles for therapeutic applications are prepared from mild steel but the existing synthesis technique is very cumbersome. The entire process takes around 100 days with multiple steps which lack proper understanding. In the current work, maghemite nanoparticles of cuboidal and spheroidal morphologies were prepared from mild steel chips by a novel cost effective oil reduction technique for magnetically guided intravascular drug delivery. The technique developed in this work yields isometric sized γ-Fe 2 O 3 nanoparticles in 6 h with higher saturation magnetization as compared to the existing similar solid state synthesis route. Mass and heat flow kinetics during the heating and quenching steps were studied with the help of Finite element simulations. Qualitative and quantitative analysis of the γ-Fe 2 O 3 phase is performed with the help of x-ray diffraction, transmission electron microscope and x-ray photoelectron spectroscopy. Mechanism for the α-Fe 2 O 3 (haematite) to γ-Fe 2 O 3 (maghemite) phase evolution during the synthesis process is also investigated. Maghemite (γ-Fe 2 O 3 ) nanoparticles were prepared bya novel cost effective oil reduction technique as mentioned below in the figure. The raw materials included mild steel chips which is one of the most abundant engineering materials. These particles can be used as ideal nanocarriers for targeted drug delivery through the vascular network.

Bioelectrochemistry of heme peptide at seamless three-dimensional carbon nanotubes/graphene hybrid films for highly sensitive electrochemical biosensing.

PubMed

Komori, Kikuo; Terse-Thakoor, Trupti; Mulchandani, Ashok

2015-02-18

A seamless three-dimensional hybrid film consisting of carbon nanotubes grown at the graphene surface (CNTs/G) is a promising material for the application to highly sensitive enzyme-based electrochemical biosensors. The CNTs/G film was used as a conductive nanoscaffold for enzymes. The heme peptide (HP) was immobilized on the surface of the CNTs/G film for amperometric sensing of H2O2. Compared with flat graphene electrodes modified with HP, the catalytic current for H2O2 reduction at the HP-modified CNTs/G electrode increased due to the increase in the surface coverage of HP. In addition, microvoids in the CNTs/G film contributed to diffusion of H2O2 to modified HP, resulting in the enhancement of the catalytic cathodic currents. The kinetics of the direct electron transfer from the CNTs/G electrode to compound I and II of modified HP was also analyzed.

Recovery of zinc and manganese, and other metals (Fe, Cu, Ni, Co, Cd, Cr, Na, K) from Zn-MnO2 and Zn-C waste batteries: Hydroxyl and carbonate co-precipitation from solution after reducing acidic leaching with use of oxalic acid

NASA Astrophysics Data System (ADS)

Sobianowska-Turek, A.; Szczepaniak, W.; Maciejewski, P.; Gawlik-Kobylińska, M.

2016-09-01

The article discusses the current situation of the spent batteries and portable accumulators management. It reviews recycling technologies of the spent batteries and portable accumulators which are used in the manufacturing installations in the world. Also, it presents the authors' research results on the reductive acidic leaching of waste material of the zinc-carbon batteries (Zn-C) and zinc-manganese batteries (alkaline Zn-MnO2) delivered by a company dealing with mechanical treatment of this type of waste stream. The research data proved that the reductive acidic leaching (H2SO4 + C2H2O4) of the battery's black mass allows to recover 85.0% of zinc and 100% of manganese. Moreover, it was found that after the reductive acidic leaching it is possible to recover nearly 100% of manganese, iron, cadmium, and chromium, 98.0% of cobalt, 95.5% of zinc, and 85.0% of copper and nickel from the solution with carbonate method. On the basis of the results, it is possible to assume that the carbonate method can be used for the preparation of manganese-zinc ferrite.

Sensitive detection of dopamine via leucodopaminechrome on polyacrylic acid-coated ceria nanorods

NASA Astrophysics Data System (ADS)

Sheng, Weiqin; Zheng, Liang; Liu, Yan; Zhao, Xueqin; Weng, Jian; Zhang, Yang

2017-09-01

The major hurdle in detection of dopamine (DA) by electro-analysis is the presence of physiological interferents with a similar oxidation potential of DA. The conventional method is to enlarge the difference of their oxidation potentials. Here, we report an unconventional method to detect DA via leucodopaminechrome on CeO2 nanorods. Leucodopaminechrome is produced from the cyclization of dopamine-quinone, a product of two-electron oxidation of DA. Thus, its concentration is proportional to the DA concentration. Determining DA is demonstrated by measuring the reduction current of leucodopaminechrome on CeO2 nanorods. CeO2 nanorods demonstrate high electrocatalytic activity for reduction of leucodopaminechrome with a low potential at -0.27 V. The low detection potential of leucodopaminechrome can avoid the interference from ascorbic acid (AA) and uric acid (UA). Therefore, detecting DA via leucodopaminechrome is an effective method to avoid interference from AA and UA, and the suggested biosensor also displays good reproducibility and stability.

Influence of TiO2 hollow sphere size on its photo-reduction activity for toxic Cr(VI) removal.

PubMed

Cai, Jiabai; Wu, Xueqing; Zheng, Fengying; Li, Shunxing; Wu, Yaling; Lin, Yanping; Lin, Liting; Liu, Biwen; Chen, Qiaoying; Lin, Luxiu

2017-03-15

After polystyrene@titanium dioxide (PS@TiO 2 ) composite with different size was calcined at designated temperature, TiO 2 hollow sphere with controllable size was obtained for high efficient photo-reduction of Cr(VI). The feature of the TiO 2 hollow sphere was investigated by SEM, TEM, XRD, UV-Vis, and photoluminescence. The photo-reduction of Cr(VI) were measured for the performance assessment of the TiO 2 hollow sphere, Cr(VI) was used as an electron acceptor. After irradiation for 2h, the photo-reduction rate of Cr(VI) (pH=2.82) for TiO 2 (450nm) was 96%, which exhibited an increase of 5% and 8% compared with TiO 2 (370nm) and TiO 2 (600nm). The absorption edges of TiO 2 hollow sphere (450nm) was largest with the increasing of hollow sphere size from 370 to 600nm. The optimal hollow sphere size of TiO 2 was 450nm for the photo-reduction of Cr(VI), because the light-harvesting efficiency (the best of absorption edge) and photo-generated electron-hole separation rate (the best of photo-reduction rate) of TiO 2 hollow sphere were controlled by its hollow sphere size. In addition, we find that the behavior of the hydrogen production was inhibited by the coexistence Cr(VI) solution. This study can improve our understanding of the mechanism for the activity enhancement by the optimal hollow sphere size of TiO 2 . Copyright © 2016 Elsevier Inc. All rights reserved.

High-performance of bare and Ti-doped α-MnO2 nanoparticles in catalyzing the Oxygen Reduction Reaction

NASA Astrophysics Data System (ADS)

Pargoletti, E.; Cappelletti, G.; Minguzzi, A.; Rondinini, S.; Leoni, M.; Marelli, M.; Vertova, A.

2016-09-01

Nanostructured MnO2 has unique electrocatalytic properties towards the Oxygen Reduction Reaction (ORR, the main cathodic reaction in metal-air devices), representing an excellent alternative to the expensive platinum. Herein, we report the hydrothermal synthesis of bare and 5% Ti-doped α-MnO2 nanoparticles using two different oxidizing agents, namely ammonium persulfate for MH_N samples and potassium permanganate for MH_K ones. The physico-chemical characterizations show that oxidant cations induce different structural, morphological and surface properties of the final powders. Hence, correlations between the different α-MnO2 characteristics and their electrocatalytic performances towards the ORR are drawn, highlighting the diverse effect even on the kinetic point of view. The ORR activity in alkaline media is examined by means of Staircase - Linear Sweep Voltammetry (S-LSV), using Gas Diffusion Electrode (GDE) as the air-cathode. The presence of these nanoparticles in the GDEs leads to a significant shift of the ORR onset potential (∼100 mV) towards less cathodic values, underlining the electrocatalytic efficiency of all the nanopowders. Furthermore, high exchange current densities (j0) are determined for GDEs with Ti-doped MnO2, comparable to the well-performing Pd45Pt5Sn50, and making it a promising material for the ORR.

Theoretical estimation of equilibrium sulfur isotope fractionations among aqueous sulfite species: Implications for isotope models of microbial sulfate reduction

NASA Astrophysics Data System (ADS)

Eldridge, D. L.; Farquhar, J.; Guo, W.

2015-12-01

Sulfite (sensu lato), an intermediate in a variety sulfur redox processes, plays a particularly important role in microbial sulfate reduction. It exists intracellularly as multiple species between sets of enzymatic reactions that transform sulfate to sulfide, with the exact speciation depending on pH, T, and ionic strength. However, the complex speciation of sulfite is ignored in current isotope partitioning models of microbial sulfate reduction and simplified solely to the pyramidal SO32- (sulfite sensu stricto), due to a lack of appropriate constraints. We theoretically estimated the equilibrium sulfur isotope fractionations (33S/32S, 34S/32S, 36S/32S) among all documented sulfite species in aqueous solution, including sulfite (SO32-), bisulfite isomers and dimers ((HS)O3-, (HO)SO2-, S2O52-), and SO2(aq), through first principles quantum mechanical calculations. The calculations were performed at B3LYP/6-31+G(d,p) level using cluster models with 30-40 water molecules surrounding the solute. Our calculated equilibrium fractionation factors compare well to the available experimental constraints and suggest that the minor and often-ignored tetrahedral (HS)O3- isomer of bisulfite strongly influences isotope partitioning behavior in the sulfite system under most environmentally relevant conditions, particularly fractionation magnitudes and unusual temperature dependence. For example, we predict that sulfur isotope fractionation between sulfite and bulk bisulfite in solution should have an apparent inverse temperature dependence due to the influence of (HS)O3- and its increased stability at higher temperatures. Our findings highlight the need to appropriately account for speciation/isomerization of sulfur species in sulfur isotope studies. We will also present similar calculation results of other aqueous sulfur compounds (e.g., H2S/HS-, SO42-, S2O32-, S3O62-, and poorly documented SO22- species), and discuss the implication of our results for microbial sulfate reduction models and other sulfur-redox processes in nature.

Application of nitrogen-doped TiO2 nano-tubes in dye-sensitized solar cells

NASA Astrophysics Data System (ADS)

Tran, Vy Anh; Truong, Trieu Thinh; Phan, Thu Anh Pham; Nguyen, Trang Ngoc; Huynh, Tuan Van; Agresti, Antonio; Pescetelli, Sara; Le, Tien Khoa; Di Carlo, Aldo; Lund, Torben; Le, So-Nhu; Nguyen, Phuong Tuyet

2017-03-01

Our research aimed to improve the overall energy conversion efficiency of DSCs by applying nitrogen-doped TiO2 nano-tubes (N-TNT) for the preparation of DSCs photo-anodes. The none-doped TiO2 nano-tubes (TNTs) were synthesized by alkaline hydrothermal treatment of Degussa P25 TiO2 particles in 10 M NaOH. The nano-tubes were N-doped by reflux in various concentrations of NH4NO3. The effects of nitrogen doping on the structure, morphology, and crystallography of N-TNT were analyzed by transmission electron microscopy (TEM), infrared spectroscopy (IR), Raman spectroscopy, and X-ray photoelectron spectra (XPS). DSCs fabricated with doped N-TNT and TNT was characterized by J-V measurements. Results showed that nitrogen doping significantly enhanced the efficiency of N-TNT cells, reaching the optimum value (η = 7.36%) with 2 M nitrogen dopant, compared to η = 4.75% of TNT cells. The high efficiency of the N-TNT cells was attributed to increased current density due to the reduction of dark current in the DSCs.

Electrochemical CO 2 Reduction on Oxide-Derived Cu Surface with Various Oxide Thicknesses

DOE PAGES

Liang, Zhixiu; Fu, Jie; Vukmirovic, Miomir B.; ...

2018-03-26

Here, cuprous oxide on copper foil electrodes prepared via electrochemical deposition and thermal annealing are investigated towards CO 2 electrochemical reduction at low overpotential. The thickness of the electrochemical deposited Cu 2O was controlled by varying the constant-current deposition time. The surface morphology and roughness were examined with SEM and CV respectively. The electrode fabricated by cuprous oxide deposited for 20 min demonstrated the best faradic efficiency (7.02%) and specific activity (0.123 mA/cm 2) towards format/formic acid formation at -0.5 V vs. RHE in CO 2 saturated 0.5 M K 2CO 3 among studied samples.

Electrochemical CO 2 Reduction on Oxide-Derived Cu Surface with Various Oxide Thicknesses

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

Liang, Zhixiu; Fu, Jie; Vukmirovic, Miomir B.

Here, cuprous oxide on copper foil electrodes prepared via electrochemical deposition and thermal annealing are investigated towards CO 2 electrochemical reduction at low overpotential. The thickness of the electrochemical deposited Cu 2O was controlled by varying the constant-current deposition time. The surface morphology and roughness were examined with SEM and CV respectively. The electrode fabricated by cuprous oxide deposited for 20 min demonstrated the best faradic efficiency (7.02%) and specific activity (0.123 mA/cm 2) towards format/formic acid formation at -0.5 V vs. RHE in CO 2 saturated 0.5 M K 2CO 3 among studied samples.

O2 reduction to H2O by the multicopper oxidases.

PubMed

Solomon, Edward I; Augustine, Anthony J; Yoon, Jungjoo

2008-08-14

In nature the four electron reduction of O2 to H2O is carried out by Cytochrome c oxidase (CcO) and the multicopper oxidases (MCOs). In the former, Cytochrome c provides electrons for pumping protons to produce a gradient for ATP synthesis, while in the MCOs the function is the oxidation of substrates, either organic or metal ions. In the MCOs the reduction of O2 is carried out at a trinuclear Cu cluster (TNC). Oxygen intermediates have been trapped which exhibit unique spectroscopic features that reflect novel geometric and electronic structures. These intermediates have both intact and cleaved O-O bonds, allowing the reductive cleavage of the O-O bond to be studied in detail both experimentally and computationally. These studies show that the topology of the TNC provides a unique geometric and electronic structure particularly suited to carry out this key reaction in nature.

O2 Reduction to H2O by the Multicopper Oxidases

PubMed Central

Solomon, Edward I.; Augustine, Anthony J.; Yoon, Jungjoo

2010-01-01

In nature the four electron reduction of O2 to H2O is carried out by Cytochrome c Oxidase (CcO) and the multicopper oxidases (MCOs). In the former, Cytochrome c provides electrons for pumping protons to produce a gradient for ATP synthesis, while in the MCOs the function is the oxidation of substrates, either organic or metal ions. In the MCOs the reduction of O2 is carried out at a trinuclear Cu cluster (TNC). Oxygen intermediates have been trapped which exhibit unique spectroscopic features that reflect novel geometric and electronic structures. These intermediates have both intact and cleaved O-O bonds, allowing the reductive cleavage of the O-O bond to be studied in detail both experimentally and computationally. These studies show that the topology of the TNC provides a unique geometric and electronic structure particularly suited to carry out this key reaction in Nature. PMID:18648693

Synthesis and photocatalytic CO2 reduction performance of Cu2O/Coal-based carbon nanoparticle composites

NASA Astrophysics Data System (ADS)

Dedong, Zhang; Maimaiti, Halidan; Awati, Abuduheiremu; Yisilamu, Gunisakezi; Fengchang, Sun; Ming, Wei

2018-05-01

The photocatalytic reduction of CO2 into hydrocarbons provides a promising approach to overcome the challenges of environmental crisis and energy shortage. Here we fabricated a cuprous oxide (Cu2O) based composite photocatalyst consisting of Cu2O/carbon nanoparticles (CNPs). To prepare the CNPs, coal samples from Wucaiwan, Xinjiang, China, were first treated with HNO3, followed by hydrogen peroxide (H2O2) oxidation to strip nanocrystalline carbon from coal. After linking with oxygen-containing group such as hydroxyl, coal-based CNPs with sp2 carbon structure and multilayer graphene lattice structure were synthesized. Subsequently, the CNPs were loaded onto the surface of Cu2O nanoparticles prepared by in-situ reduction of copper chloride (CuCl2·2H2O). The physical properties and chemical structure of the Cu2O/CNPs as well as photocatalytic activity of CO2/H2O reduction into CH3OH were measured. The results demonstrate that the Cu2O/CNPs are composed of spherical particles with diameter of 50 nm and mesoporous structure, which are suitable for CO2 adsorption. Under illumination of visible light, electron-hole pairs are generated in Cu2O. Thanks to the CNPs, the fast recombination of electron-hole pairs is suppressed. The energy gradient formed on the surface of Cu2O/CNPs facilitates the efficient separation of electron-hole pairs for CO2 reduction and H2O oxidation, leading to enhanced photocatalytic activity.

Quantification of ozone exposure- and stomatal uptake-yield response relationships for soybean in Northeast China.

PubMed

Zhang, Weiwei; Feng, Zhaozhong; Wang, Xiaoke; Liu, Xiaobing; Hu, Enzhu

2017-12-01

High ground-level O 3 is a new threat to agricultural production in Northeast China with the increasing ambient O 3 concentration. Little is known about its impacts on soybean production in this key agricultural region. Accumulated O 3 exposure-response and stomatal O 3 flux-response relationships were developed during two continuous growing seasons to evaluate O 3 -induced yield reduction of four typical soybean cultivars in Northeast China. Results showed that critical levels of AOT40 (accumulated hourly O 3 concentrations over a threshold of 40nmol·mol -1 ), SUM06 (sum of all hourly average O 3 concentrations over 0.06μmol·mol -1 ) and W126 (sum of O 3 concentrations weighted by a sigmoidal function) in relation to 5% reduction in relative seed yield were 4.2, 7.6 and 6.8μmol·mol -1 ·h, respectively. The effect of O 3 on plants was influenced by leaf position in canopy. An improved Jarvis stomatal conductance model including leaf (node) position fitted well with field measurements. The best linear relationship between stomatal O 3 flux and relative soybean yield was obtained when phytotoxic ozone dose was integrated over a threshold of 9.6nmol·m -2 ·s -1 (POD 9.6 ) to represent the detoxification capacity of soybean. POD 9.6 and the commonly used POD 6 in relation to 5% reduction in relative seed yield of soybean were 0.9mmol·m -2 and 1.8mmol·m -2 , respectively. O 3 concentrations above ~38nmol·mol -1 contributed to POD 9.6 and caused seed yield loss in soybean. Current annual yield loss of soybean at ambient O 3 was estimated to range between 23.4% and 30.2%. The O 3 dose-response relationships and corresponding thresholds obtained here will benefit regional O 3 risk assessment on soybean production in Northeast China. Copyright © 2017 Elsevier B.V. All rights reserved.

Magnesiothermic reduction for direct synthesis of Ti-Nb alloy at 1073 K (800 °C)

NASA Astrophysics Data System (ADS)

Choi, Kyunsuk; Lee, Kwang Hee; Ali, Basit; Choi, Sang-Hoon; Park, Kyoung-Tae; Sohn, Il

2017-09-01

Direct fabrication of titanium (Ti) and niobium (Nb) alloys by direct magnesiothermic reduction from the respective initial metal oxides and complex oxides has been studied. TiO2, Nb2O5, and complex TiNb2O7 oxides were used as raw materials with Mg used as a reductant. To ensure a high chemical potential of the reactants to drive the spontaneous magnesiothermic reduction of the oxide mixtures, excess Mg five times higher than the required stoichiometric molar ratio was added. Samples were heated in a glove box under recycled and purified Ar atmosphere at 1073 K (800 °C) for 10 h. After the reduction of TiO2, intermediate oxide phases of Ti6O could still be observed, but reduction of Nb2O5 and TiNb2O7 showed metallic Nb and Ti-Nb to be present with negligible oxides according to the scanning electron microscope-energy dispersive spectroscopy and x ray diffraction analysis. This indicated that direct fabrication of Ti-Nb alloys through a complex TiNb2O7 oxide is possible and can be more efficient than alloying pure metallic elements of Ti and Nb.

Construction and Characterization of a Chitosan-Immobilized-Enzyme and β-Cyclodextrin-Included-Ferrocene-Based Electrochemical Biosensor for H2O2 Detection

PubMed Central

Dong, Wenbo; Wang, Kaiyin; Chen, Yu; Li, Weiping; Ye, Yanchun; Jin, Shaohua

2017-01-01

An electrochemical detection biosensor was prepared with the chitosan-immobilized-enzyme (CTS-CAT) and β-cyclodextrin-included-ferrocene (β-CD-FE) complex for the determination of H2O2. Ferrocene (FE) was included in β-cyclodextrin (β-CD) to increase its stability. The structure of the β-CD-FE was characterized. The inclusion amount, inclusion rate, and electrochemical properties of inclusion complexes were determined to optimize the reaction conditions for the inclusion. CTS-CAT was prepared by a step-by-step immobilization method, which overcame the disadvantages of the conventional preparation methods. The immobilization conditions were optimized to obtain the desired enzyme activity. CTS-CAT/β-CD-FE composite electrodes were prepared by compositing the CTS-CAT with the β-CD-FE complex on a glassy carbon electrode and used for the electrochemical detection of H2O2. It was found that the CTS-CAT could produce a strong reduction peak current in response to H2O2 and the β-CD-FE could amplify the current signal. The peak current exhibited a linear relationship with the H2O2 concentration in the range of 1.0 × 10−7–6.0 × 10−3 mol/L. Our work provided a novel method for the construction of electrochemical biosensors with a fast response, good stability, high sensitivity, and a wide linear response range based on the composite of chitosan and cyclodextrin. PMID:28773229

[Effects of organic and inorganic fertilizers on emission and sources of N2O in vegetable soils.

PubMed

Lin, Wei; Ding, Jun Jun; Li, Yu Zhong; Xu, Chun Ying; Li, Qiao Zhen; Zheng, Qian; Zhuang, Shan

2018-05-01

To clarify the microbial pathway of the N 2 O production and consumption under different fertilizers and provide theoretical basis for the reduction of N 2 O emission and rational management of fertilization in vegetable soils, we examined dynamics of N 2 O flux and isotope signatures under different fertilizer treatments in the vegetable soils of Beijing, by setting up four treatments (organic-acetylene, organic-nonacetylene, inorganic-acetylene, inorganic-nonacetylene) and using the stable isotope technique of natural N 2 O abundance. The results showed that the cumulative N 2 O emission from organic-acetylene group, organic-nonacetylene group, inorganic-acetylene group and inorganic-nonacetylene group was (374±37), (283±34), (458±36), (355±41) g·m -2 in cabbage growing season, respectively. N 2 O fluxes were significantly lower in treatments with organic fertilizer than those with inorganic fertilizer and significantly higher in acetylene group than nonacetylene group. The degree of N 2 O reduction were similar in both fertilizer treatments, and higher nitrification was found in inorganic fertilizer than organic fertilizer treatments. Acetylene only inhibited partial nitrification and partial N 2 O reduction at the peak of N 2 O emission. When the emission was reduced, N 2 O reduction could be completely suppressed. Therefore, the inorganic fertilizer might trigger nitrification and promote higher N 2 O emission. The high concentration of N 2 O could withstand that acetylene to inhibite N 2 O reduction. Hence, using organic fertilizers instead of some inorganic ones could effectively reduce N 2 O emission in vegetable soils of Beijing. The N 2 O concentration threshold should be considered when we identify N 2 O source by acetylene inhibition method.

Climate change impacts of US reactive nitrogen.

PubMed

Pinder, Robert W; Davidson, Eric A; Goodale, Christine L; Greaver, Tara L; Herrick, Jeffrey D; Liu, Lingli

2012-05-15

Fossil fuel combustion and fertilizer application in the United States have substantially altered the nitrogen cycle, with serious effects on climate change. The climate effects can be short-lived, by impacting the chemistry of the atmosphere, or long-lived, by altering ecosystem greenhouse gas fluxes. Here we develop a coherent framework for assessing the climate change impacts of US reactive nitrogen emissions, including oxides of nitrogen, ammonia, and nitrous oxide (N(2)O). We use the global temperature potential (GTP), calculated at 20 and 100 y, in units of CO(2) equivalents (CO(2)e), as a common metric. The largest cooling effects are due to combustion sources of oxides of nitrogen altering tropospheric ozone and methane concentrations and enhancing carbon sequestration in forests. The combined cooling effects are estimated at -290 to -510 Tg CO(2)e on a GTP(20) basis. However, these effects are largely short-lived. On a GTP(100) basis, combustion contributes just -16 to -95 Tg CO(2)e. Agriculture contributes to warming on both the 20-y and 100-y timescales, primarily through N(2)O emissions from soils. Under current conditions, these warming and cooling effects partially offset each other. However, recent trends show decreasing emissions from combustion sources. To prevent warming from US reactive nitrogen, reductions in agricultural N(2)O emissions are needed. Substantial progress toward this goal is possible using current technology. Without such actions, even greater CO(2) emission reductions will be required to avoid dangerous climate change.

Climate change impacts of US reactive nitrogen

PubMed Central

Pinder, Robert W.; Davidson, Eric A.; Goodale, Christine L.; Greaver, Tara L.; Herrick, Jeffrey D.; Liu, Lingli

2012-01-01

Fossil fuel combustion and fertilizer application in the United States have substantially altered the nitrogen cycle, with serious effects on climate change. The climate effects can be short-lived, by impacting the chemistry of the atmosphere, or long-lived, by altering ecosystem greenhouse gas fluxes. Here we develop a coherent framework for assessing the climate change impacts of US reactive nitrogen emissions, including oxides of nitrogen, ammonia, and nitrous oxide (N2O). We use the global temperature potential (GTP), calculated at 20 and 100 y, in units of CO2 equivalents (CO2e), as a common metric. The largest cooling effects are due to combustion sources of oxides of nitrogen altering tropospheric ozone and methane concentrations and enhancing carbon sequestration in forests. The combined cooling effects are estimated at −290 to −510 Tg CO2e on a GTP20 basis. However, these effects are largely short-lived. On a GTP100 basis, combustion contributes just −16 to −95 Tg CO2e. Agriculture contributes to warming on both the 20-y and 100-y timescales, primarily through N2O emissions from soils. Under current conditions, these warming and cooling effects partially offset each other. However, recent trends show decreasing emissions from combustion sources. To prevent warming from US reactive nitrogen, reductions in agricultural N2O emissions are needed. Substantial progress toward this goal is possible using current technology. Without such actions, even greater CO2 emission reductions will be required to avoid dangerous climate change. PMID:22547815

End-Tidal CO2 Tension Is Predictive of Effective Nocturnal Oxygen Therapy in Patients with Chronic Heart Failure and Central Sleep Apnea.

PubMed

Sugimura, Koichiro; Shinozaki, Tsuyoshi; Fukui, Shigefumi; Ogawa, Hiromasa; Shimokawa, Hiroaki

2016-05-01

Central sleep apnea (CSA) is characterized by recurring cycles of crescendo-decrescendo ventilation during sleep, and enhances sympathetic nerve activity. Thus CSA has a prognostic impact in patients with chronic heart failure (CHF). Although nocturnal oxygen (O2) therapy decreases frequency of CSA and improves functional exercise capacity, it is also known that some non-responders to the therapy exist. We thus aimed to identify predictors of responders to nocturnal O2 therapy in CHF patients with CSA. In 12 CHF patients with CSA hospitalized at our department, sleep study was performed at 2 consecutive nights. Patients nasally inhaled O2 at either the first or second night in a randomized manner. To predict the percentage reduction in apnea-hypopnea index (%ΔAHI) in response to the nocturnal O2 therapy, we performed multiple regression analysis with a stepwise method with variables including age, brain-natriuretic peptide, circulation time, baseline AHI, hypercapnic ventilatory response and end-tidal carbon dioxide tension (PETCO2). Nocturnal O2 therapy significantly decreased AHI (from 32 ± 13 /h to 12 ± 10 /h, P < 0.0001). Among the possible predictors, PETCO2 was the only variable that is predictive of % changes in AHI. Receiver operating characteristics analysis determined 4.25% as the optimal cutoff PETCO2 level to identify responder to nocturnal O2 therapy (> 50% reduction of AHI), with 88.9% of sensitivity and 66.7% of specificity. In conclusion, PETCO2 is useful to predict the efficacy of O2 therapy in CHF patients with CSA, providing important information to the current nocturnal O2 therapy.

Isotopologue fractionation during nitrous oxide reduction in soil

NASA Astrophysics Data System (ADS)

Jinuntuya, M.; Sutka, R. L.; Ostrom, P. H.; Gandhi, H.; Ostrom, N. E.

2007-12-01

Reduction of N2O is a challenge to studies using isotope values to resolve global budgets and microbial sources of this critical greenhouse gas. Prior research has demonstrated that the difference in δ15N between the central (α) and outer (β) N atoms in the N2O can be used to distinguish N2O derived from nitrification and denitrification (Sutka et al., 2003; 2006; Toyoda et al., 2005). If the intramolecular distribution of 15N, however, is altered during reduction, apportionments of N2O to nitrification and denitrification will be inaccurate. Isotopologue analyses of N2O within soil mesocosm experiments were used to investigate fractionation during N2O reduction at four different levels of water filled pores space (WFPS) 60, 80, 100 and 110%. Uncultivated successional soils were obtained from the Kellogg Biological Station Long Term Ecological Research Site located in Michigan (KBS LTER). Isotopic enrichment factors (ɛ) for δ15N, δ18O, δ15Nα and δ15Nβ ranged from -4.2 to -9.0, -12.5 to -23.6, -6.4 to -10.0 and -2.0 to -7.9, respectively. With the exception of SP, lower fractionation factors were observed at higher WFPS demonstrating the importance of diffusion in limiting the expression of enzymatic fractionation. Isotopic discrimination in SP during N2O reduction was small and the ɛ values varied between -4.5 and 0 ‰. Strong correlations were evident between δ18O and δ15N during reduction and segregation against 18O was 2.7 times greater than 15N. Similarly, 18O was discriminated against approximately 2.0 times more than 15Nα. These relationships (1) provide a definitive means for establishing that isotope effects during reduction are present and (2) may provide a means to determine the source signatures even when reduction occurs.

Temperature Independent Catalytic Two-Electron Reduction of Dioxygen by Ferrocenes with a Tris[2-(2-pyridyl)ethyl]amine-Copper(II) Catalyst in the Presence of Perchloric Acid

PubMed Central

Das, Dipanwita; Lee, Yong-Min; Ohkubo, Kei; Nam, Wonwoo; Karlin, Kenneth D.; Fukuzumi, Shunichi

2013-01-01

Selective two-electron plus two-proton (2e−/2H+) reduction of O2 to hydrogen peroxide by ferrocene (Fc) or 1,1′-dimethylferrocene (Me2Fc) in the presence of perchloric acid is catalyzed efficiently by a mononuclear copper(II) complex, [CuII(tepa)]2+ {tepa = tris[2-(2-pyridyl)ethyl]amine} (1) in acetone. The E1/2 value for [CuII(tepa)]2+ as measured by cyclic voltammetry is 0.07 V vs Fc/Fc+ in acetone, being significantly positive, which makes it possible to use relatively weak one-electron reductants such as Fc and Me2Fc for the overall two-electron reduction of O2. Fast electron transfer from Fc or Me2Fc to 1 affords the corresponding CuI complex, [CuI(tepa)]+ (2), which reacts at low temperature (193 K) with O2, however only in presence of HClO4 to afford the hydroperoxo complex, [CuII(tepa)(OOH)]2+ (3). The detailed kinetic study on the homogeneous catalytic system reveals the rate-determining step to be the O2-binding process in the presence of HClO4 at lower temperature as well as at room temperature. The O2-binding kinetics in the presence of HClO4 were studied, demonstrating that the rate of formation of the hydroperoxo complex (3) as well as the overall catalytic reaction remained virtually the same with changing temperature. The apparent lack of an activation energy for the catalytic two-electron reduction of O2 is shown to result from the existence of a pre-equilibrium between 2 and O2 prior to the formation of the hydroperoxo complex 3. No further reduction of [CuII(tepa)(OOH)]2+ (3) by Fc or Me2Fc occurred, and instead 3 is protonated by HClO4 to yield H2O2 accompanied by regeneration of 1, thus completing the catalytic cycle for the two-electron reduction of O2 by Fc or Me2Fc. PMID:23394287

Turning on the protonation-first pathway for electrocatalytic CO 2 reduction by manganese bipyridyl tricarbonyl complexes

DOE PAGES

Ngo, Ken T.; McKinnon, Meaghan; Mahanti, Bani; ...

2017-01-24

Electrocatalytic reduction of CO 2 to CO is reported for the complex, { fac-Mn I([(MeO) 2Ph] 2bpy)(CO) 3(CH 3CN)}(OTf), containing four pendant methoxy groups, where [(MeO) 2Ph] 2bpy = 6,6'-bis(2,6-dimethoxyphenyl)-2,2'-bipyridine. In addition to a steric influence similar to that previously established for the 6,6'-dimesityl-2,2'-bipyridine ligand in [ fac-MnI(mes 2bpy)(CO) 3(CH 3CN)](OTf), which prevents Mn 0–Mn 0 dimerization, the [(MeO) 2Ph] 2bpy ligand introduces an additional electronic influence combined with a weak allosteric hydrogen-bonding interaction that significantly lowers the activation barrier for C–OH bond cleavage from the metallocarboxylic acid intermediate. This provides access to the thus far elusive protonation-first pathway, minimizingmore » the required overpotential for electrocatalytic CO 2 to CO conversion by Mn(I) polypyridyl catalysts, while concurrently maintaining a respectable turnover frequency. Comprehensive electrochemical and computational studies here confirm the positive influence of the [(MeO) 2Ph] 2bpy ligand framework on electrocatalytic CO 2 reduction and its dependence upon the concentration and p K a of the external Bronsted acid proton source (water, methanol, trifluoroethanol, and phenol) that is required for this class of manganese catalyst. Linear sweep voltammetry studies show that both phenol and trifluoroethanol as proton sources exhibit the largest protonation-first catalytic currents in combination with { fac-Mn I([(MeO) 2Ph] 2bpy)(CO) 3(CH 3CN)}(OTf), saving up to 0.55 V in overpotential with respect to the thermodynamically demanding reduction-first pathway, while bulk electrolysis studies confirm a high product selectivity for CO formation. As a result, to gain further insight into catalyst activation, time-resolved infrared (TRIR) spectroscopy combined with pulse-radiolysis (PR-TRIR), infrared spectroelectrochemistry, and density functional theory calculations were used to establish the v(CO) stretching frequencies and energetics of key redox intermediates relevant to catalyst activation.« less

Incorporation of indium in TiO2-based photoanodes for enhancing the photovoltaic conversion efficiency of dye-sensitized solar cells

NASA Astrophysics Data System (ADS)

Beula, R. Jeba; Devadason, Suganthi; Vidhya, B.

2018-06-01

Sol-gel-assisted spin-coating method was used to prepare TiO2 photoelectrodes doped with four different concentrations of indium 0.025, 0.05, 0.075 and 0.1 M. The crystalline phase and average crystallite size of the pure- and indium-doped TiO2 films were found using X-ray diffractometer. Raman analysis was performed for the pure- and In-doped TiO2 films to confirm the structure of anatase phase. UV-visible and photoluminescence spectrophotometer were used to analyze the optical properties of the films. A shift towards a lower wavelength in the absorption spectrum and widening of band gap were noted for the doped TiO2 films. Reduction in the peak intensity was observed in the PL spectra to indicate the inhibiting action of electron-hole recombination. A maximum (2.71%) light to current efficiency is noted for the dye-sensitized solar cells (DSSC) fabricated based on 0.025M In-doped TiO2 electrode.

Reduction on NOx emissions on urban areas by changing specific vehicle fleets: effects on NO2 and O3 concentration

NASA Astrophysics Data System (ADS)

Goncalves, M.; Jimenez, P.; Baldasano, J.

2007-12-01

The largest amount of NOx emissions in urban areas comes from on-road traffic, which is the largest contributor to urban air pollution (Colvile et al., 2001). Currently different strategies are being tested in order to reduce its effects; many of them oriented to the reduction of the unitary vehicles emissions, by alternative fuels use (such as biofuels, natural gas or hydrogen) or introduction of new technologies (such as hybrid electric vehicles or fuel cells). Atmospheric modelling permits to predict their consequences on tropospheric chemistry (Vautard et al., 2007). Hence, this work assesses the changes on NO2 and O3 concentrations when substituting a 10 per cent of the urban private cars fleets by petrol hybrid electric cars (HEC) or by natural gas cars (NGC) in Madrid and Barcelona urban areas (Spain). These two cities are selected in order to highlight the different patterns of pollutants transport (inland vs. coastal city) and the different responses to emissions reductions. The results focus on a typical summertime episode of air pollution, by means of the Eulerian air quality model ARW- WRF/HERMES/CMAQ, applied with high resolution (1-hr, 1km2) since of the complexity of both areas under study. The detailed emissions scenarios are implemented in the HERMES traffic emissions module, based on the Copert III-EEA/EMEP-CORINAIR (Nztiachristos and Samaras, 2000) methodology. The HEC introduction reduces NOx emissions from on-road traffic in a 10.8 per cent and 8.2 per cent; and the NGC introduction in a 10.3 per cent and 7.8 per cent, for Madrid and Barcelona areas, respectively. The scenarios also affect the NMVOCs reduction (ranging from -3.1 to -6.9 per cent), influencing the tropospheric photochemistry through the NOx/NMVOCs ratio. The abatement of the NO photooxidation but also to the reduction on primary NO2 involves a decrease on NO2 levels centred on urban areas. For example, the NO2 24-hr average concentration in downtown areas reduces up to 8 per cent (-6 μg m-3 on average). The urban areas are VOC-controlled, therefore the reduction on NOx emissions involves a minor increase on tropospheric O3 concentration (Jiménez and Baldasano, 2004), up to 1.5 per cent at some points. Nevertheless, the O3 precursors reduction has positive effects in the downwind areas affected by the urban plume, slightly reducing the O3 levels, but at the regional scale the reduction applied on urban traffic emissions has negligible effects. Both scenarios tested are very similar in terms of emissions reductions and air quality changes, which means that the NOx/NMVOCs ratio do not involve an O3-sensitivity regime variation among scenarios. The HEC scenario is more effective in reducing NO2 levels in urban areas than the NGC scenario (with maximum reductions affecting a larger area) and involves a larger increase in urban O3 concentration.

Lewis Acid-Induced Change from Four- to Two-Electron Reduction of Dioxygen Catalyzed by Copper Complexes Using Scandium Triflate

PubMed Central

Kakuda, Saya; Rolle, Clarence; Ohkubo, Kei; Siegler, Maxime A.; Karlin, Kenneth D.; Fukuzumi, Shunichi

2015-01-01

Mononuclear copper complexes, [(tmpa)CuII(CH3CN)](ClO4)2 (1, tmpa = tris(2-pyridylmethyl)amine) and [(BzQ)CuII(H2O)2](ClO4)2 (2, BzQ = bis(2-quinolinylmethyl)benzylamine)], act as efficient catalysts for the selective two-electron reduction of O2 by ferrocene derivatives in the presence of scandium triflate (Sc(OTf)3), in acetone, whereas 1 catalyzes the four-electron reduction of O2 by the same reductant in the presence of Brønsted acids such as triflic acid. Following formation of the peroxo-bridged dicopper(II) complex [(tmpa)CuII(O2)CuII(tmpa)]2+, the two-electron reduced product of O2 with Sc3+ is observed to be scandium peroxide ([Sc3+(O22−)]+). In the presence of three equiv of hexamethylphosphoric triamide (HMPA), [Sc3+(O22−)]+ was oxidized by [Fe(bpy)3]3+ (bpy = 2,2′-bipyridine) to the known superoxide species [(HMPA)3Sc3+(O2•−)]2+ as detected by EPR spectroscopy. A kinetic study revealed that the rate-determining step of the catalytic cycle for the two-electron reduction of O2 with 1 is electron transfer from Fc* to 1 to give a cuprous complex which is highly reactive toward O2, whereas the rate-determining step with 2 is changed to the reaction of the cuprous complex with O2 following electron transfer from ferrocene derivatives to 2. The explanation for the change in catalytic O2-reaction stoichiometry from four-electron with Brønsted acids to two-electron reduction in the presence of Sc3+ and also for the change in the rate-determining step is clarified based on a kinetics interrogation of the overall catalytic cycle as well as each step of the catalytic cycle with study of the observed effects of Sc3+ on copper-oxygen intermediates. PMID:25659416

Hierarchical Mesoporous NiO/MnO2@PANI Core-Shell Microspheres, Highly Efficient and Stable Bifunctional Electrocatalysts for Oxygen Evolution and Reduction Reactions.

PubMed

He, Junkai; Wang, Mingchao; Wang, Wenbo; Miao, Ran; Zhong, Wei; Chen, Sheng-Yu; Poges, Shannon; Jafari, Tahereh; Song, Wenqiao; Liu, Jiachen; Suib, Steven L

2017-12-13

We report on the new facile synthesis of mesoporous NiO/MnO 2 in one step by modifying inverse micelle templated UCT (University of Connecticut) methods. The catalyst shows excellent electrocatalytic activity and stability for both the oxygen evolution reaction (OER) and the oxygen reduction reaction (ORR) in alkaline media after further coating with polyaniline (PANI). For electrochemical performance, the optimized catalyst exhibits a potential gap, ΔE, of 0.75 V to achieve a current of 10 mA cm -2 for the OER and -3 mA cm -2 for the ORR in 0.1 M KOH solution. Extensive characterization methods were applied to investigate the structure-property of the catalyst for correlations with activity (e.g., XRD, BET, SEM, HRTEM, FIB-TEM, XPS, TGA, and Raman). The high electrocatalytic activity of the catalyst closely relates to the good electrical conductivity of PANI, accessible mesoporous structure, high surface area, as well as the synergistic effect of the specific core-shell structure. This work opens a new avenue for the rational design of core-shell structure catalysts for energy conversion and storage applications.

Cryptic oxygen cycling in anoxic marine zones.

PubMed

Garcia-Robledo, Emilio; Padilla, Cory C; Aldunate, Montserrat; Stewart, Frank J; Ulloa, Osvaldo; Paulmier, Aurélien; Gregori, Gerald; Revsbech, Niels Peter

2017-08-01

Oxygen availability drives changes in microbial diversity and biogeochemical cycling between the aerobic surface layer and the anaerobic core in nitrite-rich anoxic marine zones (AMZs), which constitute huge oxygen-depleted regions in the tropical oceans. The current paradigm is that primary production and nitrification within the oxic surface layer fuel anaerobic processes in the anoxic core of AMZs, where 30-50% of global marine nitrogen loss takes place. Here we demonstrate that oxygenic photosynthesis in the secondary chlorophyll maximum (SCM) releases significant amounts of O 2 to the otherwise anoxic environment. The SCM, commonly found within AMZs, was dominated by the picocyanobacteria Prochlorococcus spp. Free O 2 levels in this layer were, however, undetectable by conventional techniques, reflecting a tight coupling between O 2 production and consumption by aerobic processes under apparent anoxic conditions. Transcriptomic analysis of the microbial community in the seemingly anoxic SCM revealed the enhanced expression of genes for aerobic processes, such as nitrite oxidation. The rates of gross O 2 production and carbon fixation in the SCM were found to be similar to those reported for nitrite oxidation, as well as for anaerobic dissimilatory nitrate reduction and sulfate reduction, suggesting a significant effect of local oxygenic photosynthesis on Pacific AMZ biogeochemical cycling.

A hybrid DNA-templated gold nanocluster for enhanced enzymatic reduction of oxygen

DOE PAGES

Chakraborty, Saumen; Babanova, Sofia; Rocha, Reginaldo C.; ...

2015-08-19

We report the synthesis and characterization of a new DNA-templated gold nanocluster (AuNC) of ~1 nm in diameter and possessing ~7 Au atoms. When integrated with bilirubin oxidase (BOD) and single walled carbon nanotubes (SWNTs), the AuNC acts as an enhancer of electron transfer (ET) and lowers the overpotential of electrocatalytic oxygen reduction reaction (ORR) by ~15 mV as compared to the enzyme alone. In addition, the presence of AuNC causes significant enhancements in the electrocatalytic current densities at the electrode. Control experiments show that such enhancement of ORR by the AuNC is specific to nanoclusters and not to plasmonicmore » gold particles. Rotating ring disk electrode (RRDE) measurements confirm 4e– reduction of O 2 to H 2O with minimal production of H 2O 2, suggesting that the presence of AuNC does not perturb the mechanism of ORR catalyzed by the enzyme. This unique role of the AuNC as enhancer of ET at the enzyme-electrode interface makes it a potential candidate for the development of cathodes in enzymatic fuel cells, which often suffer from poor electronic communication between the electrode surface and the enzyme active site. In conclusion, the AuNC displays phosphorescence with large Stokes shift and microsecond lifetime.« less

Sc-substituted La0.6Sr0.4FeO3-δ mixed conducting oxides as promising electrodes for symmetrical solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Liu, Xuejiao; Han, Da; Zhou, Yucun; Meng, Xie; Wu, Hao; Li, Junliang; Zeng, Fanrong; Zhan, Zhongliang

2014-01-01

The main barrier to symmetrical solid oxide fuel cells (SOFCs), where the same catalytic materials are used simultaneously as the anodes and the cathodes, is to identify a redox-stable catalyst that exhibits superior catalytic activities for both fuel oxidation and oxygen reduction reactions. Here we report a Sc-substituted La0.6Sr0.4FeO3-δ oxide, La0.6Sr0.4Fe0.9Sc0.1O3-δ, that shows great promise as a new symmetrical electrode material with good structural stability and reasonable conductivities in air and hydrogen. We further demonstrate that nano-scale La0.6Sr0.4Fe0.9Sc0.1O3-δ catalysts impregnated into the porous La0.9Sr0.1Ga0.8Mg0.2O3-δ backbones exhibit good catalytic activities for oxygen reduction and hydrogen oxidation reactions and thereby yield low polarization resistances, e.g., 0.015 Ω cm2 in air and 0.29 Ω cm2 in hydrogen with appropriate current collection at 800 °C. Thin La0.9Sr0.1Ga0.8Mg0.2O3-δ electrolyte fuel cells with such symmetrical La0.6Sr0.4Fe0.9Sc0.1O3-δ catalysts showed maximum power densities of 0.56 and 0.32 W cm-2 when operating on 97% H2-3% H2O at 800 and 700 °C, respectively.

Insulation Resistance Degradation in Ni-BaTiO3 Multilayer Ceramic Capacitors

NASA Technical Reports Server (NTRS)

Liu, Donhang (David)

2015-01-01

Insulation resistance (IR) degradation in Ni-BaTiO3 multilayer ceramic capacitors has been characterized by the measurement of both time to failure and direct-current (DC) leakage current as a function of stress time under highly accelerated life test conditions. The measured leakage current-time dependence data fit well to an exponential form, and a characteristic growth time ?SD can be determined. A greater value of tau(sub SD) represents a slower IR degradation process. Oxygen vacancy migration and localization at the grain boundary region results in the reduction of the Schottky barrier height and has been found to be the main reason for IR degradation in Ni-BaTiO3 capacitors. The reduction of barrier height as a function of time follows an exponential relation of phi (??)=phi (0)e(exp -2?t), where the degradation rate constant ??=??o??(????/????) is inversely proportional to the mean time to failure (MTTF) and can be determined using an Arrhenius plot. For oxygen vacancy electromigration, a lower barrier height phi(0) will favor a slow IR degradation process, but a lower phi(0) will also promote electronic carrier conduction across the barrier and decrease the insulation resistance. As a result, a moderate barrier height phi(0) (and therefore a moderate IR value) with a longer MTTF (smaller degradation rate constant ??) will result in a minimized IR degradation process and the most improved reliability in Ni-BaTiO3 multilayer ceramic capacitors.

Mechanism of oxygen reduction reaction on Pt(111) in alkaline solution: Importance of chemisorbed water on surface

DOE PAGES

Liu, Shizhong; White, Michael G.; Liu, Ping

2016-06-30

Here, we report a detailed mechanistic study of the oxygen reduction reaction (ORR) on Pt(111) in alkaline solution, combining density functional theory and kinetic Monte Carlo simulations. A complex reaction network including four possible pathways via either 2e – or 4e – transfer is established and is able to reproduce the experimental measured polarization curve at both low- and high-potential regions. Our results show that it is essential to account for solvation by water and the dynamic coverage of *OH to describe the reaction kinetics well. In addition, a chemisorbed water (*H 2O)-mediated mechanism including 4e – transfers is identified,more » where the reduction steps via *H 2O on the surface are potential-independent and only the final removal of *OH from the surface in the form of OH –(aq) contributes to the current. For the ORR in alkaline solutions, such a mechanism is more competitive than the associative and dissociative mechanisms typically used to describe the ORR in acid solution. Finally, *OH and **O 2 intermediates are found to be critically important for tuning the ORR activity of Pt in alkaline solution. To enhance the activity, the binding of Pt should be tuned in such a way that *OH binding is weak enough to release more surface sites under working conditions, while **O 2 binding is strong enough to enable the ORR via the 4e – transfer mechanism.« less

Effects of MgO on the Reduction of Vanadium Titanomagnetite Concentrates with Char

NASA Astrophysics Data System (ADS)

Chen, Chao; Sun, TiChang; Wang, XiaoPing; Hu, TianYang

2017-10-01

The effects of MgO on the carbothermic reduction behavior of vanadium titanomagnetite concentrates (VTC) from Chengde, China, were investigated via temperature-programmed heating under nitrogen atmosphere in a sealed furnace. Gaseous product content was measured by using an infrared gas analyzer, and it was found that the addition of MgO to VTC with char decreased the reduction rate and reduction degree, and the utilization of CO in VTC reduction was also reduced. X-ray diffraction results showed that magnesium titanate (Mg2TiO4) was formed but FeTi2O5 was not observed in the VTC reduction process by adding 6 wt.% MgO, which can be explained by thermodynamic analysis. Scanning electron microscopy revealed that the enrichment of Mg in the unreacted core was the main reason that the further reduction of VTC was restricted. However, comparatively pure particles of Mg2TiO4 were generated, and the titanium and iron were separated well due to the combination of magnesium and titanium.

Amperometric biosensor based on reductive H2O2 detection using pentacyanoferrate-bound polymer for creatinine determination.

PubMed

Nieh, Chi-Hua; Tsujimura, Seiya; Shirai, Osamu; Kano, Kenji

2013-03-12

Pentacyanoferrate-bound poly(1-vinylimidazole) (PVI[Fe(CN)5]) was selected as a mediator for amperometric creatinine determination based on the reductive H2O2 detection. Creatinine amidohydrolase (CNH), creatine amidohydrolase (CRH), sarcosine oxidase (SOD), peroxidase (POD), and PVI[Fe(CN)5] were crosslinked with poly(ethylene glycol) diglycidyl ether (PEGDGE) on a glassy carbon (GC) electrode for a creatinine biosensor fabrication. Reduction current was monitored at -0.1V in the presence of creatinine and O2. It is revealed that PVI[Fe(CN)5] is suitable as a mediator for a bioelectrocatalytic reaction of POD, since PVI[Fe(CN)5] neither reacts with reactants nor works as an electron acceptor of SOD. The amounts of PVI[Fe(CN)5], PEGDGE, and enzymes were optimized toward creatinine detection. Nafion as a protecting film successfully prevented the enzyme layer from interferences. The detection limit and linear range in creatinine determination were 12μM and 12-500μM (R(2)=0.993), respectively, and the sensitivity was 11mAcm(-2)M(-1), which is applicable for urine creatinine tests. The results of the creatinine determination for four urine samples measured with this proposed method were compared with Jaffe method, and a good correlation was obtained between the results. Copyright © 2013 Elsevier B.V. All rights reserved.

MAC-sparing effect of nitrous oxide in sevoflurane anesthetized sheep and its reversal with systemic atipamezole administration

PubMed Central

Scanu, Antonio; Melosu, Valentino; Careddu, Giovanni Mario; Sotgiu, Giovanni

2018-01-01

Introduction Nitrous oxide (N2O) is an anesthetic gas with antinociceptive properties and reduces the minimum alveolar concentration (MAC) for volatile anesthetic agents, potentially through mechanisms involving central alpha2-adrenoceptors. We hypothesized that 70% N2O in the inspired gas will significantly reduce the MAC of sevoflurane (MACSEVO) in sheep, and that this effect can be reversed by systemic atipamezole. Materials and methods Animals were initially anesthetized with SEVO in oxygen (O2) and exposed to an electrical current as supramaximal noxious stimulus in order to determine MACSEVO (in duplicates). Thereafter, 70% N2O was added to the inspired gas and the MAC re-determined in the presence of N2O (MACSN). A subgroup of sheep were anesthetized a second time with SEVO/N2O for re-determination of MACSN, after which atipamezole (0.2 mg kg-1, IV) was administered for MACSNA determinations. Sheep were anesthetized a third time, initially with only SEVO/O2 to re-determine MACSEVO, after which atipamezole (0.2 mg kg-1, IV) was administered for determination of MACSA. Results MACSEVO was 2.7 (0.3)% [mean (standard deviation)]. Addition of N2O resulted in a 37% reduction of MACSEVO to MACSN of 1.7 (0.2)% (p <0.0001). Atipamezole reversed this effect, producing a MACSNA of 3.1 (0.7)%, which did not differ from MACSEVO (p = 0.12). MACSEVO did not differ from MACSA (p = 0.69). Cardiorespiratory variables were not different among experimental groups except a lower ETCO2 in animals exposed to SEVO/N2O. Conclusions N2O produces significant MACSEVO-reduction in sheep; this effect is completely reversed by IV atipamezole confirming the involvement of alpha2-adrenoreceptors in the MAC-sparing action of N2O. PMID:29315308

Efficient solar-assisted O2 reduction by a cofacial iron porphyrin dimer integrated to a p-CuBi2O4 photocathode prepared by a simple novel method.

PubMed

Zahran, Zaki N; Mohamed, Eman A; Naruta, Yoshinori; Haleem, Ashraf

2017-10-04

A cofacial iron porphyrin hetero-dimer, Fe2TPFPP-TMP showed high electro-catalytic activity, selectivity, and stability for the O2 reduction to H2O both in homogeneous non-aqueous and heterogeneous neutral aqueous solutions. Moreover, when it is integrated to FTO/p-CuBi2O4 (FTO = fluorine doped tin oxide) photocathode prepared by a simple novel method, a remarkable efficient solar-assisted O2 reduction is achieved in neutral potassium phosphate (KPi) or basic NaOH solutions saturated with O2. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Proton-coupled electron-transfer reduction of dioxygen catalyzed by a saddle-distorted cobalt phthalocyanine.

PubMed

Honda, Tatsuhiko; Kojima, Takahiko; Fukuzumi, Shunichi

2012-03-07

Proton-coupled electron-transfer reduction of dioxygen (O(2)) to afford hydrogen peroxide (H(2)O(2)) was investigated by using ferrocene derivatives as reductants and saddle-distorted (α-octaphenylphthalocyaninato)cobalt(II) (Co(II)(Ph(8)Pc)) as a catalyst under acidic conditions. The selective two-electron reduction of O(2) by dimethylferrocene (Me(2)Fc) and decamethylferrocene (Me(10)Fc) occurs to yield H(2)O(2) and the corresponding ferrocenium ions (Me(2)Fc(+) and Me(10)Fc(+), respectively). Mechanisms of the catalytic reduction of O(2) are discussed on the basis of detailed kinetics studies on the overall catalytic reactions as well as on each redox reaction in the catalytic cycle. The active species to react with O(2) in the catalytic reaction is switched from Co(II)(Ph(8)Pc) to protonated Co(I)(Ph(8)PcH), depending on the reducing ability of ferrocene derivatives employed. The protonation of Co(II)(Ph(8)Pc) inhibits the direct reduction of O(2); however, the proton-coupled electron transfer from Me(10)Fc to Co(II)(Ph(8)Pc) and the protonated [Co(II)(Ph(8)PcH)](+) occurs to produce Co(I)(Ph(8)PcH) and [Co(I)(Ph(8)PcH(2))](+), respectively, which react immediately with O(2). The rate-determining step is a proton-coupled electron-transfer reduction of O(2) by Co(II)(Ph(8)Pc) in the Co(II)(Ph(8)Pc)-catalyzed cycle with Me(2)Fc, whereas it is changed to the electron-transfer reduction of [Co(II)(Ph(8)PcH)](+) by Me(10)Fc in the Co(I)(Ph(8)PcH)-catalyzed cycle with Me(10)Fc. A single crystal of monoprotonated [Co(III)(Ph(8)Pc)](+), [Co(III)Cl(2)(Ph(8)PcH)], produced by the proton-coupled electron-transfer reduction of O(2) by Co(II)(Ph(8)Pc) with HCl, was obtained, and the crystal structure was determined in comparison with that of Co(II)(Ph(8)Pc). © 2012 American Chemical Society

Change of Cu+ species and synergistic effect of copper and cerium during reduction-oxidation treatment for preferential CO oxidation

NASA Astrophysics Data System (ADS)

Zhang, Hao; Zhao, Xiaozhou; Wang, Shuang; Zeng, Shanghong; Su, Haiquan

2018-05-01

The CuO-CeO2@SiO2 catalyst with flower-sphere morphology was prepared by the impregnation method and then experienced the reduction-oxidation treatment at different temperatures. The multi-technique characterization shows that the reduction-oxidation treatment can remodel CuO, improve textural and surface properties and change Cu+ content and synergistic effect of copper and cerium. The importance of this work lies in the fact that the decrease of Cu+ content and synergistic effect of copper and cerium that occurs in the reduction-oxidation process results in the decrease of catalytic activity over the CuO-CeO2@SiO2 catalyst for preferential CO oxidation. The process of reaction in rich-hydrogen streams is equivalent to a reduction procedure which decreases Cu+ content and synergistic effect of copper and cerium.

Carbon-doped boron nitride nanosheet as a promising catalyst for N2O reduction by CO or SO2 molecule: A comparative DFT study

NASA Astrophysics Data System (ADS)

Esrafili, Mehdi D.; Saeidi, Nasibeh

2018-06-01

We report for the first time, the catalytic activity of the experimentally available carbon-doped boron nitride nanosheet (C-BNNS) towards the reduction of N2O in the presence of CO or SO2 molecule. According to our density functional theory calculations, C-doping can introduce high spin density into BN monolayer which is mainly localized over the C and its neighboring N atoms. The Hirshfeld charge density analysis reveals that the electron-rich C-BNNS acts as an electron donating support to activate N2O molecule which is an important step in the reduction of N2O. The N2O reduction reaction starts with the dissociative adsorption of N2O over the C-BNNS surface, yielding the N2 molecule and an activated oxygen moiety (Oads) adsorbed over the C atom. The reaction then proceeds via the elimination of Oads by a CO or SO2 molecule. The obtained low activation energies clearly indicate that the metal-free C-BNNS surface can be regarded as a highly active catalyst for the reduction of N2O. The results of this study may open new avenues in searching low cost and highly active BN-based catalysts for low temperature reduction of N2O.

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

PubMed Central

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

Electrodeposition mechanism of quaternary compounds Cu2ZnSnS4: Effect of the additives

NASA Astrophysics Data System (ADS)

Tang, Aiyue; Li, Zhilin; Wang, Feng; Dou, Meiling; Liu, Jingjun; Ji, Jing; Song, Ye

2018-01-01

The electrodeposition mechanism of pure phase Cu2ZnSnS4 (CZTS) thin film with subsequent annealing was investigated in detail. An electrolyte design principle of quaternary compounds was proposed. The complex ions of Cu(H2C6H5O7)+, Cu2(C6H5O7)+, Zn(C4H5O6)+, Sn(H2C6H5O7)+ and Sn2(C6H5O7)+, which influenced the reduction process and played important roles in co-deposition, were identified by UV spectra. Electrochemical studies indicated that trisodium citrate and tartaric acid could narrow the co-deposition potential range of the four elements to -0.8 V to -1.2 V (vs. SCE). The cause was the synergetic effect that trisodium citrate inhibited the reduction of Cu2+ and Sn2+ and tartaric acid promoted the reduction of Zn2+. The reduction of S2O32- was mainly attributed to the induction effect of the metallic ions, and the H+ dissociated from tartaric acid could also promote the cathode process of S2O32-. The reaction mechanism could be summarized as the following steps: (I) Cu(H2C6H5O7)+, Cu2(C6H5O7)+ → Cu, Sn(H2C6H5O7)+, Sn2(C6H5O7)+ → Sn, Zn(C4H5O6)+ → Zn; (II) the desorption of (H2C6H5O7)- and (C6H5O7)-, and the reduction of S2O32- induced by metallic ions and H+. The mechanism studies provided a path of electrolyte design for multicomponent compounds.

Supercapacitor electrode of nano-Co3O4 decorated with gold nanoparticles via in-situ reduction method

NASA Astrophysics Data System (ADS)

Tan, Yongtao; Liu, Ying; Kong, Lingbin; Kang, Long; Ran, Fen

2017-09-01

Nano-Co3O4 decorated with gold nanoparticles is synthesized by a simple method of in-situ reduction of HAuCl4 by sodium citrate for energy storage application, and the effect of gold content in the product on electrochemical performance is investigated in detail. Introducing gold nanoparticles into nano-Co3O4 bulk would contribute to reduce internal resistance of charge transmission. The results show that after in-situ reduction reaction gold nanoparticles imbed uniformly into nano-Co3O4 with irregular nanoparticles. The gold nanoparticles decorated nano-Co3O4 exhibits specific capacitance of 681 F g-1 higher than that of pristine Co3O4 of 368 F g-1. It is interesting that a good cycle life with the specific capacitance retention of 83.1% is obtained after 13000 cycles at 5 A g-1, which recovers to initial specific capacitance value when the test current density is turned to 2 A g-1. In addition, the device of asymmetric supercapacitor, assembled with gold nanoparticles decorated nano-Co3O4 as the positive electrode and activated carbon as the negative electrode, exhibits good energy density of 25 Wh kg-1, which is comparable to the asymmetric device assembled with normal nano-Co3O4, or the symmetric device assembled just with activated carbon.

Characterization of the insulator barrier and the superconducting transition temperature in GdBa{sub 2}Cu{sub 3}O{sub 7−δ}/BaTiO{sub 3} bilayers for application in tunnel junctions

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

Navarro, H., E-mail: henrynavarro@cab.cnea.gov.ar; Sirena, M.; Haberkorn, N.

2015-07-28

The optimization of the superconducting properties in a bottom electrode and the quality of an insulator barrier are the first steps in the development of superconductor/insulator/superconductor tunnel junctions. Here, we study the quality of a BaTiO{sub 3} tunnel barrier deposited on a 16 nm thick GdBa{sub 2}Cu{sub 3}O{sub 7−δ} thin film by using conductive atomic force microscopy. We find that the tunnel current is systematically reduced (for equal applied voltage) by increasing the BaTiO{sub 3} barrier thickness between 1.6 and 4 nm. The BaTiO{sub 3} layers present an energy barrier of ≈1.2 eV and an attenuation length of 0.35–0.5 nm (depending on the appliedmore » voltage). The GdBa{sub 2}Cu{sub 3}O{sub 7−δ} electrode is totally covered by a BaTiO{sub 3} thickness above 3 nm. The presence of ferroelectricity was verified by piezoresponse force microscopy for a 4 nm thick BaTiO{sub 3} top layer. The superconducting transition temperature of the bilayers is systematically suppressed by increasing the BaTiO{sub 3} thickness. This fact can be associated with stress at the interface and a reduction of the orthorhombicity of the GdBa{sub 2}Cu{sub 3}O{sub 7−δ}. The reduction in the orthorhombicity is expected by considering the interface mismatch and it can also be affected by reduced oxygen stoichiometry (poor oxygen diffusion across the BaTiO{sub 3} barrier)« less

Three-dimensional graphene networks as a new substrate for immobilization of laccase and dopamine and its application in glucose/O2 biofuel cell.

PubMed

Zhang, Yijia; Chu, Mi; Yang, Lu; Tan, Yueming; Deng, Wenfang; Ma, Ming; Su, Xiaoli; Xie, Qingji

2014-08-13

We report here three-dimensional graphene networks (3D-GNs) as a novel substrate for the immobilization of laccase (Lac) and dopamine (DA) and its application in glucose/O2 biofuel cell. 3D-GNs were synthesized with an Ni(2+)-exchange/KOH activation combination method using a 732-type sulfonic acid ion-exchange resin as the carbon precursor. The 3D-GNs exhibited an interconnected network structure and a high specific surface area. DA was noncovalently functionalized on the surface of 3D-GNs with 3,4,9,10-perylene tetracarboxylic acid (PTCA) as a bridge and used as a novel immobilized mediating system for Lac-based bioelectrocatalytic reduction of oxygen. The 3D-GNs-PTCA-DA nanocomposite modified glassy carbon electrode (GCE) showed stable and well-defined redox current peaks for the catechol/o-quinone redox couple. Due to the mediated electron transfer by the 3D-GNs-PTCA-DA nanocomposite, the Nafion/Lac/3D-GNs-PTCA-DA/GCE exhibited high catalytic activity for oxygen reduction. The 3D-GNs are proven to be a better substrate for Lac and its mediator immobilization than 2D graphene nanosheets (2D-GNs) due to the interconnected network structure and high specific surface area of 3D-GNs. A glucose/O2 fuel cell using Nafion/Lac/3D-GNs-PTCA-DA/GCE as the cathode and Nafion/glucose oxidase/ferrocence/3D-GNs/GCE as the anode can output a maximum power density of 112 μW cm(-2) and a short-circuit current density of 0.96 mA cm(-2). This work may be helpful for exploiting the popular 3D-GNs as an efficient electrode material for many other biotechnology applications.

Synthesis and characterization of different MnO2 morphologies for lithium-air batteries

NASA Astrophysics Data System (ADS)

Choi, Hyun-A.; Jang, Hyuk; Hwang, Hyein; Choi, Mincheol; Lim, Dongwook; Shim, Sang Eun; Baeck, Sung-Hyeon

2014-09-01

Manganese dioxide (MnO2) was synthesized in the forms of nanorods, nanoparticles, and mesoporous structures and the characteristics of these materials were investigated. Crystallinities were studied by x-ray diffraction and morphologies by scanning and transmission electron microscopy. Average pore sizes and specific surface areas were analyzed using the Barret-Joyner-Halenda and Brunauer-Emmett-Teller methods, respectively. Samples were also studied by cyclic voltammetry using 1M aqueous KOH solution saturated with either O2 or N2 as electrolytes to investigate their ORR (oxygen reduction reaction) and OER (oxygen evolution reaction) activities. Of the samples produced, mesoporous MnO2 exhibited the highest ORR and OER catalytic activities. Mesoporous MnO2 supported on a gas diffusion layer was also used as a catalyst on the air electrode (cathode) of a lithium-air battery in organic electrolyte. The charge-discharge behavior of mesoporous MnO2 was investigated at a current density 0.2 mAcm-2 in a pure oxygen environment. Mesoporous MnO2 electrodes showed stable cycleability up to 65 cycles at a cell capacity of 700 mAhg-1.

Heterojunctions of silver-iron oxide on graphene for laser-coupled oxygen reduction reactions.

PubMed

Chen, Wei-Quan; Chung, Min-Chuan; Valinton, Joey Andrew A; Penaloza, David P; Chuang, Shiow-Huey; Chen, Chun-Hu

2018-05-30

We report a two-step hybridization of N-doped graphene and Ag-decorated Fe2O3 hematite to realize a balanced oxygen adsorption/desorption equilibrium and a laser-coupled ORR (LORR). The stable plateau currents with n values of 3.9 in a wide potential range (0.2-0.7 V) and 7.5% peroxide inhibition of the LORR are found to be directly associated with the Ag/Fe2O3 heterojunction, where interactions of semiconductor band gap excitation and plasmonic resonance-induced hot electrons are proposed to occur.

Advances in Photocatalytic CO₂ Reduction with Water: A Review.

PubMed

Nahar, Samsun; Zain, M F M; Kadhum, Abdul Amir H; Hasan, Hassimi Abu; Hasan, Md Riad

2017-06-08

In recent years, the increasing level of CO₂ in the atmosphere has not only contributed to global warming but has also triggered considerable interest in photocatalytic reduction of CO₂. The reduction of CO₂ with H₂O using sunlight is an innovative way to solve the current growing environmental challenges. This paper reviews the basic principles of photocatalysis and photocatalytic CO₂ reduction, discusses the measures of the photocatalytic efficiency and summarizes current advances in the exploration of this technology using different types of semiconductor photocatalysts, such as TiO₂ and modified TiO₂, layered-perovskite Ag/ALa₄Ti₄O 15 (A = Ca, Ba, Sr), ferroelectric LiNbO₃, and plasmonic photocatalysts. Visible light harvesting, novel plasmonic photocatalysts offer potential solutions for some of the main drawbacks in this reduction process. Effective plasmonic photocatalysts that have shown reduction activities towards CO₂ with H₂O are highlighted here. Although this technology is still at an embryonic stage, further studies with standard theoretical and comprehensive format are suggested to develop photocatalysts with high production rates and selectivity. Based on the collected results, the immense prospects and opportunities that exist in this technique are also reviewed here.

Thermogravimetric and Magnetic Studies of the Oxidation and Reduction Reaction of SmCoO3 to Nanostructured Sm2O3 and Co

NASA Astrophysics Data System (ADS)

Kelly, Brian; Cichocki, Ronald; Poirier, Gerald; Unruh, Karl

The SmCoO3 to nanostructured Sm2O3 and Co oxidation and reduction reaction has been studied by thermogravimetric analysis (TGA) measurements in forming gas (FG) and inert N2 atmospheres, x-ray diffraction (XRD) and vibrating sample magnetometry (VSM). The TGA measurements showed two clearly resolvable reduction processes when heating in FG, from the initial SmCoO3 phase through an intermediate nanostructured mixture of Sm2O3 and CoO when heated to 330°C for several minutes, and then the conversion of CoO to metallic Co when heated above 500°C. These phases were confirmed by XRD and VSM. Similar measurements in N2 yielded little mass change below 900°C and coupled reduction processes at higher temperatures. Isoconversional measurements of the CoO to Co reduction reaction in FG yielded activation energies above 2eV/atom in the nanostructured system. This value is several times larger than those reported in the literature or obtained by similar measurements of bulk mixtures of Sm2O3 and CoO, suggesting the nanostructuring was the source of the large increase in activation energy.

Influence of an Inorganic Interlayer on Exciton Separation in Hybrid Solar Cells

PubMed Central

2015-01-01

It has been shown that in hybrid polymer–inorganic photovoltaic devices not all the photogenerated excitons dissociate at the interface immediately, but can instead exist temporarily as bound charge pairs (BCPs). Many of these BCPs do not contribute to the photocurrent, as their long lifetime as a bound species promotes various charge carrier recombination channels. Fast and efficient dissociation of BCPs is therefore considered a key challenge in improving the performance of polymer–inorganic cells. Here we investigate the influence of an inorganic energy cascading Nb2O5 interlayer on the charge carrier recombination channels in poly(3-hexylthiophene-2,5-diyl) (P3HT)–TiO2 and PbSe colloidal quantum dot–TiO2 photovoltaic devices. We demonstrate that the additional Nb2O5 film leads to a suppression of BCP formation at the heterojunction of the P3HT cells and also a reduction in the nongeminate recombination mechanisms in both types of cells. Furthermore, we provide evidence that the reduction in nongeminate recombination in the P3HT–TiO2 devices is due in part to the passivation of deep midgap trap states in the TiO2, which prevents trap-assisted Shockley–Read–Hall recombination. Consequently a significant increase in both the open-circuit voltage and the short-circuit current was achieved, in particular for P3HT-based solar cells, where the power conversion efficiency increased by 39%. PMID:26548399

Electrochemistry of free chlorine and monochloramine and its relevance to the presence of Pb in drinking water.

PubMed

Rajasekharan, Vishnu V; Clark, Brandi N; Boonsalee, Sansanee; Switzer, Jay A

2007-06-15

The commonly used disinfectants in drinking water are free chlorine (in the form of HOCl/OCl-) and monochloramine (NH2Cl). While free chlorine reacts with natural organic matter in water to produce chlorinated hydrocarbon byproducts, there is also concern that NH2Cl may react with Pbto produce soluble Pb(II) products--leading to elevated Pb levels in drinking water. In this study, electrochemical methods are used to compare the thermodynamics and kinetics of the reduction of these two disinfectants. The standard reduction potential for NH2Cl/Cl- was estimated to be +1.45 V in acidic media and +0.74 V in alkaline media versus NHE using thermodynamic cycles. The kinetics of electroreduction of the two disinfectants was studied using an Au rotating disk electrode. The exchange current densities estimated from Koutecky-Levich plots were 8.2 x 10(-5) and 4.1 x 10(-5) A/cm2, and by low overpotential experiments were 7.5 +/- 0.3 x 10(-5) and 3.7 +/- 0.4 x 10(-5) A/cm2 for free chlorine and NH2Cl, respectively. The rate constantforthe electrochemical reduction of free chlorine at equilibrium is approximately twice as large as that for the reduction of NH2Cl. Equilibrium potential measurements show that free chlorine will oxidize Pb to PbO2 above pH 1.7, whereas NH2Cl will oxidize Pb to PbO2 only above about pH 9.5, if the total dissolved inorganic carbon (DIC) is 18 ppm. Hence, NH2Cl is not capable of producing a passivating PbO2 layer on Pb, and could lead to elevated levels of dissolved Pb in drinking water.

Analysis of reverse gate leakage mechanism of AlGaN/GaN HEMTs with N2 plasma surface treatment

NASA Astrophysics Data System (ADS)

Liu, Hui; Zhang, Zongjing; Luo, Weijun

2018-06-01

The mechanism of reverse gate leakage current of AlGaN/GaN HEMTs with two different surface treatment methods are studied by using C-V, temperature dependent I-V and theoretical analysis. At the lower reverse bias region (VR >- 3.5 V), the dominant leakage current mechanism of the device with N2 plasma surface treatment is the Poole-Frenkel emission current (PF), and Trap-Assisted Tunneling current (TAT) is the principal leakage current of the device which treated by HCl:H2O solution. At the higher reverse bias region (VR <- 3.5 V), both of the two samples show good agreement with the surface leakage mechanism. The leakage current of the device with N2 plasma surface treatment is one order of magnitude smaller than the device which treated by HCl:H2O solution. This is due to the recovery of Ga-N bond in N2 plasma surface treatment together with the reduction of the shallow traps in post-gate annealing (PGA) process. The measured results agree well with the theoretical calculations and demonstrate N2 plasma surface treatment can reduce the reverse leakage current of the AlGaN/GaN HEMTs.

A ternary Cu2O-Cu-CuO nanocomposite: a catalyst with intriguing activity.

PubMed

Sasmal, Anup Kumar; Dutta, Soumen; Pal, Tarasankar

2016-02-21

In this work, the syntheses of Cu2O as well as Cu(0) nanoparticle catalysts are presented. Copper acetate monohydrate produced two distinctly different catalyst particles with varying concentrations of hydrazine hydrate at room temperature without using any surfactant or support. Then both of them were employed separately for 4-nitrophenol reduction in aqueous solution in the presence of sodium borohydride at room temperature. To our surprise, it was noticed that the catalytic activity of Cu2O was much higher than that of the metal Cu(0) nanoparticles. We have confirmed the reason for the exceptionally high catalytic activity of cuprous oxide nanoparticles over other noble metal nanoparticles for 4-nitrophenol reduction. A plausible mechanism has been reported. The unusual activity of Cu2O nanoparticles in the reduction reaction has been observed because of the in situ generated ternary nanocomposite, Cu2O-Cu-CuO, which rapidly relays electrons and acts as a better catalyst. In this ternary composite, highly active in situ generated Cu(0) is proved to be responsible for the hydride transfer reaction. The mechanism of 4-nitrophenol reduction has been established from supporting TEM studies. To further support our proposition, we have prepared a compositionally similar Cu2O-Cu-CuO nanocomposite using Cu2O and sodium borohydride which however displayed lower rate of reduction than that of the in situ produced ternary nanocomposite. The evolution of isolated Cu(0) nanoparticles for 4-nitrophenol reduction from Cu2O under surfactant-free condition has also been taken into consideration. The synthetic procedures of cuprous oxide as well as its catalytic activity in the reduction of 4-nitrophenol are very convenient, fast, cost-effective, and easily operable in aqueous medium and were followed spectrophotometrically. Additionally, the Cu2O-catalyzed 4-nitrophenol reduction methodology was extended further to the reduction of electronically diverse nitroarenes. This concise catalytic process in aqueous medium at room temperature revealed an unprecedented catalytic performance which would draw attention across the whole research community.

BDD anodic treatment of 6:2 fluorotelomer sulfonate (6:2 FTSA). Evaluation of operating variables and by-product formation.

PubMed

Urtiaga, Ane; Soriano, Alvaro; Carrillo-Abad, Jordi

2018-06-01

The concerns about the undesired impacts on human health and the environment of long chain perfluorinated alkyl substances (PFASs) have driven industrial initiatives to replace PFASs by shorter chain fluorinated homologues. 6:2 fluorotelomer sulfonic acid (6:2 FTSA) is applied as alternative to PFOS in metal plating and fluoropolymer manufacture. This study reports the electrochemical treatment of aqueous 6:2 FTSA solutions on microcrystalline BDD anodes. Bench scale batch experiments were performed, focused on assessing the effect of the electrolyte and the applied current density (5-600 A m -2 ) on the removal of 6:2 FTSA, the reduction of total organic carbon (TOC) and the fluoride release. Results showed that at the low range of applied current density (J = 50 A m -2 ), using NaCl, Na 2 SO 4 and NaClO 4 , the electrolyte exerted a minimal effect on removal rates. The formation of toxic inorganic chlorine species such as ClO 4 - was not observed. When using Na 2 SO 4 electrolyte, increasing the applied current density to 350-600 A m -2 promoted a notable enhancement of the 6:2 FTSA removal and defluorination rates, pointing to the positive contribution of electrogenerated secondary oxidants to the overall removal rate. 6:2 FTSA was transformed into shorter-chain PFCAs, and eventually into CO 2 and fluoride, as TOC reduction was >90%. Finally, it was demonstrated that diffusion in the liquid phase was controlling the overall kinetic rate, although with moderate improvements due to secondary oxidants at very high current densities. Copyright © 2018 Elsevier Ltd. All rights reserved.

Prevention of Hypoxemia During Apnea Testing: A Comparison of Oxygen Insufflation And Continuous Positive Airway Pressure.

PubMed

Kramer, Andreas H; Couillard, Philippe; Bader, Ryan; Dhillon, Peter; Kutsogiannis, Demetrios J; Doig, Christopher J

2017-08-01

Apnea testing is an essential step in the clinical diagnosis of brain death. Current international guidelines recommend placement of an oxygen (O 2 ) insufflation catheter into the endotracheal tube to prevent hypoxemia, but use of a continuous positive airway pressure (CPAP) valve may be more effective at limiting arterial partial pressure of O 2 (PO 2 ) reduction. We performed a multicenter study assessing consecutive apnea tests in 14 intensive care units (ICUs) in two cities utilizing differing protocols. In one city, O 2 catheters are placed and arterial blood gases (ABGs) performed at intervals determined by the attending physician. In the other city, a resuscitation bag with CPAP valve is attached to the endotracheal tube, and ABGs performed every 3-5 min. We assessed arterial PO 2 , partial pressure of carbon dioxide (PCO 2 ), pH, and blood pressure at the beginning and termination of each apnea test. Thirty-six apnea tests were performed using an O 2 catheter and 50 with a CPAP valve. One test per group was aborted because of physiological instability. There were no significant differences in the degree of PO 2 reduction (-59 vs. -32 mmHg, p = 0.72), rate of PCO 2 rise (3.2 vs. 3.9 mmHg per min, p = 0.22), or pH decline (-0.02 vs. -0.03 per min, p = 0.06). Performance of ABGs at regular intervals was associated with shorter test duration (10 vs. 7 min, p < 0.0001), smaller PCO 2 rise (30 vs. 26 mmHg, p = 0.0007), and less pH reduction (-0.20 vs. -0.17, p = 0.0012). Lower pH at completion of the apnea test was associated with greater blood pressure decline (p = 0.006). Both methods of O 2 supplementation are associated with similar changes in arterial PO 2 and PCO 2 . Performance of ABGs at regular intervals shortens apnea test duration and may avoid excessive pH reduction and consequent hemodynamic effects.

Cooperative Electrocatalytic O 2 Reduction Involving Co(salophen) with p- Hydroquinone as an Electron–Proton Transfer Mediator

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

Anson, Colin W.; Stahl, Shannon S.

2017-12-01

The molecular cobalt complex, Co(salophen), and para-hydroquinone (H2Q) serve as effective cocatalysts for the electrochemical reduction of O2 to water. Mechanistic studies reveal redox cooperativity between Co(salophen) and H2Q. H2Q serves as an electron-proton transfer mediator (EPTM) that enables electrochemical O2 reduction at higher potentials and with faster rates than is observed with Co(salophen) alone. Replacement of H2Q with the higher potential EPTM, 2-chloro-H2Q, allows for faster O2 reduction rates at higher applied potential. These results demonstrate a unique strategy to achieve improved performance with molecular electrocatalyst systems.

Investigation of interface property in Al/SiO2/ n-SiC structure with thin gate oxide by illumination

NASA Astrophysics Data System (ADS)

Chang, P. K.; Hwu, J. G.

2017-04-01

The reverse tunneling current of Al/SiO2/ n-SiC structure employing thin gate oxide is introduced to examine the interface property by illumination. The gate current at negative bias decreases under blue LED illumination, yet increases under UV lamp illumination. Light-induced electrons captured by interface states may be emitted after the light sources are off, leading to the recovery of gate currents. Based on transient characteristics of gate current, the extracted trap level is close to the light energy for blue LED, indicating that electron capture induced by lighting may result in the reduction of gate current. Furthermore, bidirectional C- V measurements exhibit a positive voltage shift caused by electron trapping under blue LED illumination, while a negative voltage shift is observed under UV lamp illumination. Distinct trapping and detrapping behaviors can be observed from variations in I- V and C- V curves utilizing different light sources for 4H-SiC MOS capacitors with thin insulators.

GaAs metal-oxide-semiconductor based non-volatile flash memory devices with InAs quantum dots as charge storage nodes

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

Islam, Sk Masiul, E-mail: masiulelt@gmail.com; Chowdhury, Sisir; Sarkar, Krishnendu

2015-06-24

Ultra-thin InP passivated GaAs metal-oxide-semiconductor based non-volatile flash memory devices were fabricated using InAs quantum dots (QDs) as charge storing elements by metal organic chemical vapor deposition technique to study the efficacy of the QDs as charge storage elements. The grown QDs were embedded between two high-k dielectric such as HfO{sub 2} and ZrO{sub 2}, which were used for tunneling and control oxide layers, respectively. The size and density of the QDs were found to be 5 nm and 1.8×10{sup 11} cm{sup −2}, respectively. The device with a structure Metal/ZrO{sub 2}/InAs QDs/HfO{sub 2}/GaAs/Metal shows maximum memory window equivalent to 6.87 V. Themore » device also exhibits low leakage current density of the order of 10{sup −6} A/cm{sup 2} and reasonably good charge retention characteristics. The low value of leakage current in the fabricated memory device is attributed to the Coulomb blockade effect influenced by quantum confinement as well as reduction of interface trap states by ultra-thin InP passivation on GaAs prior to HfO{sub 2} deposition.« less

Smart Solution Chemistry to Sn-Containing Intermetallic Compounds through a Self-Disproportionation Process.

PubMed

Zhang, Yuelan; Li, Liping; Li, Qi; Fan, Jianming; Zheng, Jing; Li, Guangshe

2016-09-26

Developing new methods to synthesize intermetallics is one of the most critical issues for the discovery and application of multifunctional metal materials; however, the synthesis of Sn-containing intermetallics is challenging. In this work, we demonstrated for the first time that a self-disproportionation-induced in situ process produces cavernous Sn-Cu intermetallics (Cu3 Sn and Cu6 Sn5 ). The successful synthesis is realized by introducing inorganic metal salts (SnCl2 ⋅2 H2 O) to NaOH aqueous solution to form an intermediate product of reductant (Na2 SnO2 ) and by employing steam pressures that enhance the reduction ability. Distinct from the traditional in situ reduction, the current reduction process avoided the uncontrolled phase composition and excessive use of organic regents. An insight into the mechanism was revealed for the Sn-Cu case. Moreover, this method could be extended to other Sn-containing materials (Sn-Co, Sn-Ni). All these intermetallics were attempted in the catalytic effect on thermal decompositions of ammonium perchlorate. It is demonstrated that Cu3 Sn showed an outstanding catalytic performance. The superior property might be primarily originated from the intrinsic chemical compositions and cavernous morphology as well. We supposed that this smart solution reduction methodology reported here would provide a new recognition for the reduction reaction, and its modified strategy may be applied to the synthesis of other metals, intermetallics as well as some unknown materials. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Evaluation of current techniques for isolation of chars as natural adsorbents

USGS Publications Warehouse

Chun, Y.; Sheng, G.; Chiou, C.T.

2004-01-01

Chars in soils or sediments may potentially influence the soil/sediment sorption behavior. Current techniques for the isolation of black carbon including chars rely often on acid demineralization, base extraction, and chemical oxidation to remove salts and minerals, humic acid, and refractory kerogen, respectively. Little is known about the potential effects of these chemical processes on the char surface and adsorptive properties. This study examined the effects of acid demineralization, base extraction, and acidic Cr2O72- oxidation on the surface areas, surface acidity, and benzene adsorption characteristics of laboratory-produced pinewood and wheat-residue chars, pure or mixed with soils, and a commercial activated carbon. Demineralization resulted in a small reduction in the char surface area, whereas base extraction showed no obvious effect. Neither demineralization nor base extraction caused an appreciable variation in benzene adsorption and presumably the char surface properties. By contrast, the Cr2O 72- oxidation caused a >31% reduction in char surface area. The Boehm titration, supplemented by FTIR spectra, indicated that the surface acidity of oxidized chars increased by a factor between 2.3 and 12 compared to nonoxidized chars. Benzene adsorption with the oxidized chars was lower than that with the non-oxidized chars by a factor of >8.9; both the decrease in char surface area and the increase in char surface acidity contributed to the reduction in char adsorptive power. Although the Cr 2O72- oxidation effectively removes resistant kerogen, it is not well suited for the isolation of chars as contaminant adsorbents because of its destructive nature. Alternative nondestructive techniques that preserve the char surface properties and effectively remove kerogen must be sought.

Electrochemical Reduction of Dissolved Oxygen in Alkaline, Solid Polymer Electrolyte Films.

PubMed

Novitski, David; Kosakian, Aslan; Weissbach, Thomas; Secanell, Marc; Holdcroft, Steven

2016-11-30

Mass transport of oxygen through an ionomer contained within the cathode catalyst layer in an anion exchange membrane fuel cell is critical for a functioning fuel cell, yet is relatively unexplored. Moreover, because water is a reactant in the oxygen reduction reaction (ORR) in alkaline media, an adequate supply of water is required. In this work, ORR mass transport behavior is reported for methylated hexamethyl-p-terphenyl polymethylbenzimidazoles (HMT-PMBI), charge balanced by hydroxide ions (IEC from 2.1 to 2.5 mequiv/g), and commercial Fumatec FAA-3 membranes. Electrochemical mass transport parameters are determined by potential step chronoamperometry using a Pt microdisk solid-state electrochemical cell, in air at 60 °C, with relative humidity controlled between 70% and 98%. The oxygen diffusion coefficient (D bO2 ), oxygen concentration (c bO2 ), and oxygen permeability (D bO2 ·c bO2 ) were obtained by nonlinear curve fitting of the current transients using the Shoup-Szabo equation. Mass transport parameters are correlated to water content of the ionomer membrane. It is found that the oxygen diffusion coefficients decreased by 2 orders of magnitude upon reducing the water content of the ionomer membrane by lowering the relative humidity. The limitation of the Shoup-Szabo equation for extracting ORR mass transport parameters using thin ionomer films was evaluated by numerical modeling of the current transients, which revealed that a significant discrepancy (up to 29% under present conditions) was evident for highly hydrated membranes for which the oxygen diffusion coefficient was largest, and in which the oxygen depletion region reached the ionomer/gas interface during the chronoamperometric analysis.

A full understanding of oxygen reduction reaction mechanism on Au(1 1 1) surface

NASA Astrophysics Data System (ADS)

Yang, Yang; Dai, Changqing; Fisher, Adrian; Shen, Yanchun; Cheng, Daojian

2017-09-01

Oxygen reduction and hydrogen peroxide reduction are technologically important reactions in energy-conversion devices. In this work, a full understanding of oxygen reduction reaction (ORR) mechanism on Au(1 1 1) surface is investigated by density functional theory (DFT) calculations, including the reaction mechanisms of O2 dissociation, OOH dissociation, and H2O2 dissociation. Among these ORR mechanisms on Au(1 1 1), the activation energy of \\text{O}2* hydrogenation reaction is much lower than that of \\text{O}2* dissociation, indicating that \\text{O}2* hydrogenation reaction is more appropriate at the first step than \\text{O}2* dissociation. In the following, H2O2 can be formed with the lower activation energy compared with the OOH dissociation reaction, and finally H2O2 could be generated as a detectable product due to the high activation energy of H2O2 dissociation reaction. Furthermore, the potential dependent free energy study suggests that the H2O2 formation is thermodynamically favorable up to 0.4 V on Au(1 1 1), reducing the overpotential for 2e - ORR process. And the elementary step of first H2O formation becomes non-spontaneous at 0.4 V, indicating the difficulty of 4e - reduction pathway. Our DFT calculations show that H2O2 can be generated on Au(1 1 1) and the first electron transfer is the rate determining step. Our results show that gold surface could be used as a good catalyst for small-scale manufacture and on-site production of H2O2.

Aerobic sulfate reduction in microbial mats

NASA Technical Reports Server (NTRS)

Canfield, Donald E.; Des Marais, David J.

1991-01-01

Measurements of bacterial sulfate reduction and dissolved oxygen (O2) in hypersaline bacterial mats from Baja California, Mexico, revealed that sulfate reduction occurred consistently within the well-oxygenated photosynthetic zone of the mats. This evidence that dissimilatory sulfate reduction can occur in the presence of O2 challenges the conventional view that sulfate reduction is a strictly anaerobic process. At constant temperature, the rates of sulfate reduction in oxygenated mats during daytime were similar to rates in anoxic mats at night: thus, during a 24-hour cycle, variations in light and O2 have little effect on rates of sulfate reduction in these mats.

Synthesis and characterization of metal nanoparticles templated chitosan-SiO2 catalyst for the reduction of nitrophenols and dyes.

PubMed

Ali, Fayaz; Khan, Sher Bahadar; Kamal, Tahseen; Alamry, Khalid A; Bakhsh, Esraa M; Asiri, Abdullah M; Sobahi, Tariq R A

2018-07-15

Different metal nanoparticles (MNPs) templated on chitosan-silica (CH-SiO 2 ) nanocomposite fiber were prepared via simple and fast method of the metal ions uptake by fiber and their subseqent reduction using strong reducing agent. The performance difference of CH-SiO 2 templated with Cu, Co, Ag and Ni nanoparticles for both reduction of 4-nitroaniline (4-NA) and decolorization of congo red (CR) was investigated. The Cu nanoparticles loaded CH-SiO 2 (Cu/CH-SiO 2 ), showed high catalytic efficiencies in the reduction of 4-NA and CR, as compared to other loaded MNP fibers. The apparent rate constants of 6.17 × 10 -3  s -1 and 1.68 × 10 -2  s -1 and turnover frequencies (TOF) of 4.693 h -1 and 3.965 h -1 were observed for the reduction of 4-NA and CR, respectively. In addition, the catalytic activity of Cu/CH-SiO 2 catalyst was also examined and found efficient in the reduction of nitrophenols (2-NP, 3-NP and 4-NP), and other dyes. Thus, Cu/CH-SiO 2 with excellent catalytic activity can also be employed for other applications. Copyright © 2018 Elsevier Ltd. All rights reserved.

Rocks, when Stressed, turn into a Battery that is Rechargeable

NASA Astrophysics Data System (ADS)

Lau, B. T.; Takeuchi, A. H.; Freund, F. T.

2006-12-01

Igneous rocks, when subjected to deviatory stresses, turn into a battery. We report on gabbro (Shanxi, China). We use steel pistons to load repeatedly ~10 cm3 in the center of 30 x 30 x 0.9 cm3 tiles, from 0 to 60 MPa, 1/3 failure strength, at 0.2 MPa/sec with 20-30 min at constant load. Instantly upon loading, a current begins to flow, increasing to 200-300 pA, equivalent to 30,000 to 50,000 A/km3. Under constant load the current continues to flow for at least 24 hrs with barely 10-20% reduction. During unloading the current stops but resumes during repetitive loading-unloading cycles for at least 22 times. One part of the current is carried by electrons. The electrons flow from the stressed rock into the steel pistons, through the external circuit to the edges of the tile. The other part is carried by holes. The holes flow inside the rock, from the stressed to the unstressed rock and to the edges of the tile. There they meet the electrons, thereby closing the circuit. Both types of charge carriers, electrons and holes, are associated with oxygen anions that changed their valence from 2- to 1- (peroxy). An O- among O2- represents a defect electron in the O2- sublattice, known as positive hole or p-hole for short. In unstressed rocks the O- exist in an electrically inactive form as O- pairs, chemically equivalent to peroxy links, O3X-OO-XO3 with X = Si4+, Al3+ etc. Deviatory stresses cause the peroxy links to break, allowing electrons from neighboring O2- to jump in and p-holes to jump out. The p-holes can spread into and through the unstressed rock using energy levels in the valence band. To observe sustained currents the battery circuit has to close.

Involvement of Caveolin in Low K+-induced Endocytic Degradation of Cell-surface Human Ether-a-go-go-related Gene (hERG) Channels*

PubMed Central

Massaeli, Hamid; Sun, Tao; Li, Xian; Shallow, Heidi; Wu, Jimmy; Xu, Jianmin; Li, Wentao; Hanson, Christian; Guo, Jun; Zhang, Shetuan

2010-01-01

Reduction in the rapidly activating delayed rectifier K+ channel current (IKr) due to either mutations in the human ether-a-go-go-related gene (hERG) or drug block causes inherited or drug-induced long QT syndrome. A reduction in extracellular K+ concentration ([K+]o) exacerbates long QT syndrome. Recently, we demonstrated that lowering [K+]o promotes degradation of IKr in rabbit ventricular myocytes and of the hERG channel stably expressed in HEK 293 cells. In this study, we investigated the degradation pathways of hERG channels under low K+ conditions. We demonstrate that under low K+ conditions, mature hERG channels and caveolin-1 (Cav1) displayed a parallel time-dependent reduction. Mature hERG channels coprecipitated with Cav1 in co-immunoprecipitation analysis, and internalized hERG channels colocalized with Cav1 in immunocytochemistry analysis. Overexpression of Cav1 accelerated internalization of mature hERG channels in 0 mm K+o, whereas knockdown of Cav1 impeded this process. In addition, knockdown of dynamin 2 using siRNA transfection significantly impeded hERG internalization and degradation under low K+o conditions. In cultured neonatal rat ventricular myocytes, knockdown of caveolin-3 significantly impeded low K+o-induced reduction of IKr. Our data indicate that a caveolin-dependent endocytic route is involved in low K+o-induced degradation of mature hERG channels. PMID:20605793

Electron-beam-induced topographical, chemical, and structural patterning of amorphous titanium oxide films.

PubMed

Kern, P; Müller, Y; Patscheider, J; Michler, J

2006-11-30

Electrolytically deposited amorphous TiO2 films on steel are remarkably sensitive to electron beam (e-beam) irradiation at moderate energies at 20 keV, resulting in controlled local oxide reduction and crystallization, opening the possibility for local topographical, chemical, and structural modifications within a biocompatible, amorphous, and semiconducting matrix. The sensitivity is shown to vary significantly with the annealing temperature of as-deposited films. Well-defined irradiation conditions in terms of probe current IP (5 microA) and beam size were achieved with an electron probe microanalyzer. As shown by atomic force and optical microscopy, micro-Raman spectroscopy, wavelength-dispersive X-ray (WDX), and Auger analyses, e-beam exposure below 1 Acm-2 immediately leads to electron-stimulated oxygen desorption, resulting in a well-defined volume loss primarily limited to the irradiated zone under the electron probe and in a blue color shift in this zone because of the presence of Ti2O3. Irradiation at 5 Acm(-2) (IP = 5 microA) results in local crystallization into anatase phase within 1 s of exposure and in reduction to TiO after an extended exposure of 60 s. Further reduction to the metallic state could be observed after 60 s of exposure at approximately 160 Acm(-2). The local reduction could be qualitatively sensed with WDX analysis and Auger line scans. An estimation of the film temperature in the beam center indicates that crystallization occurs at less than 150 degrees C, well below the atmospheric crystallization temperature of the present films. The high e-beam sensitivity in combination with the well-defined volume loss from oxygen desorption allows for precise electron lithographic topographical patterning of the present oxides. Irradiation effects leading to the observed reduction and crystallization phenomena under moderate electron energies are discussed.

Catalase and ascorbate peroxidase-representative H2O2-detoxifying heme enzymes in plants.

PubMed

Anjum, Naser A; Sharma, Pallavi; Gill, Sarvajeet S; Hasanuzzaman, Mirza; Khan, Ekhlaque A; Kachhap, Kiran; Mohamed, Amal A; Thangavel, Palaniswamy; Devi, Gurumayum Devmanjuri; Vasudhevan, Palanisamy; Sofo, Adriano; Khan, Nafees A; Misra, Amarendra Narayan; Lukatkin, Alexander S; Singh, Harminder Pal; Pereira, Eduarda; Tuteja, Narendra

2016-10-01

Plants have to counteract unavoidable stress-caused anomalies such as oxidative stress to sustain their lives and serve heterotrophic organisms including humans. Among major enzymatic antioxidants, catalase (CAT; EC 1.11.1.6) and ascorbate peroxidase (APX; EC 1.11.1.11) are representative heme enzymes meant for metabolizing stress-provoked reactive oxygen species (ROS; such as H2O2) and controlling their potential impacts on cellular metabolism and functions. CAT mainly occurs in peroxisomes and catalyzes the dismutation reaction without requiring any reductant; whereas, APX has a higher affinity for H2O2 and utilizes ascorbate (AsA) as specific electron donor for the reduction of H2O2 into H2O in organelles including chloroplasts, cytosol, mitochondria, and peroxisomes. Literature is extensive on the glutathione-associated H2O2-metabolizing systems in plants. However, discussion is meager or scattered in the literature available on the biochemical and genomic characterization as well as techniques for the assays of CAT and APX and their modulation in plants under abiotic stresses. This paper aims (a) to introduce oxidative stress-causative factors and highlights their relationship with abiotic stresses in plants; (b) to overview structure, occurrence, and significance of CAT and APX in plants; (c) to summarize the principles of current technologies used to assay CAT and APX in plants; (d) to appraise available literature on the modulation of CAT and APX in plants under major abiotic stresses; and finally, (e) to consider a brief cross-talk on the CAT and APX, and this also highlights the aspects unexplored so far.

Influence of V2O5 Content on the Gas-Based Direct Reduction of Hongge Vanadium Titanomagnetite Pellets with Simulated Shaft Furnace Gases

NASA Astrophysics Data System (ADS)

Li, Wei; Fu, Guiqin; Chu, Mansheng; Zhu, Miaoyong

2018-01-01

The influence of V2O5 content on the gas-based direct reduction of Hongge vanadium titanomagnetite pellets (HVTMP) was investigated with simulated shaft furnace gases, and the content levels were selected as 0 wt.%, 2 wt.%, 4 wt.%, and 6 wt.%, respectively. The results indicated that, with the increase of V2O5 content, the reduction was accelerated at an early stage due to the increase of the original porosity of the HVTMP. However, as the reduction proceeded, a slowing down in the reduction rate was observed, which was attributed to the formation of hardly reducible Fe2VO4. Major phases of reduced HVTMP were Fe2VO4, FeTiO3, and metallic iron. The morphology showed that the size of metallic iron particles of reduced HVTMP decreased with the increase of V2O5 content, V-bearing oxides embedded into the Ti-rich phases, and further reduction was restricted. This study not only established a relationship between the V2O5 content of HVTMP and its reduction behavior but could also contribute greatly to the effective utilization of Hongge vanadium titanomagnetite in shaft furnace.

MoO2-ordered mesoporous carbon nanocomposite as an anode material for lithium-ion batteries.

PubMed

Zeng, Lingxing; Zheng, Cheng; Deng, Cuilin; Ding, Xiaokun; Wei, Mingdeng

2013-03-01

In the present work, the nanocomposite of MoO2-ordered mesoporous carbon (MoO2-OMC) was synthesized for the first time using a carbon thermal reduction route and the mesoporous carbon as the nanoreactor. The synthesized nanocomposite was characterized by X-ray diffraction (XRD), thermogravimetric analysis (TGA), N2 adsorption-desorption, scanning electron microscopy (SEM), and transmission electron microscopy (TEM) measurements. Furthermore, this nanocomposite was used as an anode material for Li-ion intercalation and exhibited large reversible capacity, high rate performance, and good cycling stability. For instance, a high reversible capacity of 689 mAh g(-1) can remain after 50 cycles at a current density of 50 mA g(-1). It is worth mentioning that the MoO2-OMC nanocomposite electrode can attain a high reversible capacity of 401 mAh g(-1) at a current density as high as 2 A g(-1). These results might be due to the intrinsic characteristics of nanocomposite, which offered a better accommodation of the strain and volume changes and a shorter path for Li-ion and electron transport, leading to the improved capacity and enhanced rate capability.

Effects of substrate heating and post-deposition annealing on characteristics of thin MOCVD HfO2 films

NASA Astrophysics Data System (ADS)

Gopalan, Sundararaman; Ramesh, Sivaramakrishnan; Dutta, Shibesh; Virajit Garbhapu, Venkata

2018-02-01

It is well known that Hf-based dielectrics have replaced the traditional SiO2 and SiON as gate dielectric materials for conventional CMOS devices. By using thicker high-k materials such as HfO2 rather than ultra-thin SiO2, we can bring down leakage current densities in MOS devices to acceptable levels. HfO2 is also one of the potential candidates as a blocking dielectric for Flash memory applications for the same reason. In this study, effects of substrate heating and oxygen flow rate while depositing HfO2 thin films using CVD and effects of post deposition annealing on the physical and electrical characteristics of HfO2 thin films are presented. It was observed that substrate heating during deposition helps improve the density and electrical characteristics of the films. At higher substrate temperature, Vfb moved closer to zero and also resulted in significant reduction in hysteresis. Higher O2 flow rates may improve capacitance, but also results in slightly higher leakage. The effect of PDA depended on film thickness and O2 PDA improved characteristics only for thick films. For thinner films forming gas anneal resulted in better electrical characteristics.

Towards scalable binderless electrodes: carbon coated silicon nanofiber paper via Mg reduction of electrospun SiO2 nanofibers.

PubMed

Favors, Zachary; Bay, Hamed Hosseini; Mutlu, Zafer; Ahmed, Kazi; Ionescu, Robert; Ye, Rachel; Ozkan, Mihrimah; Ozkan, Cengiz S

2015-02-06

The need for more energy dense and scalable Li-ion battery electrodes has become increasingly pressing with the ushering in of more powerful portable electronics and electric vehicles (EVs) requiring substantially longer range capabilities. Herein, we report on the first synthesis of nano-silicon paper electrodes synthesized via magnesiothermic reduction of electrospun SiO2 nanofiber paper produced by an in situ acid catalyzed polymerization of tetraethyl orthosilicate (TEOS) in-flight. Free-standing carbon-coated Si nanofiber binderless electrodes produce a capacity of 802 mAh g(-1) after 659 cycles with a Coulombic efficiency of 99.9%, which outperforms conventionally used slurry-prepared graphite anodes by over two times on an active material basis. Silicon nanofiber paper anodes offer a completely binder-free and Cu current collector-free approach to electrode fabrication with a silicon weight percent in excess of 80%. The absence of conductive powder additives, metallic current collectors, and polymer binders in addition to the high weight percent silicon all contribute to significantly increasing capacity at the cell level.

Rapid and controllable flame reduction of TiO2 nanowires for enhanced solar water-splitting.

PubMed

Cho, In Sun; Logar, Manca; Lee, Chi Hwan; Cai, Lili; Prinz, Fritz B; Zheng, Xiaolin

2014-01-08

We report a new flame reduction method to generate controllable amount of oxygen vacancies in TiO2 nanowires that leads to nearly three times improvement in the photoelectrochemical (PEC) water-splitting performance. The flame reduction method has unique advantages of a high temperature (>1000 °C), ultrafast heating rate, tunable reduction environment, and open-atmosphere operation, so it enables rapid formation of oxygen vacancies (less than one minute) without damaging the nanowire morphology and crystallinity and is even applicable to various metal oxides. Significantly, we show that flame reduction greatly improves the saturation photocurrent densities of TiO2 nanowires (2.7 times higher), α-Fe2O3 nanowires (9.4 times higher), ZnO nanowires (2.0 times higher), and BiVO4 thin film (4.3 times higher) in comparison to untreated control samples for PEC water-splitting applications.

Promotional effect of surface hydroxyls on electrochemical reduction of CO 2 over SnO x/Sn electrode

DOE PAGES

Cui, Chaonan; Han, Jinyu; Zhu, Xinli; ...

2016-01-16

In this study, tin oxide (SnO x) formation on tin-based electrode surfaces during CO 2 electrochemical reduction can have a significant impact on the activity and selectivity of the reaction. In the present study, density functional theory (DFT) calculations have been performed to understand the role of SnO x in CO 2 reduction using a SnO monolayer on the Sn(112) surface as a model for SnO x. Water molecules have been treated explicitly and considered actively participating in the reaction. The results showed that H 2O dissociates on the perfect SnO monolayer into two hydroxyl groups symmetrically on the surface.more » CO 2 energetically prefers to react with the hydroxyl, forming a bicarbonate (HCO 3(t)*) intermediate, which can then be reduced to either formate (HCOO*) by hydrogenating the carbon atom or carboxyl (COOH*) by protonating the oxygen atom. Both steps involve a simultaneous Csingle bondO bond breaking. Further reduction of HCOO* species leads to the formation of formic acid in the acidic solution at pH < 4, while the COOH* will decompose to CO and H 2O via protonation. Whereas the oxygen vacancy (VO) in the oxide monolayer maybe formed by the reduction, it can be recovered by H 2O dissociation, resulting in two embedded hydroxyl groups. The results show that the hydroxylated surface with two symmetric hydroxyls is energetically more favorable for CO 2 reduction than the hydroxylated VO surface with two embedded hydroxyls. The reduction potential for the former has a limiting-potential of –0.20 V (RHE), lower than that for the latter (–0.74 V (RHE)). Compared to the pure Sn electrode, the formation of SnO x monolayer on the electrode under the operating conditions promotes CO 2 reduction more effectively by forming surface hydroxyls, thereby providing a new channel via COOH* to the CO formation, although formic acid is still the major reduction product.« less

Oxygen reduction reaction on highly-durable Pt/nanographene fuel cell catalyst synthesized employing in-liquid plasma

NASA Astrophysics Data System (ADS)

Amano, Tomoki; Kondo, Hiroki; Takeda, Keigo; Ishikawa, Kenji; Kano, Hiroyuki; Hiramatsu, Mineo; Sekine, Makoto; Hori, Masaru

2016-09-01

We recently have established ultrahigh-speed synthesis method of nanographene materials employing in-liquid plasma, and reported high durability of Pt/nanographene composites as a fuel cell catalyst. Crystallinity and domain size of nanographene materials were essential to their durability. However, their mechanism is not clarified yet. In this study, we investigated the oxygen reduction reaction using three-types of nanographene materials with different crystallinity and domain sizes, which were synthesized using ethanol, 1-propanol and 1-butanol, respectively. According to our previous studies, the nanographene material synthesized using the lower molecular weight alcohol has the higher crystallinity and larger domain size. Pt nanoparticles were supported on the nanographene surfaces by reducing 8 wt% H2PtCl6 diluted with H2O. Oxygen reduction current densities at a potential of 0.2 V vs. RHE were 5.43, 5.19 and 3.69 mA/cm2 for the samples synthesized using ethanol, 1-propanol and 1-butanol, respectively. This means that the higher crystallinity nanographene showed the larger oxygen reduction current density. The controls of crystallinity and domain size of nanographene materials are essential to not only their durability but also highly efficiency as catalyst electrodes.

Terrestrial nitrous oxide cycles and atmospheric effects

NASA Technical Reports Server (NTRS)

Whitten, R. C.; Lawless, J. G.; Banin, A.

1984-01-01

The basic processes that cause N2O emission from soils are briefly discussed, and the rate of the processes is shown to vary widely in space and time, depending on soil, climate, and agrotechnical conditions. Although significant amounts of N2O are indeed emitted from the land, the complexity of the soil processes involved and the wide variation of measured rates still prevents the quantitative evaluation, global budgeting, and reliable prediction of atmospheric N2O. Increased atmospheric N2O abundance increases the levels of odd-nitrogen in the stratosphere, which, in turn, decreases the stratospheric ozone density via a catalytic cycle. Using appropriate atmospheric models and current chemical kinetic data, it has been found that the dependence of ozone reduction on N2O increase is nearly linear; a simulated doubling of N2O leads to a predicted decrease of about 14 percent in total ozone column density. A 10 percent increase in N2O yields a predicted increase in nonmelanoma skin cancer of several percent, and a possible raising of surface temperature of 0.03 K.

Battery Relevant Electrochemistry of Ag 7Fe 3(P 2O 7 ) 4 : Contrasting Contributions from the Redox Chemistries of Ag + and Fe 3+

DOE PAGES

Zhang, Yiman; Kirshenbaum, Kevin C.; Marschilok, Amy C.; ...

2016-10-12

Ag 7Fe 3(P 2O 7 ) 4 is an example of an electrochemical displacement material which contains two different electrochemically active metal cations, where one cation (Ag +) forms metallic silver nanoparticles external to the crystals of Ag 7Fe 3(P 2O 7 ) 4 via an electrochemical reduction displacement reaction, while the other cation (Fe +3) is electrochemically reduced with the retention of iron cations within the anion structural framework concomitant with lithium insertion. These contrasting redox chemistries within one pure cathode material enable high rate capability and reversibility when Ag 7Fe 3(P 2O 7 ) 4 is employed asmore » cathode material in a lithium ion battery (LIB). Further, pyrophosphate materials are thermally and electrically stable, desirable attributes for cathode materials in LIBs. In this article, a bimetallic pyrophosphate material Ag 7Fe 3(P 2O 7 ) 4 is synthesized and confirmed to be a single phase by Rietveld refinement. Electrochemistry of Ag 7Fe 3(P 2O 7 ) 4 is reported for the first time in the context of lithium based batteries using cyclic voltammetry and galvanostatic discharge–charge cycling. The reduction displacement reaction and the lithium (de)insertion processes are investigated using ex situ X-ray absorption spectroscopy and X-ray diffraction of electrochemically reduced and oxidized Ag 7Fe 3(P 2O 7 ) 4. Ag 7Fe 3(P 2O 7 ) 4 exhibits good reversibility at the iron centers indicated by ~80% capacity retention over 100 cycles following the initial formation cycle and excellent rate capability exhibited by ~70% capacity retention upon a 4-fold increase in current.« less

Battery Relevant Electrochemistry of Ag 7Fe 3(P 2O 7 ) 4 : Contrasting Contributions from the Redox Chemistries of Ag + and Fe 3+

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

Zhang, Yiman; Kirshenbaum, Kevin C.; Marschilok, Amy C.

Ag 7Fe 3(P 2O 7 ) 4 is an example of an electrochemical displacement material which contains two different electrochemically active metal cations, where one cation (Ag +) forms metallic silver nanoparticles external to the crystals of Ag 7Fe 3(P 2O 7 ) 4 via an electrochemical reduction displacement reaction, while the other cation (Fe +3) is electrochemically reduced with the retention of iron cations within the anion structural framework concomitant with lithium insertion. These contrasting redox chemistries within one pure cathode material enable high rate capability and reversibility when Ag 7Fe 3(P 2O 7 ) 4 is employed asmore » cathode material in a lithium ion battery (LIB). Further, pyrophosphate materials are thermally and electrically stable, desirable attributes for cathode materials in LIBs. In this article, a bimetallic pyrophosphate material Ag 7Fe 3(P 2O 7 ) 4 is synthesized and confirmed to be a single phase by Rietveld refinement. Electrochemistry of Ag 7Fe 3(P 2O 7 ) 4 is reported for the first time in the context of lithium based batteries using cyclic voltammetry and galvanostatic discharge–charge cycling. The reduction displacement reaction and the lithium (de)insertion processes are investigated using ex situ X-ray absorption spectroscopy and X-ray diffraction of electrochemically reduced and oxidized Ag 7Fe 3(P 2O 7 ) 4. Ag 7Fe 3(P 2O 7 ) 4 exhibits good reversibility at the iron centers indicated by ~80% capacity retention over 100 cycles following the initial formation cycle and excellent rate capability exhibited by ~70% capacity retention upon a 4-fold increase in current.« less

Morphology Control of Carbon-Free Spinel NiCo 2 O 4 Catalysts for Enhanced Bifunctional Oxygen Reduction and Evolution in Alkaline Media

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

Devaguptapu, Surya V.; Hwang, Sooyeon; Karakalos, Stavros

Spinel NiCo 2O 4 is considered a promising precious metal-free catalyst that is also carbon-free for oxygen electrocatalysis. Current efforts mainly focus on optimal chemical doping and substituent to tune its electronic structures for enhanced activity. Here, we study its morphology control and elucidate the morphology-dependent catalyst performance for bifunctional oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Three types of NiCo 2O 4 catalysts with significantly distinct morphologies were prepared using temple-free, Pluronic-123 (P-123) soft, and SiO 2 hard templates, respectively, via hydrothermal methods following by a calcination. While the hard-template yields sphere-like dense structures, soft-template assists themore » formation of a unique nano-needle cluster assembly containing abundant meso- and macro pores. Furthermore, the effect of morphology of NiCo 2O 4 on their corresponding bifunctional catalytic performance was systematically investigated. The flower-like nano-needle assembly NiCo 2O 4 catalyst via the soft template method exhibited the highest catalytic activity and stability for both ORR and OER. In particular, it exhibited an onset and half-wave potentials of 0.94 and 0.82 V vs. RHE, respectively, for the ORR in alkaline media. Although it is still inferior to Pt, the NiCo 2O 4 represents one of the best ORR catalyst compared to other reported carbon-free oxides. Meanwhile, remarkable OER activity and stability were achieved with an onset potential of 1.48 V and a current density of 15 mA/cm 2 at 1.6 V, showing no activity loss after 20,000 potential cycles (0 to 1.9 V). The demonstrated stability is even superior to Ir for the OER. The morphology-controlled approach provides an effective solution to create a robust 3D architecture with increased surface areas and enhanced mass transfer. More importantly, the soft template can yield high degree of spinel crystallinity with ideal stoichiometric ratios between Ni and Co, thus promoting structural integrity with enhanced electrical conductivity and catalytic properties.« less

Morphology Control of Carbon-Free Spinel NiCo 2 O 4 Catalysts for Enhanced Bifunctional Oxygen Reduction and Evolution in Alkaline Media

DOE PAGES

Devaguptapu, Surya V.; Hwang, Sooyeon; Karakalos, Stavros; ...

2017-12-06

Spinel NiCo 2O 4 is considered a promising precious metal-free catalyst that is also carbon-free for oxygen electrocatalysis. Current efforts mainly focus on optimal chemical doping and substituent to tune its electronic structures for enhanced activity. Here, we study its morphology control and elucidate the morphology-dependent catalyst performance for bifunctional oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). Three types of NiCo 2O 4 catalysts with significantly distinct morphologies were prepared using temple-free, Pluronic-123 (P-123) soft, and SiO 2 hard templates, respectively, via hydrothermal methods following by a calcination. While the hard-template yields sphere-like dense structures, soft-template assists themore » formation of a unique nano-needle cluster assembly containing abundant meso- and macro pores. Furthermore, the effect of morphology of NiCo 2O 4 on their corresponding bifunctional catalytic performance was systematically investigated. The flower-like nano-needle assembly NiCo 2O 4 catalyst via the soft template method exhibited the highest catalytic activity and stability for both ORR and OER. In particular, it exhibited an onset and half-wave potentials of 0.94 and 0.82 V vs. RHE, respectively, for the ORR in alkaline media. Although it is still inferior to Pt, the NiCo 2O 4 represents one of the best ORR catalyst compared to other reported carbon-free oxides. Meanwhile, remarkable OER activity and stability were achieved with an onset potential of 1.48 V and a current density of 15 mA/cm 2 at 1.6 V, showing no activity loss after 20,000 potential cycles (0 to 1.9 V). The demonstrated stability is even superior to Ir for the OER. The morphology-controlled approach provides an effective solution to create a robust 3D architecture with increased surface areas and enhanced mass transfer. More importantly, the soft template can yield high degree of spinel crystallinity with ideal stoichiometric ratios between Ni and Co, thus promoting structural integrity with enhanced electrical conductivity and catalytic properties.« less

Interaction between isoprene and ozone fluxes at ecosystem level in a poplar plantation and its impact at European level

NASA Astrophysics Data System (ADS)

Zenone, T.; Hendriks, C.; Brilli, F.; Gioli, B.; Portillo Estrada, M.; Schaap, M.; Ceulemans, R.

2015-12-01

The emissions of Biogenic volatile organic compounds (BVOCs) from vegetation, mainly in form of isoprenoids, play an important role in the tropospheric ozone (O3) formation. The potential large expansion of isoprene emitter species (e.g. poplar) as biofuels feedstock might impact the ground level O3 formation. Here we report the simultaneous observations, using the eddy covariance (EC) technique, of isoprene, O3 and CO2 fluxes in a short rotation coppice (SRC) of poplar. The impact of current poplar plantations and associated isoprene emissions on ground level ozone concentrations for Europe was evaluated using a chemistry transport model (CTM) LOTOS-EUROS. The isoprene fluxes showed a well-defined seasonal and daily cycle that mirrored with the stomata O3 uptake. The isoprene emission and the stomata O3 uptake showed significant statistical relationship especially at elevated temperature. Isoprene was characterized by a remarkable peak of emissions (e.g. 38 nmol m-2s-1) occurring for few days as a consequence of the rapid variation of the air and surface temperature. During these days the photosynthetic apparatus (i.e. the CO2 fluxes) and transpiration rates did not show significant variation while we did observe a variation of the energy exchange and a reduction of the bowen ratio. The response of isoprene emissions to ambient O3 concentration follows the common form of the hormetic dose-response curve with a considerable reduction of the isoprene emissions at [O3] > 80 ppbv indicating a potential damping effect of the O3 levels on isoprene. Under the current condition the impact of SRC plantations on ozone concentrations / formation is very limited in Europe. Our findings indicate that, even with future scenarios with more SRC, or conventional poplar plantations, the impact on Ozone formation is negligible.

Pathways of organic carbon oxidation in three continental margin sediments

NASA Technical Reports Server (NTRS)

Canfield, D. E.; Jorgensen, B. B.; Fossing, H.; Glud, R.; Gundersen, J.; Ramsing, N. B.; Thamdrup, B.; Hansen, J. W.; Nielsen, L. P.; Hall, P. O.

1993-01-01

We have combined several different methodologies to quantify rates of organic carbon mineralization by the various electron acceptors in sediments from the coast of Denmark and Norway. Rates of NH4+ and Sigma CO2 liberation sediment incubations were used with O2 penetration depths to conclude that O2 respiration accounted for only between 3.6-17.4% of the total organic carbon oxidation. Dentrification was limited to a narrow zone just below the depth of O2 penetration, and was not a major carbon oxidation pathway. The processes of Fe reduction, Mn reduction and sulfate reduction dominated organic carbon mineralization, but their relative significance varied depending on the sediment. Where high concentrations of Mn-oxide were found (3-4 wt% Mn), only Mn reduction occurred. With lower Mn oxide concentrations more typical of coastal sediments, Fe reduction and sulfate reduction were most important and of a similar magnitude. Overall, most of the measured O2 flux into the sediment was used to oxidized reduced inorganic species and not organic carbon. We suspect that the importance of O2 respiration in many coastal sediments has been overestimated, whereas metal oxide reduction (both Fe and Mn reduction) has probably been well underestimated.

Electrical spin injection from CoFe2O4 into p-Si semiconductor across MgO tunnel barrier for spin electronics

NASA Astrophysics Data System (ADS)

Panda, J.; Maji, Nilay; Nath, T. K.

2017-05-01

The room temperature spin injection and detection in non magnetic p-Si semiconductor have been studied in details in our CoFe2O4 (CFO)/MgO/p-Si heterojunction. The 3-terminal tunnel contacts have been made on the device for transport measurements. The electrical transport properties have been investigated at different isothermal conditions in the temperature range of 10-300 K. The spin accumulation in non magnetic p-Si semiconductor has been observed at different bias current under the applied magnetic field parallel to the film plane in the temperature range of 40-300 K. We have observed a giant spin accumulation in p-Si semiconductor using MgO/CFO tunnel contact. The Hanley effect is used to control the reduction of spin accumulation by applying magnetic field perpendicular to the carrier spin in the p-Si. The accumulated spin signal decays as a function of applied magnetic field for fixed bias current. These results will enable utilization of the spin degree of freedom in complementary Si devices and its further development.

High Rate Oxygen Reduction in Non-aqueous Electrolytes with the Addition of Perfluorinated Additives

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

Wang, Y.; Yang, X.; Zheng, D.

2011-08-04

The discharge rate capability of Li-air batteries is substantially increased by using perfluorinated compounds as oxygen carriers. The solubility of oxygen in a non-aqueous electrolyte can be significantly increased by the introduction of such compounds, which leads to the increase in the diffusion-limited current of oxygen reduction on the gas diffusion electrode in a Li-air battery. The perfluorinated compound is found to be stable within the electrochemical window of the electrolyte. A powder microelectrode and a rotating disk electrode were used to study the gas diffusion-limited current together with a rotating disk electrode. A 5 mA cm{sup -2} discharge ratemore » is demonstrated in a lab Li-O{sub 2} cell.« less

Selective blockade of a slowly inactivating potassium current in striatal neurons by (+/-) 6-chloro-APB hydrobromide (SKF82958).

PubMed

Nisenbaum, E S; Mermelstein, P G; Wilson, C J; Surmeier, D J

1998-07-01

The ion channels of rat striatal neurons are known to be modulated by stimulation of D1 dopamine receptors. The susceptibility of depolarization-activated K+ currents to be modulated by the D1 agonist, 6-chloro-7,8-dihydroxy-3-allyl-1-phenyl-2,3,4,5-tetra-hydro-1H-3-benzaze pine (APB) was investigated using whole-cell voltage-clamp recording techniques from acutely isolated neurons. APB (0.01-100 microM) produced a concentration-dependent reduction in the total K+ current. At intermediate concentrations (ca. 10 microM), APB selectively depressed the slowly inactivating A-current (I(As)). A similar effect was produced by application of the D1 agonist, 7,8-dihydroxy-1-phenyl-2,3,4,5-tetrahydro-1-H-2-benzazepine (SKF38393, 10 microM). APB reduced I(As) rapidly, having onset and recovery time constants of 1.2 sec and 1.6 sec, respectively. Unexpectedly, the effect of APB could not be mimicked by application of Sp-adenosine 3',5'-cyclic monophosphothioate triethylamine (Sp-cAMPS, 100-200 microM), a membrane-permeable analog of cyclic AMP (cAMP), or by pretreatment with forskolin (25 microM), an activator of adenylyl cyclase. The reduction in I(As) also was not blocked by pretreatment with the D1 receptor antagonist, R(+)-SCH23390 hydrochloride (SCH23390, 10-20 microM). In addition, intracellular dialysis with guanosine-5'-O-(2-thiodiphosphate (GDP-beta-S, 200 microM) did not preclude the APB-induced inhibition of I(As), nor did dialysis with guanosine-5'-O-(3-thiotriphosphate (GTP-gamma-S, 400 microM) prevent reversal of the effect. The effect of APB was produced by a reduction in the maximal conductance of I(As) without changing the voltage-dependence of the current. Collectively, these results argue that APB does not inhibit I(As) through D1 receptors coupled to stimulation of adenylyl cyclase, but rather by allosterically regulating or blocking the channels giving rise to this current.

Sonochemically synthesized MnO2 nanoparticles as electrode material for supercapacitors.

PubMed

Gnana Sundara Raj, Balasubramaniam; Asiri, Abdullah M; Qusti, Abdullah H; Wu, Jerry J; Anandan, Sambandam

2014-11-01

In this study, manganese oxide (MnO2) nanoparticles were synthesized by sonochemical reduction of KMnO4 using polyethylene glycol (PEG) as a reducing agent as well as structure directing agent under room temperature in short duration of time and characterized by powder X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), Scanning electron microscope (SEM), Transmission electron microscopy (TEM) and Brunauer-Emmett-Teller (BET) analysis. A supercapacitor device constructed using the ultrasonically-synthesized MnO2 nanoparticles showed maximum specific capacitance (SC) of 282Fg(-1) in the presence of 1M Ca(NO3)2 as an electrolyte at a current density of 0.5mAcm(-2) in the potential range from 0.0 to 1.0V and about 78% of specific capacitance was retained even after 1000 cycles indicating its high electrochemical stability. Copyright © 2013 Elsevier B.V. All rights reserved.

Emissions Reduction Policies and Recent Trends in Southern California’s Ambient Air Quality

PubMed Central

Lurmann, Fred; Gilliland, Frank

2017-01-01

To assess accountability and effectiveness of air regulatory policies, we reviewed over 20 years of monitoring data, emissions estimates, and regulatory policies across several Southern California communities participating in a long-term study of children’s health. Between 1994 and 2011, air quality improved for NO2 and PM2.5 in virtually all the monitored communities. Average NO2 declined 28% to 53%, and PM2.5 decreased 13% to 54%. Year-to-year PM2.5 variability at lower-pollution sites was large compared to changes in long-term trends. PM10 and O3 decreases were largest in communities that were initially among the most polluted. Trends in annual average NO2, PM2.5, and PM10 concentrations in higher pollution communities were generally consistent with NOx, ROG, SOx, PM2.5, and PM10 emissions decreases. Reductions observed at one of the higher PM2.5 sites, Mira Loma, was generally within the range expected from reductions observed in ROG, NOx, SOx, and PM2.5 emissions. Despite a 38% increase in regional motor vehicle activity, vigorous economic growth, and a 30% population increase, total estimated emissions of NOx, ROG, SOx, PM2.5, and PM10 decreased by 54%, 65%, 40%, 21%, and 15%, respectively, during the 20-year time period. Emission control strategies in California have achieved dramatic reductions in ambient NO2, O3, PM2.5, and PM10. However, additional reductions will still be needed to achieve current health-based clean air standards. PMID:25947128

Effect of Initial FeO Content and CaO:SiO2 Ratio on the Reduction Smelting Kinetics of the CaO-SiO2-MgOsatd.-FeO Slag System

NASA Astrophysics Data System (ADS)

Kim, Jong Bae; Sohn, Il

2018-02-01

The effect of the initial FeO content and CaO:SiO2 ratio (CaO mass pct/SiO2 mass pct) on the reduction smelting of FeO with carbon flake addition is investigated in the CaO-MgOsatd.-SiO2-FeO slag system at 1823 K (1550 °C). Carbon rapidly reacted with FeO in the molten slag, causing both foaming and compositional changes in the slag. As FeO is reduced, the MgO saturation is modified, and solid precipitants, including MgO and other complex oxides, were observed, which significantly affected the slag properties, including the viscosity and foaming behavior. The solid-phase fraction and viscosity were estimated from changes in the measured FeO content over time using the thermochemical software FactSage. The iron recovery, which is distinguished from the amount of reduced Fe droplets, showed opposite behavior to the measured maximum foaming height and modified foaming index. According to the FeO mass transfer coefficient considering slag foaming at various initial FeO contents and CaO:SiO2 ratios, the reduction rate was optimal at higher initial FeO contents and a CaO:SiO2 ratio of 2.0, which did not correspond to the optimal iron recovery at an initial FeO content of 44 mass pct and above and a CaO:SiO2 ratio of 1.2. The results showed that slag foaming may increase the reduction kinetics, but the slag composition needs to be optimized for greater iron recovery.

SCR atmosphere induced reduction of oxidized mercury over CuO-CeO2/TiO2 catalyst.

PubMed

Li, Hailong; Wu, Shaokang; Wu, Chang-Yu; Wang, Jun; Li, Liqing; Shih, Kaimin

2015-06-16

CuO-CeO2/TiO2 (CuCeTi) catalyst synthesized by a sol-gel method was employed to investigate mercury conversion under a selective catalytic reduction (SCR) atmosphere (NO, NH3 plus O2). Neither NO nor NH3 individually exhibited an inhibitive effect on elemental mercury (Hg(0)) conversion in the presence of O2. However, Hg(0) conversion over the CuCeTi catalyst was greatly inhibited under SCR atmosphere. Systematic experiments were designed to investigate the inconsistency and explore the in-depth mechanisms. The results show that the copresence of NO and NH3 induced reduction of oxidized mercury (Hg(2+), HgO in this study), which offset the effect of catalytic Hg(0) oxidation, and hence resulted in deactivation of Hg(0) conversion. High NO and NH3 concentrations with a NO/NH3 ratio of 1.0 facilitated Hg(2+) reduction and therefore lowered Hg(0) conversion. Hg(2+) reduction over the CuCeTi catalyst was proposed to follow two possible mechanisms: (1) direct reaction, in which NO and NH3 react directly with HgO to form N2 and Hg(0); (2) indirect reaction, in which the SCR reaction consumed active surface oxygen on the CuCeTi catalyst, and reduced species on the CuCeTi catalyst surface such as Cu2O and Ce2O3 robbed oxygen from adjacent HgO. Different from the conventionally considered mechanisms, that is, competitive adsorption responsible for deactivation of Hg(0) conversion, this study reveals that oxidized mercury can transform into Hg(0) under SCR atmosphere. Such knowledge is of fundamental importance in developing efficient and economical mercury control technologies for coal-fired power plants.

General Observation of Photocatalytic Oxygen Reduction to Hydrogen Peroxide by Organic Semiconductor Thin Films and Colloidal Crystals.

PubMed

Gryszel, Maciej; Sytnyk, Mykhailo; Jakešová, Marie; Romanazzi, Giuseppe; Gabrielsson, Roger; Heiss, Wolfgang; Głowacki, Eric Daniel

2018-04-25

Low-cost semiconductor photocatalysts offer unique possibilities for industrial chemical transformations and energy conversion applications. We report that a range of organic semiconductors are capable of efficient photocatalytic oxygen reduction to H 2 O 2 in aqueous conditions. These semiconductors, in the form of thin films, support a 2-electron/2-proton redox cycle involving photoreduction of dissolved O 2 to H 2 O 2 , with the concurrent photooxidation of organic substrates: formate, oxalate, and phenol. Photochemical oxygen reduction is observed in a pH range from 2 to 12. In cases where valence band energy of the semiconductor is energetically high, autoxidation competes with oxidation of the donors, and thus turnover numbers are low. Materials with deeper valence band energies afford higher stability and also oxidation of H 2 O to O 2 . We found increased H 2 O 2 evolution rate for surfactant-stabilized nanoparticles versus planar thin films. These results evidence that photochemical O 2 reduction may be a widespread feature of organic semiconductors, and open potential avenues for organic semiconductors for catalytic applications.

Synthesis of magnetically recyclable MnFe2O4@SiO2@Ag nanocatalyst: Its high catalytic performances for azo dyes and nitro compounds reduction

NASA Astrophysics Data System (ADS)

Kurtan, U.; Amir, Md.; Yıldız, A.; Baykal, A.

2016-07-01

In this study, magnetically recycable MnFe2O4@SiO2@Ag nanocatalyst (MnFe2O4@SiO2@Ag MRCs) has been synthesized through co-precipition and chemical reduction method. XRD analysis confirmed the synthesis of single phase nanoproduct with crystallite size of 10 nm. VSM measurements showed the superparamagnetic property of the product. Catalytic studies showed that MnFe2O4@SiO2@Ag MRC could catalyze the reduction of the various azo compounds like methyl orange (MO), methylene blue (MB), eosin Y (EY), and rhodamine B (RhB) and also aromatic nitro compounds such as 4-nitrophenol (4-NP), 4-nitroaniline (4-NA) and 2-nitroaniline (2-NA). Moreover, the magnetic nanocatalyst showed an excellent reusability properties that remained unchanged after several cycles. Therefore, MnFe2O4@SiO2@Ag is the potential candidate for the application of organic pollutants for wastewater treatment.

Relationship between Eu{sup 3+} reduction and glass polymeric structure in Al{sub 2}O{sub 3}-modified borate glasses under air atmosphere

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

Jiao, Qing; Yu, Xue; Xu, Xuhui

2013-06-15

The reduction of Eu{sup 3+} to Eu{sup 2+} is realized efficiently in Eu{sub 2}O{sub 3}-doped borate glasses prepared under air condition by melting-quenching method. Luminescent spectra show an increasing tendency of Eu{sup 2+} emission with increasing Al{sub 2}O{sub 3} concentration in B{sub 2}O{sub 3}–Na{sub 2}O glasses. It is interesting that significant enhancement appeared of Eu{sup 2+} luminescence in the Al{sub 2}O{sub 3}-rich sample comparing to the samples of Al{sub 2}O{sub 3} less than 6 mol%. FTIR and Raman scattering measurements indicated that some new vibration modes assigned to the low-polymerized structure groups decomposed from the slight Al{sub 2}O{sub 3} dopantmore » samples. These results demonstrated that the polymerization of the glass structure decreased with increasing incorporation of Al{sub 2}O{sub 3} into the borate glasses, linking to the efficiency of Eu{sup 3+} self-reduction in air at high temperature. - graphical abstract: A novel europium valence reduction phenomenon occurred in Al{sub 2}O{sub 3} modified borate glasses, FTIR and Raman measurements revealed that high polymeric groups were destroyed to low polymery structures with Al{sub 2}O{sub 3} addition. - Highlights: • The efficient reduction of Eu{sup 3+} to Eu{sup 2+} is observed in the B{sub 2}O{sub 3}–Na{sub 2}O glasses. • Eu{sup 2+} luminescence is significant enhanced in the Al{sub 2}O{sub 3}-rich glasses. • The introduction of Al{sub 2}O{sub 3} changed the network structure of the borate glasses. • High polymeric borate groups in the glass matrix may be destroyed to the lower ones.« less

Dipole defects in MgAl2O4 spinel crystals

NASA Astrophysics Data System (ADS)

Ayres, F.; de Souza, S. S.; Blak, A. R.

In order to study defects of dipole origin in normal and inverse spinel structures, Thermally Stimulated Depolarisation Current (TSDC) measurements have been carried out in MgAl2O4 spinel crystals doped with Fe, Cr, Mn and Co. The TSDC spectrum of the as-received sample labelled R shows two bands at 160K and 290K. Temperatures above 700K destroy the 290K band and γ-irradiation up to 1,500kGy restores the peak. In another sample labelled UC, the 290K band, of dipole origin, is only detected after γ-irradiation. The dipole origin of the 160K band has already been verified. This band is affected neither by γ-irradiation nor by thermal treatment. The reduction of the 290K band is observed when heating the samples between 350K and 480K for three minutes at each temperature. The correlation between the thermal reduction of the 290K band and the study of V-centres in MgAl2O4 spinels indicates the possible attribution of the band to V-type centres.

Comparative analysis of the effects of tantalum doping and annealing on atomic layer deposited (Ta2O5)x(Al2O3)1-x as potential gate dielectrics for GaN/AlxGa1-xN/GaN high electron mobility transistors

NASA Astrophysics Data System (ADS)

Partida-Manzanera, T.; Roberts, J. W.; Bhat, T. N.; Zhang, Z.; Tan, H. R.; Dolmanan, S. B.; Sedghi, N.; Tripathy, S.; Potter, R. J.

2016-01-01

This paper describes a method to optimally combine wide band gap Al2O3 with high dielectric constant (high-κ) Ta2O5 for gate dielectric applications. (Ta2O5)x(Al2O3)1-x thin films deposited by thermal atomic layer deposition (ALD) on GaN-capped AlxGa1-xN/GaN high electron mobility transistor (HEMT) structures have been studied as a function of the Ta2O5 molar fraction. X-ray photoelectron spectroscopy shows that the bandgap of the oxide films linearly decreases from 6.5 eV for pure Al2O3 to 4.6 eV for pure Ta2O5. The dielectric constant calculated from capacitance-voltage measurements also increases linearly from 7.8 for Al2O3 up to 25.6 for Ta2O5. The effect of post-deposition annealing in N2 at 600 °C on the interfacial properties of undoped Al2O3 and Ta-doped (Ta2O5)0.12(Al2O3)0.88 films grown on GaN-HEMTs has been investigated. These conditions are analogous to the conditions used for source/drain contact formation in gate-first HEMT technology. A reduction of the Ga-O to Ga-N bond ratios at the oxide/HEMT interfaces is observed after annealing, which is attributed to a reduction of interstitial oxygen-related defects. As a result, the conduction band offsets (CBOs) of the Al2O3/GaN-HEMT and (Ta2O5)0.16(Al2O3)0.84/GaN-HEMT samples increased by ˜1.1 eV to 2.8 eV and 2.6 eV, respectively, which is advantageous for n-type HEMTs. The results demonstrate that ALD of Ta-doped Al2O3 can be used to control the properties of the gate dielectric, allowing the κ-value to be increased, while still maintaining a sufficient CBO to the GaN-HEMT structure for low leakage currents.

InP MOS capacitor and E-mode n-channel FET with ALD Al2O3-based high- k dielectric

NASA Astrophysics Data System (ADS)

Yen, Chih-Feng; Yeh, Min-Yen; Chong, Kwok-Keung; Hsu, Chun-Fa; Lee, Ming-Kwei

2016-07-01

The electrical characteristics of atomic-layer-deposited Al2O3/TiO2/Al2O3 on (NH4)2S-treated InP MOS capacitor and related MOSFET were studied. The electrical characteristics were improved from the reduction of native oxides and sulfur passivation on InP by (NH4)2S treatment. The high bandgap Al2O3 on TiO2 can reduce the thermionic emission, and the Al2O3 under TiO2 improves the interface-state density by self-cleaning. The high dielectric constant TiO2 is used to lower the equivalent oxide thickness. The leakage currents can reach 2.3 × 10-8 and 2.2 × 10-7 A/cm2 at ±2 MV/cm, respectively. The lowest interface-state density is 4.6 × 1011 cm-2 eV-1 with a low-frequency dispersion of 15 %. The fabricated enhancement-mode n-channel sulfur-treated InP MOSFET exhibits good electrical characteristics with a maximum transconductance of 146 mS/mm and effective mobility of 1760 cm2/V s. The subthreshold swing and threshold voltage are 117 mV/decade and 0.44 V, respectively.

Activities of Combined TiO2 Semiconductor Nanocatalysts Under Solar Light on the Reduction of CO2.

PubMed

Liu, Hongfang; Dao, Anh Quang; Fu, Chaoyang

2016-04-01

The materials based on TiO2 semiconductors are a promising option for electro-photocatalytic systems working as solar energy low-carbon fuels exchanger. These materials' structures are modified by doping metals and metal oxides, by metal sulfides sensitization, or by graphene supported membrane, enhancing their catalytic activity. The basic phenomenon of CO2 reduction to CH4 on Pd modified TiO2 under UV irradiation could be enhanced by Pd, or RuO2 co-doped TiO2. Sensitization with metal sulfide QDs is effective by moving of photo-excited electron from QDs to TiO2 particles. Based on characteristics of the catalysts various combinations of catalysts are proposed in order to creat catalyst systems with good CO2 reduction efficiency. From this critical review of the CO2 reduction to organic compounds by converting solar light and CO2 to storable fuels it is clear that more studies are still attractive and needed.

U.S. ozone air quality under changing climate and anthropogenic emissions.

PubMed

Racherla, Pavan N; Adams, Peter J

2009-02-01

We examined future ozone (O3) air quality in the United States (U.S.) under changing climate and anthropogenic emissions worldwide by performing global climate-chemistry simulations, utilizing various combinations of present (1990s) and future (Intergovernmental Panel on Climate Change (IPCC) Special Report on Emissions Scenarios (SRES) A2 2050s) climates, and present and future (2050s; IPCC SRES A2 and B1) anthropogenic emissions. The A2 climate scenario is employed here because it lies at the upper extreme of projected climate change for the 21st century. To examine the sensitivity of U.S. O3 to regional emissions increases (decreases), the IPCC SRES A2 and B1 scenarios, which have overall higher and lower O3-precursor emissions for the U.S., respectively, have been chosen. We find that climate change, by itself, significantly worsens the severity and frequency of high-O3 events ("episodes") over most locations in the U.S., with relatively small changes in average O3 air quality. These high-O3 increases due to climate change alone will erode moderately the gains made under a U.S. emissions reduction scenario (e.g., B1). The effect of climate change on high- and average-O3 increases with anthropogenic emissions. Insofar as average O3 air quality is concerned, changes in U.S. anthropogenic emissions will play the most important role in attaining (or not) near-term U.S. O3 air quality standards. However, policy makers must plan appropriately for O3 background increases due to projected increases in global CH4 abundance and non-U.S. anthropogenic emissions, as well as potential local enhancements that they could cause. These findings provide strong incentives for more-than-planned emissions reductions at locations that are currently O3-nonattainment.

Cathodic Deposition of Mg(OH)2 Coatings on Pure mg in Three mg Salts Aqueous Solutions

NASA Astrophysics Data System (ADS)

Yongjun, Zhang; Xiaomeng, Pei; Shugong, Jia

Film-forming effects of cathodic deposition on pure Mg substrate at constant DC in aqueous solutions of magnesium nitrate (Mg(NO3)2ṡ6H2O), magnesium chloride (MgCl2ṡ6H2O) and magnesium sulfate (MgSO4ṡ7H2O) respectively were investigated systematically. Typical processes were studied by potentiodynamic cathodic polarization and galvanostatic polarization and typical samples were analyzed by SEM and XRD. The results indicate that the depositing efficiency is not only the highest but stablest, and deposited coatings show the best uniformity with Mg(NO3)2ṡ6H2O solution employed as depositing medium and applied current density ≥1.0mA cm-2. Cathodic deposition leads to regular mass loss of Mg substrate. The cathodic polarization curve of pure Mg in magnesium nitrate solution shows more obvious pseudo-passivation, several Tafel regions with different slopes appearing before diffusion-limited current density region, and oxygen consumption is the major cathodic reduction reaction under specified current density. However, hydrogen evolution reaction is dominant in both Mg chloride and Mg sulfate solutions. The deposition coatings are all composed of continuous and uniform mesh-like “basic layer” adjacent to substrate and discrete distributed snowball-like particles on the microscopic scale. The phase compositions are all crystal Mg(OH)2, and the coatings deposited in Mg chloride solution have (011) preferred orientation.

Reduction of Chlorate by Iron Mediated Processes: Implications for Oxy-Chlorine Species on Mars and Earth

NASA Astrophysics Data System (ADS)

Brundrett, M.; Yan, W.; Jackson, W. A.

2017-12-01

Studies have confirmed the presence of chlorate (ClO3-) and perchlorate (ClO4-) in terrestrial systems, lunar regolith, Martian surface soils, and meteorites [1, 2, 4]. A roughly equimolar ratio of ClO3- : ClO4- has been observed for most systems with the only major exceptions the Antarctica dry valley soils (MDV) and Martian surface material, where the ClO3- : ClO4- ratios are significantly less than 1 [3, 4]. All known ClO4- production mechanisms produce molar ratios of ClO3-: ClO4- equal to or greater than 1 [5]. Post depositional processes may explain the potential reduction of ClO3-. The objective of this study was to determine the potential abiotic transformation of ClO3- by Fe (II)-bearing minerals, similar to known reactions between NO3- and Fe (II) minerals. The presence of iron-derived minerals has been established in the MDV, Martian soils, and chondrite meteorites. Batch experiments were conducted by reacting four Fe (II)-bearing minerals (wustite, siderite, magnetite, and green rust) with ClO3- at various pH (4.5, 6.5, 8.9). Chlorate reduction was rapid (half-life on the order of hours to days) and generally ClO3- was quantitatively converted to Cl-. Results of this study will increase our understanding of surface reactions that produced and transformed oxy-chlorine compounds on Mars elucidating past and present Martian surface conditions. The study also has implications into the understanding of the evolutionary processes that previously or currently dictate the abiotic geochemical processing of oxy-chlorine anions through terrestrial systems. [1] Jackson et al. (2015) EPSL 430, 470-476. [2] Rao et al. (2010) ES&T 44, 8429-8434. [3] Jackson et al. (2010) ES&T 44, 4869-4876. [4] Hecht et al. (2009) SCI 325, 64-67. [5] Rao et al. (2010) ES&T 44, 2961-2967.

Limited effect of ozone reductions on the 20-year photosynthesis trend at Harvard forest.

PubMed

Yue, Xu; Keenan, Trevor F; Munger, William; Unger, Nadine

2016-11-01

Ozone (O 3 ) damage to leaves can reduce plant photosynthesis, which suggests that declines in ambient O 3 concentrations ([O 3 ]) in the United States may have helped increase gross primary production (GPP) in recent decades. Here, we assess the effect of long-term changes in ambient [O 3 ] using 20 years of observations at Harvard forest. Using artificial neural networks, we found that the effect of the inclusion of [O 3 ] as a predictor was slight, and independent of O 3 concentrations, which suggests limited high-frequency O 3 inhibition of GPP at this site. Simulations with a terrestrial biosphere model, however, suggest an average long-term O 3 inhibition of 10.4% for 1992-2011. A decline of [O 3 ] over the measurement period resulted in moderate predicted GPP trends of 0.02-0.04 μmol C m -2  s -1  yr -1 , which is negligible relative to the total observed GPP trend of 0.41 μmol C m -2  s -1  yr -1 . A similar conclusion is achieved with the widely used AOT40 metric. Combined, our results suggest that ozone reductions at Harvard forest are unlikely to have had a large impact on the photosynthesis trend over the past 20 years. Such limited effects are mainly related to the slow responses of photosynthesis to changes in [O 3 ]. Furthermore, we estimate that 40% of photosynthesis happens in the shade, where stomatal conductance and thus [O 3 ] deposition is lower than for sunlit leaves. This portion of GPP remains unaffected by [O 3 ], thus helping to buffer the changes of total photosynthesis due to varied [O 3 ]. Our analyses suggest that current ozone reductions, although significant, cannot substantially alleviate the damages to forest ecosystems. © 2016 John Wiley & Sons Ltd.

Study of the electrochemical oxidation and reduction of C.I. Reactive Orange 4 in sodium sulphate alkaline solutions.

PubMed

del Río, A I; Molina, J; Bonastre, J; Cases, F

2009-12-15

Synthetic solutions of hydrolysed C.I. Reactive Orange 4, a monoazo textile dye commercially named Procion Orange MX-2R (PMX2R) and colour index number C.I. 18260, was exposed to electrochemical treatment under galvanostatic conditions and Na2SO4 as electrolyte. The influence of the electrochemical process as well as the applied current density was evaluated. Ti/SnO2-Sb-Pt and stainless steel electrodes were used as anode and cathode, respectively, and the intermediates generated on the cathode during electrochemical reduction were investigated. Aliquots of the solutions treated were analysed by UV-visible and FTIR-ATR spectroscopy confirming the presence of aromatic structures in solution when an electro-reduction was carried out. Electro-oxidation degraded both the azo group and aromatic structures. HPLC measures revealed that all processes followed pseudo-first order kinetics and decolourisation rates showed a considerable dependency on the applied current density. CV experiments and XPS analyses were carried out to study the behaviour of both PMX2R and intermediates and to analyse the state of the cathode after the electrochemical reduction, respectively. It was observed the presence of a main intermediate in solution after an electrochemical reduction whose chemical structure is similar to 2-amino-1,5-naphthalenedisulphonic acid. Moreover, the analysis of the cathode surface after electrochemical reduction reveals the presence of a coating layer with organic nature.

A Polycarboxyl-Decorated FeIII -Based Xerogel-Derived Multifunctional Composite (Fe3 O4 /Fe/C) as an Efficient Electrode Material towards Oxygen Reduction Reaction and Supercapacitor Application.

PubMed

Devi, Bandhana; Venkateswarulu, Mangili; Kushwaha, Himmat Singh; Halder, Aditi; Koner, Rik Rani

2018-05-02

Low cost, non-noble metal catalysts with a good oxygen reduction reaction (ORR) activity comparable to that of platinum and also having good energy storage properties are highly desirable but challenging. Several challenges are associated with the development of such materials. Herein, we demonstrate a new polycarboxyl-functionalised Fe III -based gel material, synthesised following a solvothermal method and the development of its composite (Fe 3 O 4 /Fe/C) by annealing at optimised temperature. The developed composite displayed excellent electrocatalytic activity for the oxygen reduction reaction with an onset potential of 0.87 V (vs. RHE) and a current density value of -5 mA cm -2 , which are comparable with commercial 20 wt % Pt/C. In addition, as one of the most desirable properties, the composite exhibits a better methanol tolerance and greater durability than Pt/C. The same material was explored as an energy storage material for supercapacitors, which showed a specific capacitance of 245 F g -1 at a current density of 1 A g -1 . It is expected that this Fe 3 O 4 /Fe/C composite with a disordered graphitised carbon matrix will pave a horizon for developing energy conversion and energy storage devices. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Solid State Reduction of MoO3 with Carbon via Mechanical Alloying to Synthesize Nano-Crystaline MoO2

NASA Astrophysics Data System (ADS)

Saghafi, M.; Ataie, A.; Heshmati-Manesh, S.

In this research, effect of milling time on solid state reduction of MoO3 with carbon has been investigated. It was found that mechanical activation of a mixture of MoO3 and carbon at ambient temperature by high energy ball milling was not able to reduce MoO3 to metallic molybdenum. MoO3 was converted to MoO2 at the first stage of reduction and peaks of the latter phase in X-ray diffraction patterns were detected when the milling time exceeded from 50 hours. The main effect of increased milling time at this stage was decreasing of MoO3 peak intensities and significant peak broadening due to decrease in size of crystallites. After prolonged milling, MoO3 was fully reduced to nano-crystalline MoO2 and its mean crystallite size was calculated using Williamson-Hall technique and found to be 17.5 nm. Thermodynamic investigations also confirm the possibility of reduction of MoO3 to MoO2 during the milling operation at room temperature. But, further reduction to metallic molybdenum requires thermal activation at higher temperature near 1100 K. XRD and SEM techniques were employed to evaluate the powder particles characteristics.

MOCVD (Ba{sub x}Sr{sub 1-x})Ti{sub 1+y}O{sub 3+z} (BST) thin films for high frequency tunable devices.

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

Baumann, P. K.; Kaufman, D. Y.; Im, J.

2001-01-01

We have investigated the structural and electrical characteristics of (Ba{sub x}Sr{sub 1-x})Ti{sub 1+y}O{sub 3+z} (BST) thin films synthesized at 650{sup o}C on Pt/SiO{sub 2}/Si substrates using a large area, vertical metalorganic chemical vapor deposition (MOCVD) reactor equipped with a liquid delivery system. Films with a Ba/Sr ratio of 70/30 were studied, as determined using X-ray fluorescence spectroscopy (XRF) and Rutherford backscattering spectrometry (RBS). A substantial reduction of the dielectric loss was achieved when annealing the entire capacitor structure in air at 700{sup o}C. Dielectric tunability as high as 2.3:1 was measured for BST capacitors with the currently optimized processing conditions.

Nanometer-Scale Electrical Potential Profiling Across Perovskite Solar Cells

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

Xiao, Chuanxiao; Jiang, Chun-Sheng; Ke, Weijun

2016-11-21

We used Kelvin probe force microscopy to study the potential distribution on cross-section of perovskite solar cells with different types of electron-transporting layers (ETLs). Our results explain the low open-circuit voltage and fill factor in ETL-free cells, and support the fact that intrinsic SnO2 as an alternative ETL material can make high-performance devices. Furthermore, the potential-profiling results indicate a reduction in junction-interface recombination by the optimized SnO2 layer and adding a fullerene layer, which is consistent with the improved device performance and current-voltage hysteresis.

Electrical properties of titanium dioxide nanoparticle on microelectrode: Gap size effect

NASA Astrophysics Data System (ADS)

Nadzirah, Sh.; Hashim, U.; Zakaria, M. R.; Rusop, M.

2018-05-01

TiO2 nanoparticle based interdigitated microelectrode was fabricated by spin-coating and conventional photolithography approaches. Aluminum metal was deposited by thermal evaporator on silicon dioxide substrate. The effect of aluminum microelectrode gap sizes (4, 5 and 6 µm) on the electrical performance was investigated using picoammeter. Extremely small output current values of three different gap sizes were acquired. A characteristic electrical behavior was observed for the studied geometry. The configuration demonstrated a reduction in the output current from 2.28E-10, 1.32E-9 and 2.38E-9 A with increasing gap size.

Synthesis of Superparamagnetic Core-Shell Structure Supported Pd Nanocatalysts for Catalytic Nitrite Reduction with Enhanced Activity, No Detection of Undesirable Product of Ammonium, and Easy Magnetic Separation Capability.

PubMed

Sun, Wuzhu; Yang, Weiyi; Xu, Zhengchao; Li, Qi; Shang, Jian Ku

2016-01-27

Superparamagnetic nanocatalysts could minimize both the external and internal mass transport limitations and neutralize OH(-) produced in the reaction more effectively to enhance the catalytic nitrite reduction efficiency with the depressed product selectivity to undesirable ammonium, while possess an easy magnetic separation capability. However, commonly used qusi-monodispersed superparamagnetic Fe3O4 nanosphere is not suitable as catalyst support for nitrite reduction because it could reduce the catalytic reaction efficiency and the product selectivity to N2, and the iron leakage could bring secondary contamination to the treated water. In this study, protective shells of SiO2, polymethylacrylic acid, and carbon were introduced to synthesize Fe3O4@SiO2/Pd, Fe3O4@PMAA/Pd, and Fe3O4@C/Pd catalysts for catalytic nitrite reduction. It was found that SiO2 shell could provide the complete protection to Fe3O4 nanosphere core among these shells. Because of its good dispersion, dense structure, and complete protection to Fe3O4, the Fe3O4@SiO2/Pd catalyst demonstrated the highest catalytic nitrite reduction activity without the detection of NH4(+) produced. Due to this unique structure, the activity of Fe3O4@SiO2/Pd catalysts for nitrite reduction was found to be independent of the Pd nanoparticle size or shape, and their product selectivity was independent of the Pd nanoparticle size, shape, and content. Furthermore, their superparamagnetic nature and high saturation magnetization allowed their easy magnetic separation from treated water, and they also demonstrated a good stability during the subsequent recycling experiment.

Reduction of CO2 to low carbon alcohols on CuO FCs/Fe2O3 NTs catalyst with photoelectric dual catalytic interfaces

NASA Astrophysics Data System (ADS)

Li, Peiqiang; Wang, Huying; Xu, Jinfeng; Jing, Hua; Zhang, Jun; Han, Haixiang; Lu, Fusui

2013-11-01

In this paper, the CuO FCs/Fe2O3 NTs catalyst was obtained after Fe2O3 nanotubes (Fe2O3 NTs) were decorated with CuO flower clusters (CuO FCs) by the pulse electrochemical deposition method. The in situ vertically aligned Fe2O3 NTs were prepared on the ferrous substrate by a potentiostatic anodization method. The SEM result showed the volcano-like Fe2O3 NTs were arranged in order and the CuO FCs constituted of flaky CuO distributed on the Fe2O3 NTs surface uniformly. After CuO FCs were loaded on Fe2O3 NTs, the absorption of visible light was enhanced noticeably, and its band gap narrowed to 1.78 eV from 2.03 eV. The conduction band and valence band locating at -0.73 eV and 1.05 eV, respectively were further obtained. In the PEC reduction of CO2 process, methanol and ethanol were two major products identified by chromatography. Their contents reached 1.00 mmol L-1 cm-2 and 107.38 μmol L-1 cm-2 after 6 h, respectively. This high-efficiency catalyst with photoelectric dual catalytic interfaces has a great guidance and reference significance for CO2 reduction to liquid carbon fuels.In this paper, the CuO FCs/Fe2O3 NTs catalyst was obtained after Fe2O3 nanotubes (Fe2O3 NTs) were decorated with CuO flower clusters (CuO FCs) by the pulse electrochemical deposition method. The in situ vertically aligned Fe2O3 NTs were prepared on the ferrous substrate by a potentiostatic anodization method. The SEM result showed the volcano-like Fe2O3 NTs were arranged in order and the CuO FCs constituted of flaky CuO distributed on the Fe2O3 NTs surface uniformly. After CuO FCs were loaded on Fe2O3 NTs, the absorption of visible light was enhanced noticeably, and its band gap narrowed to 1.78 eV from 2.03 eV. The conduction band and valence band locating at -0.73 eV and 1.05 eV, respectively were further obtained. In the PEC reduction of CO2 process, methanol and ethanol were two major products identified by chromatography. Their contents reached 1.00 mmol L-1 cm-2 and 107.38 μmol L-1 cm-2 after 6 h, respectively. This high-efficiency catalyst with photoelectric dual catalytic interfaces has a great guidance and reference significance for CO2 reduction to liquid carbon fuels. Electronic supplementary information (ESI) available: Reduction of CO2 to low carbon alcohols on CuO FCs/Fe2O3 NTs catalyst with photoelectric dual catalytic interfaces. See DOI: 10.1039/c3nr03352j

Cryptic oxygen cycling in anoxic marine zones

PubMed Central

Padilla, Cory C.; Stewart, Frank J.; Ulloa, Osvaldo; Paulmier, Aurélien; Gregori, Gerald; Revsbech, Niels Peter

2017-01-01

Oxygen availability drives changes in microbial diversity and biogeochemical cycling between the aerobic surface layer and the anaerobic core in nitrite-rich anoxic marine zones (AMZs), which constitute huge oxygen-depleted regions in the tropical oceans. The current paradigm is that primary production and nitrification within the oxic surface layer fuel anaerobic processes in the anoxic core of AMZs, where 30–50% of global marine nitrogen loss takes place. Here we demonstrate that oxygenic photosynthesis in the secondary chlorophyll maximum (SCM) releases significant amounts of O2 to the otherwise anoxic environment. The SCM, commonly found within AMZs, was dominated by the picocyanobacteria Prochlorococcus spp. Free O2 levels in this layer were, however, undetectable by conventional techniques, reflecting a tight coupling between O2 production and consumption by aerobic processes under apparent anoxic conditions. Transcriptomic analysis of the microbial community in the seemingly anoxic SCM revealed the enhanced expression of genes for aerobic processes, such as nitrite oxidation. The rates of gross O2 production and carbon fixation in the SCM were found to be similar to those reported for nitrite oxidation, as well as for anaerobic dissimilatory nitrate reduction and sulfate reduction, suggesting a significant effect of local oxygenic photosynthesis on Pacific AMZ biogeochemical cycling. PMID:28716941

Multiplexed enzyme-free electrochemical immunosensor based on ZnO nanorods modified reduced graphene oxide-paper electrode and silver deposition-induced signal amplification strategy.

PubMed

Sun, Guoqiang; Zhang, Lina; Zhang, Yan; Yang, Hongmei; Ma, Chao; Ge, Shenguang; Yan, Mei; Yu, Jinghua; Song, Xianrang

2015-09-15

Herein, an origami multiplexed enzyme-free electrochemical (EC) immunodevice is developed for the first time. Typically, ZnO nanorods (ZNRs) modified reduced graphene oxide (rGO)-paper electrode is used as a sensor platform, in which rGO improves the electronic transmission rate and ZNRs provide abundant sites for capture probes binding. Furthermore, by combining the large surface area of rGO and high catalytic activity of bovine serum protein (BSA)-stabilized silver nanoparticles (Ag@BSA) toward H2O2 reduction, rGO/Ag@BSA composites can be used as an excellent signal labels. The current signal is generated from the reduction of H2O2 and further amplified by a subsequent signal labels-promoted deposition of silver. Under optimal conditions, the proposed immunoassays exhibit excellent precision, high sensitivity and a wide linear range of 0.002-120 mIU mL(-1) for human chorionic gonadotropin, 0.001-110 ng mL(-1) for prostate-specific antigen, and 0.001-100 ng mL(-1) for carcinoembryonic antigen. The results for real sample analysis demonstrate that the newly constructed immunosensor arrays provide a simple and cost-effective method for clinical applications. Copyright © 2015 Elsevier B.V. All rights reserved.

In situ loading of gold nanoparticles on Fe3O4@SiO2 magnetic nanocomposites and their high catalytic activity.

PubMed

Zheng, Jinmin; Dong, Yalei; Wang, Weifeng; Ma, Yanhua; Hu, Jing; Chen, Xiaojiao; Chen, Xingguo

2013-06-07

In this work, a facile approach was successfully developed for in situ catalyzing Au nanoparticles loaded on Fe3O4@SiO2 magnetic nanospheres via Sn(2+) linkage and reduction. After the Fe3O4@SiO2 MNPs were first prepared via a sol-gel process, only one step was needed to synthesize the Fe3O4@SiO2-Au magnetic nanocomposites (Fe3O4@SiO2-Au MNCs), so that both the synthesis step and the reaction cost were remarkably decreased. Significantly, the as-synthesized Fe3O4@SiO2-Au MNCs showed high performance in the catalytic reduction of 4-nitrophenol to 4-aminophenol and could be reused for several cycles with convenient magnetic separability. This approach provided a useful platform based on Fe3O4@SiO2 MNPs for the fabrication of Au or other noble metal magnetic nanocatalysts, which would be very useful in various catalytic reductions.

A room temperature process for the fabrication of amorphous indium gallium zinc oxide thin-film transistors with co-sputtered Zr x Si1- x O2 Gate dielectric and improved electrical and hysteresis performance

NASA Astrophysics Data System (ADS)

Hung, Chien-Hsiung; Wang, Shui-Jinn; Liu, Pang-Yi; Wu, Chien-Hung; Wu, Nai-Sheng; Yan, Hao-Ping; Lin, Tseng-Hsing

2017-04-01

The use of co-sputtered zirconium silicon oxide (Zr x Si1- x O2) gate dielectrics to improve the gate controllability of amorphous indium gallium zinc oxide (α-IGZO) thin-film transistors (TFTs) through a room-temperature fabrication process is proposed and demonstrated. With the sputtering power of the SiO2 target in the range of 0-150 W and with that of the ZrO2 target kept at 100 W, a dielectric constant ranging from approximately 28.1 to 7.8 is obtained. The poly-structure formation immunity of the Zr x Si1- x O2 dielectrics, reduction of the interface trap density suppression, and gate leakage current are examined. Our experimental results reveal that the Zr0.85Si0.15O2 gate dielectric can lead to significantly improved TFT subthreshold swing performance (103 mV/dec) and field effect mobility (33.76 cm2 V-1 s-1).

Graphitic biochar as a cathode electrocatalyst support for microbial fuel cells.

PubMed

Huggins, Tyler M; Pietron, Jeremy J; Wang, Heming; Ren, Zhiyong Jason; Biffinger, Justin C

2015-11-01

Graphitic biochar (BC) was generated using high temperature gasification and alkaline post-treatment (BCw) of wood-based biomass. The BCw was evaluated as a manganese oxide electrocatalytic support (MnO/BCw) and microbial fuel cell (MFC) air cathode. Nano-structured MnO2 crystals were successfully immobilized on biomass-based graphitic sheets and characterized using physical, chemical, and electrochemical analyses. Cyclic voltammetry of MnO/BCw/Nafion inks showed electrochemical features typical of β-MnO2 with a current density of 0.9 mA cm(-2). BC showed satisfactory maximum power densities of 146.7 mW m(-2) (BCw) and 187.8 W m(-2) (MnO/BCw), compared with Vulcan Carbon (VC) (156.8 mW m(-2)) and manganese oxide VC composites (MnO/VC) (606.1 mW m(-2)). These materials were also tested as oxygen reduction reaction (ORR) catalysts for single chamber MFCs inoculated with anaerobic sludge. Our results demonstrate that BC can serve as an effective, low cost, and scalable material for MFC application. Published by Elsevier Ltd.

Understanding the influence of tellurium oxide in front Ag paste for contacting silicon solar cells with homogeneous high sheet resistance emitter

NASA Astrophysics Data System (ADS)

Ebong, Abasifreke; Bezawada, Nirupama; Batchu, Kartheek

2017-08-01

This paper investigates TeO2, one of the front Ag paste additives, to understand its role in low contact and gridline resistances for screen-printed Si solar cell. It is concluded that TeO2 aids the reduction of molten glass frit viscosity during contact co-firing. This in turn, leads to uniform flow of molten glass frit, both in the gridline bulk and interface of gridline and SiN x . Therefore, the uniform wetting and etching of SiN x and consequently larger contact area of metal to Si compared to its counterpart without TeO2. Hence, the current transport mechanism from Si to gridline can be said to be both direct and tunneling. The Raman spectra showed a blue shift in the phase of the TeO2 after contact co-firing in the gridline bulk confirming a crystalline γ-TeO2.

Insulation Resistance Degradation in Ni-BaTiO3 Multilayer Ceramic Capacitors

NASA Technical Reports Server (NTRS)

Liu, Donhang David

2015-01-01

Insulation resistance (IR) degradation in NiBaTiO3 multilayer ceramic capacitors has been characterized by the measurement of both time to failure (TTF) and direct current leakage current as a function of stress time under highly accelerated life test conditions. The measured leakage current time dependence data fit well to an exponential form, and a characteristic growth time tau (sub SD) can be determined. A greater value of tau (sub SD) represents a slower IR degradation process. Oxygen vacancy migration and localization at the grain boundary region results in the reduction of the Schottky barrier height and has been found to be the main reason for IR degradation in NiBaTiO3 capacitors. The reduction of barrier height as a function oftime follows an exponential relation of phi (t ) = phi (0) e (exp -2Kt), where 13 the degradation rate constant K Koe (Ek/kT) is inversely proportional to the mean TTF (MTTF) and can be determined using an Arrhenius plot. For oxygen vacancy electromigration, a lower barrier height phi (0) will favor a slow IR degradation process, but a lower phi (0) will also promote electronic carrier conduction across the barrier and decrease the IR. As a result, a moderate barrier height phi (0) (and therefore a moderate IR value) with a longer MTTF (smaller degradation rate constant K) will result in a minimized IR degradation process and the most improved reliability in NiBaTiO3 multilayer ceramic capacitors.

How light-harvesting semiconductors can alter the bias of reversible electrocatalysts in favor of H2 production and CO2 reduction.

PubMed

Bachmeier, Andreas; Wang, Vincent C C; Woolerton, Thomas W; Bell, Sophie; Fontecilla-Camps, Juan C; Can, Mehmet; Ragsdale, Stephen W; Chaudhary, Yatendra S; Armstrong, Fraser A

2013-10-09

The most efficient catalysts for solar fuel production should operate close to reversible potentials, yet possess a bias for the fuel-forming direction. Protein film electrochemical studies of Ni-containing carbon monoxide dehydrogenase and [NiFeSe]-hydrogenase, each a reversible electrocatalyst, show that the electronic state of the electrode strongly biases the direction of electrocatalysis of CO2/CO and H(+)/H2 interconversions. Attached to graphite electrodes, these enzymes show high activities for both oxidation and reduction, but there is a marked shift in bias, in favor of CO2 or H(+) reduction, when the respective enzymes are attached instead to n-type semiconductor electrodes constructed from CdS and TiO2 nanoparticles. This catalytic rectification effect can arise for a reversible electrocatalyst attached to a semiconductor electrode if the electrode transforms between semiconductor- and metallic-like behavior across the same narrow potential range (<0.25 V) that the electrocatalytic current switches between oxidation and reduction.

Corticospinal excitability is associated with hypocapnia but not changes in cerebral blood flow

PubMed Central

Hartley, Geoffrey L.; Watson, Cody L.; Ainslie, Philip N.; Tokuno, Craig D.; Greenway, Matthew J.; Gabriel, David A.; O'Leary, Deborah D.

2016-01-01

Key points Reductions in cerebral blood flow (CBF) may be implicated in the development of neuromuscular fatigue; however, the contribution from hypocapnic‐induced reductions (i.e. P ETC O2) in CBF versus reductions in CBF per se has yet to be isolated.We assessed neuromuscular function while using indomethacin to selectively reduce CBF without changes in P ETC O2 and controlled hyperventilation‐induced hypocapnia to reduce both CBF and P ETC O2.Increased corticospinal excitability appears to be exclusive to reductions in P ETC O2 but not reductions in CBF, whereas sub‐optimal voluntary output from the motor cortex is moderately associated with decreased CBF independent of changes in P ETC O2.These findings suggest that changes in CBF and P ETC O2 have distinct roles in modulating neuromuscular function. Abstract Although reductions in cerebral blood flow (CBF) may be involved in central fatigue, the contribution from hypocapnia‐induced reductions in CBF versus reductions in CBF per se has not been isolated. This study examined whether reduced arterial PCO2 (P aC O2), independent of concomitant reductions in CBF, impairs neuromuscular function. Neuromuscular function, as indicated by motor‐evoked potentials (MEPs), maximal M‐wave (M max) and cortical voluntary activation (cVA) of the flexor carpi radialis muscle during isometric wrist flexion, was assessed in ten males (29 ± 10 years) during three separate conditions: (1) cyclooxygenase inhibition using indomethacin (Indomethacin, 1.2 mg kg−1) to selectively reduce CBF by 28.8 ± 10.3% (estimated using transcranial Doppler ultrasound) without changes in end‐tidal PCO2 (P ETC O2); (2) controlled iso‐oxic hyperventilation‐induced reductions in P aC O2 (Hypocapnia), P ETC O2  = 30.1 ± 4.5 mmHg with related reductions in CBF (21.7 ± 6.3%); and (3) isocapnic hyperventilation (Isocapnia) to examine the potential direct influence of hyperventilation‐mediated activation of respiratory control centres on CBF and changes in neuromuscular function. Change in MEP amplitude (%M max) from baseline was greater in Hypocapnia tha in Isocapnia (11.7 ± 9.8%, 95% confidence interval (CI) [2.6, 20.7], P = 0.01) and Indomethacin (13.3 ± 11.3%, 95% CI [2.8, 23.7], P = 0.01) with a large Cohen's effect size (d ≥ 1.17). Although not statistically significant, cVA was reduced with a moderate effect size in Indomethacin (d = 0.7) and Hypocapnia (d = 0.9) compared to Isocapnia. In summary, increased corticospinal excitability – as reflected by larger MEP amplitude – appears to be exclusive to reduced P aC O2, but not reductions in CBF per se. Sub‐optimal voluntary output from the motor cortex is moderately associated with decreased CBF, independent of reduced P aC O2. PMID:26836470

SrNb2O6 nanoplates as efficient photocatalysts for the preferential reduction of CO2 in the presence of H2O.

PubMed

Xie, Shunji; Wang, Yu; Zhang, Qinghong; Deng, Weiping; Wang, Ye

2015-02-25

We successfully synthesized SrNb2O6 with nanoplate morphology by a facile hydrothermal method. The SrNb2O6 nanoplate without any promoters or co-catalysts exhibited promising photocatalytic performance for the preferential reduction of CO2 with H2O vapour to CO and CH4 due to its high electron-hole separation and high CO2 chemisorption abilities.

Nitric Oxide Reduction to Ammonia by TiO 2 Electrons in Colloid Solution via Consecutive One-Electron Transfer Steps

DOE PAGES

Goldstein, Sara; Behar, David; Rajh, Tijana; ...

2015-03-02

The reaction mechanism of nitric oxide (NO) reduction by excess electrons on TiO 2 nanoparticles (e TiO2–) has been studied under anaerobic conditions. TiO 2 was loaded with 10–130 electrons per particle using γ-irradiation of acidic TiO 2 colloid solutions containing 2-propanol. The study is based on time-resolved kinetics and reactants and products analysis. The reduction of NO by e TiO2– is interpreted in terms of competition between a reaction path leading to formation of NH 3 and a path leading to N 2O and N 2. The proposed mechanism involves consecutive one-electron transfers of NO, and its reduction intermediatesmore » HNO, NH 2O•, and NH 2OH. The results show that e TiO2– does not reduce N 2O and N 2. Second-order rate constants of e TiO2– reactions with NO (740 ± 30 M –1 s –1) and NH 2OH (270 ± 30 M –1 s –1) have been determined employing the rapid-mixing stopped-flow technique and that with HNO (>1.3 × 10 6 M –1 s –1) was derived from fitting the kinetic traces to the suggested reaction mechanism, which is discussed in detail.« less

Preparation of porous lead from shape-controlled PbO bulk by in situ electrochemical reduction in ChCl-EG deep eutectic solvent

NASA Astrophysics Data System (ADS)

Ru, Juanjian; Hua, Yixin; Xu, Cunying; Li, Jian; Li, Yan; Wang, Ding; Zhou, Zhongren; Gong, Kai

2015-12-01

Porous lead with different shapes was firstly prepared from controlled geometries of solid PbO bulk by in situ electrochemical reduction in choline chloride-ethylene glycol deep eutectic solvents at cell voltage 2.5 V and 353 K. The electrochemical behavior of PbO powders on cavity microelectrode was investigated by cyclic voltammetry. It is indicated that solid PbO can be directly reduced to metal in the solvent and a nucleation loop is apparent. Constant voltage electrolysis demonstrates that PbO pellet can be completely converted to metal for 13 h, and the current efficiency and specific energy consumption are about 87.79% and 736.82 kWh t-1, respectively. With the electro-deoxidation progress on the pellet surface, the reduction rate reaches the fastest and decreases along the distance from surface to inner center. The morphologies of metallic products are porous and mainly consisted of uniform particles which connect with each other by finer strip-shaped grains to remain the geometry and macro size constant perfectly. In addition, an empirical model of the electro-deoxidation process from spherical PbO bulk to porous lead is also proposed. These findings provide a novel and simple route for the preparation of porous metals from oxide precursors in deep eutectic solvents at room temperature.

Alternative Anodes for the Electrolytic Reduction of Uranium Dioxide

NASA Astrophysics Data System (ADS)

Merwin, Augustus

Reprocessing of spent nuclear fuel is an essential step in closing the nuclear fuel cycle. In order to consume current stockpiles, ceramic uranium dioxide spent nuclear fuel will be subjected to an electrolytic reduction process. The current reduction process employs a platinum anode and a stainless steel alloy 316 cathode in a molten salt bath consisting of LiCl-2wt% Li 2O and occurs at 700°C. A major shortcoming of the existing process is the degradation of the platinum anode under the severely oxidizing conditions encountered during electrolytic reduction. This work investigates alternative anode materials for the electrolytic reduction of uranium oxide. The high temperature and extreme oxidizing conditions encountered in these studies necessitated a unique set of design constraints on the system. Thus, a customized experimental apparatus was designed and constructed. The electrochemical experiments were performed in an electrochemical reactor placed inside a furnace. This entire setup was housed inside a glove box, in order to maintain an inert atmosphere. This study investigates alternative anode materials through accelerated corrosion testing. Surface morphology was studied using scanning electron microscopy. Surface chemistry was characterized using energy dispersive spectroscopy and Raman spectroscopy. Electrochemical behavior of candidate materials was evaluated using potentiodynamic polarization characteristics. After narrowing the number of candidate electrode materials, ferrous stainless steel alloy 316, nickel based Inconel 718 and elemental tungsten were chosen for further investigation. Of these materials only tungsten was found to be sufficiently stable at the anodic potential required for electrolysis of uranium dioxide in molten salt. The tungsten anode and stainless steel alloy 316 cathode electrode system was studied at the required reduction potential for UO2 with varying lithium oxide concentrations. Electrochemical impedance spectroscopy showed mixed (kinetic and diffusion) control and an overall low impedance due to extreme corrosion. It was observed that tungsten is sufficiently stable in LiCl - 2wt% Li 2O at 700°C at the required anodic potential for the reduction of uranium oxide. This study identifies tungsten to be a superior anode material to platinum for the electrolytic reduction of uranium oxide, both in terms of superior corrosion behavior and reduced cost, and thus recommends that tungsten be further investigated as an alternative anode for the electrolytic reduction of uranium dioxide.

Role of maximal heart rate and arterial O2 saturation on the decrement of VO2max in moderate acute hypoxia in trained and untrained men.

PubMed

Mollard, P; Woorons, X; Letournel, M; Cornolo, J; Lamberto, C; Beaudry, M; Richalet, J-P

2007-03-01

We aimed to evaluate 1) the altitude where maximal heart rate (HR (max)) decreases significantly in both trained and untrained subjects in moderate acute hypoxia, and 2) if the HR (max) decrease could partly explain the drop of V.O (2max). Seventeen healthy males, nine trained endurance athletes (TS) and eight untrained individuals (US) were studied. Subjects performed incremental exercise tests at sea level and at 5 simulated altitudes (1000, 1500, 2500, 3500, 4500 meters). Power output (PO), heart rate (HR), arterial oxygen saturation (SaO (2)), oxygen uptake (V.O (2)), arterialized blood pH and lactate were measured. Both groups showed a progressive reduction in V.O (2max). The decrement in HR (max) (DeltaHR (max)) was significant from 1000 m for TS and 2500 m for US and more important in TS than US (at 1500 m and 3500 m). At maximal exercise, TS had a greater reduction in SaO (2) (DeltaSaO (2)) at each altitude. DeltaHR (max) observed in TS was correlated with DeltaSaO (2). When the two groups were pooled, simple regressions showed that DeltaV.O (2max) was correlated with both DeltaSaO (2) and DeltaHR (max). However, a multiple regression analysis demonstrated that DeltaSaO (2) alone may account for DeltaV.O (2max). Furthermore, in spite of a greater reduction in SaO (2) and HR (max) in TS, no difference was evidenced in relative DeltaV.O (2max) between groups. Thus, in moderate acute hypoxia, the reduction in SaO (2) is the primary factor to explain the drop of V.O (2max) in trained and untrained subjects.

Rate Controlling Step in the Reduction of Iron Oxides; Kinetics and Mechanism of Wüstite-Iron Step in H2, CO and H2/CO Gas Mixtures

NASA Astrophysics Data System (ADS)

El-Geassy, Abdel-Hady A.

2017-09-01

Wüstite (W1 and W2) micropellets (150-50 μm) were prepared from the reduction of pure Fe2O3 and 2.1% SiO2-doped Fe2O3 in 40%CO/CO2 gas mixture at 1000°C which were then isothermally reduced in H2, CO and H2/CO gas mixtures at 900-1100°C. The reduction reactions was followed by Thermogravimetric Analysis (TG) technique. The effect of gas composition, gas pressure and temperature on the rate of reduction was investigated. The different phases formed during the reduction were chemically and physically characterized. In SiO2-doped wüstite, fayalite (Fe2SiO3) was identified. At the initial reduction stages, the highest rate was obtained in H2 and the lowest was in CO gas. In H2/CO gas mixtures, the measured rate did not follow a simple additive equation. The addition of 5% H2 to CO led to a measurable increase in the rate of reduction compared with that in pure CO. Incubation periods were observed at the early reduction stages of W1 in CO at lower gas pressure (<0.25 atm). In SiO2-doped wüstite, reaction rate minimum was detected in H2 and H2-rich gas mixtures at 925-950°C. The influence of addition of H2 to CO or CO to H2 on the reduction reactions, nucleation and grain growth of iron was intensively studied. Unlike in pure wüstite, the presence of fayalite enhances the reduction reactions with CO and CO-rich gas mixtures. The chemical reaction equations of pure wüstite with CO are given showing the formation of carbonyl-like compound [Fem(CO2)n]*. The apparent activation energy values, at the initial stages, ranged from 53.75 to 133.97 kJ/mole indicating different reaction mechanism although the reduction was designed to proceed by the interfacial chemical reaction.

Influence of the current density on the electrochemical treatment of concentrated 1-butyl-3-methylimidazolium chloride solutions on diamond electrodes.

PubMed

Marcionilio, Suzana M L de Oliveira; Alves, Gisele M; E Silva, Rachel B Góes; Marques, Pablo J Lima; Maia, Poliana D; Neto, Brenno A D; Linares, José J

2016-10-01

This paper focuses on the influence of the current density treatment of a concentrated 1-butyl-3-methylimidazolium chloride (BMImCl) solution on an electrochemical reactor with a boron-doped diamond (BDD) anode. The decrease in the total organic carbon (TOC) and the BMImCl concentration demonstrate the capability of BDD in oxidizing ionic liquids (ILs) and further mineralizing (to CO2 and NO3 (-)) more rapidly at higher current densities in spite of the reduced current efficiency of the process. Moreover, the presence of Cl(-) led to the formation of oxychlorinated anions (mostly ClO3 (-) and ClO4 (-)) and, in combination with the ammonia generated in the cathode from the nitrate reduction, chloramines, more intensely at higher current density. Finally, the analysis of the intermediates formed revealed no apparent influence of the current density on the BMImCl degradation mechanism. The current density presents therefore a complex influence on the IL treatment process that is discussed throughout this paper.

Radiation and chemistry in the stratosphere - Sensitivity to O2 absorption cross sections in the Herzberg continuum

NASA Technical Reports Server (NTRS)

Froidevaux, L.; Yung, Y. L.

1982-01-01

It is suggested that the discrepancies between observed and modeled vertical profiles of such halocarbons as CFCl3, as well as the problem of simultaneously fitting N2O, CH4, CF2Cl2 and CFCl3 profiles with a single eddy diffusion model, are due to an overestimation of the molecular oxygen absorption cross sections in the 200-220 nm spectral region. The replacement of current O2 cross sections in this range with values that are in better agreement with results for the compounds cited leads to N2O, CF2Cl2 and CFCl3 concentration reductions of factors 0.70, 0.62 and 0.19, respectively. Profiles of CH4, H2 and CO remain unchanged, and the predicted concentration of HNO3 above 30 km is reduced by about 50% for yet another improved fit with observations. It is noted that the correction proposed produces a 30% ozone increase near the 20-25 km peak.

Aluminium oxide nanoparticles induced morphological changes, cytotoxicity and oxidative stress in Chinook salmon (CHSE-214) cells.

PubMed

Srikanth, Koigoora; Mahajan, Amit; Pereira, Eduarda; Duarte, Armando Costa; Venkateswara Rao, Janapala

2015-10-01

Aluminium oxide nanoparticles (Al2 O3 NPs) are increasingly used in diverse applications that has raised concern about their safety. Recent studies suggested that Al2 O3 NPs induced oxidative stress may be the cause of toxicity in algae, Ceriodaphnia dubia, Caenorhabditis elegans and Danio rerio. However, there is paucity on the toxicity of Al2 O3 NPs on fish cell lines. The current study was aimed to investigate Al2 O3 NPs induced cytotoxicity, oxidative stress and morphological abnormality of Chinnok salmon cells (CHSE-214). A dose-dependent decline in cell viability was observed in CHSE-214 cells exposed to Al2 O3 NPs. Oxidative stress induced by Al2 O3 NPs in CHSE-214 cells has resulted in the significant reduction of superoxide dismutase, catalase and glutathione in a dose-dependent manner. However, a significant increase in glutathione sulfo-transferase and lipid peroxidation was observed in CHSE-214 cells exposed to Al2 O3 NPs in a dose-dependent manner. Significant morphological changes in CHSE-214 cells were observed when exposed to Al2 O3 NPs at 6, 12 and 24 h. The cells started to detach and appear spherical at 6 h followed by loss of cellular contents resulting in the shrinking of the cells. At 24 h, the cells started to disintegrate and resulted in cell death. Our data demonstrate that Al2 O3 NPs induce cytotoxicity and oxidative stress in a dose-dependent manner in CHSE-214 cells. Thus, our current work may serve as a base-line study for future evaluation of toxicity studies using CHSE-214 cells. Copyright © 2015 John Wiley & Sons, Ltd.

Highly stable CuO incorporated TiO(2) catalyst for photo-catalytic hydrogen production from H(2)O.

PubMed

Bandara, J; Udawatta, C P K; Rajapakse, C S K

2005-11-01

A CuO incorporated TiO(2) catalyst was found to be an active photo-catalyst for the reduction of H(2)O under sacrificial conditions. The catalytic activity originates from the photogeneration of excited electrons in the conduction bands of both TiO(2) and CuO resulting in a build-up of excess electrons in the conduction band of CuO. Consequently, the accumulation of excess electrons in CuO causes a negative shift in the Fermi level of CuO. The efficient inter-particle charge transfer leads to a higher catalytic activity and the formation of highly reduced states of TiO(2)/CuO, which are stable even under oxygen saturated condition. Negative shift in the Fermi level of CuO of the catalyst TiO(2)/CuO gains the required over-voltage necessary for efficient water reduction reaction. The function of CuO is to help the charge separation and to act as a water reduction site. The amount of CuO and crystalline structure were found to be crucial for the catalytic activity and the optimum CuO loading was ca. approximately 5-10%(w/w).

High thermal stability of abrupt SiO2/GaN interface with low interface state density

NASA Astrophysics Data System (ADS)

Truyen, Nguyen Xuan; Taoka, Noriyuki; Ohta, Akio; Makihara, Katsunori; Yamada, Hisashi; Takahashi, Tokio; Ikeda, Mitsuhisa; Shimizu, Mitsuaki; Miyazaki, Seiichi

2018-04-01

The effects of postdeposition annealing (PDA) on the interface properties of a SiO2/GaN structure formed by remote oxygen plasma-enhanced chemical vapor deposition (RP-CVD) were systematically investigated. X-ray photoelectron spectroscopy clarified that PDA in the temperature range from 600 to 800 °C has almost no effects on the chemical bonding features at the SiO2/GaN interface, and that positive charges exist at the interface, the density of which can be reduced by PDA at 800 °C. The capacitance-voltage (C-V) and current density-SiO2 electric field characteristics of the GaN MOS capacitors also confirmed the reduction in interface state density (D it) and the improvement in the breakdown property of the SiO2 film after PDA at 800 °C. Consequently, a high thermal stability of the SiO2/GaN structure with a low fixed charge density and a low D it formed by RP-CVD was demonstrated. This is quite informative for realizing highly robust GaN power devices.

Reductive Dissolution of PuO2(am): The Effect of Fe(II) and Hydroquinone

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

Rai, Dhanpat; Gorby, Yuri A.; Fredrickson, Jim K.

2002-06-01

SYNOPIS-Reducing agents commonly present in geologic environments can increase solubility of PuO2(am), which is otherwise very insoluble, by many orders of magnitude through reduction of Pu(IV) to Pu(III). The reduction reactions involving Fe(II) and hydroquinone, hitherto unquantified under environmental pH values, were found to be relatively fast and controlled the extent of PuO2(am) dissolution: a decrease in redox potential (pe + pH) resulted in concomitant increase in PuO2(am) solubility.

Source identification of nitrous oxide emission pathways from a single-stage nitritation-anammox granular reactor.

PubMed

Ali, Muhammad; Rathnayake, Rathnayake M L D; Zhang, Lei; Ishii, Satoshi; Kindaichi, Tomonori; Satoh, Hisashi; Toyoda, Sakae; Yoshida, Naohiro; Okabe, Satoshi

2016-10-01

Nitrous oxide (N2O) production pathway in a signal-stage nitritation-anammox sequencing batch reactor (SBR) was investigated based on a multilateral approach including real-time N2O monitoring, N2O isotopic composition analysis, and in-situ analyses of spatial distribution of N2O production rate and microbial populations in granular biomass. N2O emission rate was high in the initial phase of the operation cycle and gradually decreased with decreasing NH4(+) concentration. The average emission of N2O was 0.98 ± 0.42% and 1.35 ± 0.72% of the incoming nitrogen load and removed nitrogen, respectively. The N2O isotopic composition analysis revealed that N2O was produced via NH2OH oxidation and NO2(-) reduction pathways equally, although there is an unknown influence from N2O reduction and/or anammox N2O production. However, the N2O isotopomer analysis could not discriminate the relative contribution of nitrifier denitrification and heterotrophic denitrification in the NO2(-) reduction pathway. Various in-situ techniques (e.g. microsensor measurements and FISH (fluorescent in-situ hybridization) analysis) were therefore applied to further identify N2O producers. Microsensor measurements revealed that approximately 70% of N2O was produced in the oxic surface zone, where nitrifiers were predominantly localized. Thus, NH2OH oxidation and NO2 reduction by nitrifiers (nitrifier-denitrification) could be responsible for the N2O production in the oxic zone. The rest of N2O (ca. 30%) was produced in the anammox bacteria-dominated anoxic zone, probably suggesting that NO2(-) reduction by coexisting putative heterotrophic denitrifiers and some other unknown pathway(s) including the possibility of anammox process account for the anaerobic N2O production. Further study is required to identify the anaerobic N2O production pathways. Our multilateral approach can be useful to quantitatively examine the relative contributions of N2O production pathways. Good understanding of the key N2O production pathways is essential to establish a strategy to mitigate N2O emission from biological nitrogen removal processes. Copyright © 2016 Elsevier Ltd. All rights reserved.

Modeling Joule Heating Effect on Lunar O2 Generation via Electrolytic Reduction.

NASA Technical Reports Server (NTRS)

Dominquez, Jesus; Poizeau, Sophie; Sibille, Laurent

2009-01-01

Kennedy Space Center is leading research work on lunar O2 generation via electrolytic reduction of regolith; the metal oxide present in the regolith is dissociated in oxygen anions and metal cations leading to the generation of gaseous oxygen at the anode and liquid metal at the cathode. Electrical resistance of molten regolith is high, leading to heating of the melt when electrical current is applied between the electrodes (Joule heating). The authors have developed a 3D model using a rigorous approach for two coupled physics (thermal and electrical potential) to not only study the effect of Joule heating on temperature distribution throughout the molten regolith but also to evaluate and optimize the design of the electrolytic cells. This paper presents the results of the thermal analysis performed on the model and used to validate the design of the electrolytic cell.

Innovative techniques for the production of energetic radicals for lunar processing including cold plasma processing of local planetary ores

NASA Technical Reports Server (NTRS)

Bullard, D.; Lynch, D. C.

1992-01-01

Hydrogen reduction of ilmenite has been studied by a number of investigators as a potential means for recovery of oxygen from lunar soil. Interest in this process has always rested with the simplicity of the flow diagram and the utilization of established technology. Effective utilization of hydrogen in the reduction process at temperatures of 1200 C and below has always been disappointing and, as such, has led other investigators to focus attention on other systems. Effective utilization of hydrogen in the reduction of ilmenite can be significantly enhanced in the presence of a non-equilibrium hydrogen plasma. Ilmenite at solid specimen temperatures of 600 C to 970 C were reacted in a hydrogen plasma. Those experiments revealed that hydrogen utilization can be significantly enhanced. At a specimen temperature of 850 C the fraction of H2 reacted was 24 percent compared to the 7 percent theoretical limit calculated with thermodynamic theory for the same temperature. An added advantage for a hydrogen plasma involves further reduction of TiO2. Reduction of the iron oxide in ilmenite yields TiO2 and metallic iron as by products. Titanium forms a number of oxides including TiO, Ti2O3, Ti3O5 and the Magneli oxides (Ti4O7 to Ti50O99). In conventional processing of ilmenite with hydrogen it is possible to reduce TiO2 to Ti7O13 within approximately an hour, but with poor utilization of hydrogen on the order of one mole of H2 per thousand. In the cold or non-equilibrium plasma TiO2 can be rapidly reduced to Ti2O3 with hydrogen utilization exceeding 10 percent. Based on design considerations of the plasma reactor greater utilization of the hydrogen in the reduction of TiO2 is possible.

Impact of process parameters on the structural and electrical properties of metal/PZT/Al2O3/silicon gate stack for non-volatile memory applications

NASA Astrophysics Data System (ADS)

Singh, Prashant; Jha, Rajesh Kumar; Singh, Rajat Kumar; Singh, B. R.

2018-02-01

In this paper, we present the structural and electrical properties of the Al2O3 buffer layer on non-volatile memory behavior using Metal/PZT/Al2O3/Silicon structures. Metal/PZT/Silicon and Metal/Al2O3/Silicon structures were also fabricated and characterized to obtain capacitance and leakage current parameters. Lead zirconate titanate (PZT::35:65) and Al2O3 films were deposited by sputtering on the silicon substrate. Memory window, PUND, endurance, breakdown voltage, effective charges, flat-band voltage and leakage current density parameters were measured and the effects of process parameters on the structural and electrical characteristics were investigated. X-ray data show dominant (110) tetragonal phase of the PZT film, which crystallizes at 500 °C. The sputtered Al2O3 film annealed at different temperatures show dominant (312) orientation and amorphous nature at 425 °C. Multiple angle laser ellipsometric analysis reveals the temperature dependence of PZT film refractive index and extinction coefficient. Electrical characterization shows the maximum memory window of 3.9 V and breakdown voltage of 25 V for the Metal/Ferroelectric/Silicon (MFeS) structures annealed at 500 °C. With 10 nm Al2O3 layer in the Metal/Ferroelectric/Insulator/Silicon (MFeIS) structure, the memory window and breakdown voltage was improved to 7.21 and 35 V, respectively. Such structures show high endurance with no significant reduction polarization charge for upto 2.2 × 109 iteration cycles.

Fabrication of a novel metal chromite - Carbon nanotube composite for the highly efficient electrocatalytic reduction of hydrogen peroxide

NASA Astrophysics Data System (ADS)

Shahnavaz, Zohreh; Abd Hamid, Sharifah Bee

2017-06-01

The new electrocatalyst, ZnCr2O4/MWCNTs composite was successfully synthesized by hydrothermal method followed by calcination at 500 °C. A potential application of ZnCr2O4/MWCNTs composite modified electrode as enzyme-free sensor to monitor H2O2 has been studied. The sensor exhibited a high sensitivity of 1717.14 μA mM-1 cm-2 and a low detection limit down to 0.11 μM with a linear wide range from 50 μM to 34.8 mM with a fast response time of 2 s. In addition, modified electrode performance was investigated by measuring current responses of the sensor for three weeks to confirm the great stability of the proposed sensor. Along with these considerable analytical advantages, the as-prepared composite showed very high specificity to H2O2 with complete elimination of interference from uric acid, ascorbic acid, dopamine and glucose. The sensor gave satisfactory results in a real sample, when employed for determination of H2O2 in lens cleaning solution.

Rethinking Sensitized Luminescence in Lanthanide Coordination Polymers and MOFs: Band Sensitization and Water Enhanced Eu Luminescence in [Ln(C15H9O5)3(H2O)3]n (Ln = Eu, Tb).

PubMed

Einkauf, Jeffrey D; Kelley, Tanya T; Chan, Benny C; de Lill, Daniel T

2016-08-15

A coordination polymer [Ln(C15H9O9)3(H2O)3]n (1-Ln = Eu(III), Tb(III)) assembled from benzophenonedicarboxylate was synthesized and characterized. The organic component is shown to sensitize lanthanide-based emission in both compounds, with quantum yields of 36% (Eu) and 6% (Tb). Luminescence of lanthanide coordination polymers is currently described from a molecular approach. This methodology fails to explain the luminescence of this system. It was found that the band structure of the organic component rather than the molecular triplet state was able to explain the observed luminescence. Deuterated (Ln(C15H9O9)3(D2O)3) and dehydrated (Ln(C15H9O9)3) analogues were also studied. When bound H2O was replaced by D2O, lifetime and emission increased as expected. Upon dehydration, lifetimes increased again, but emission of 1-Eu unexpectedly decreased. This reduction is reasoned through an unprecedented enhancement effect of the compound's luminescence by the OH/OD oscillators in the organic-to-Eu(III) energy transfer process.

Highly Sensitive Ethanol Chemical Sensor Based on Novel Ag-Doped Mesoporous α-Fe2O3 Prepared by Modified Sol-Gel Process.

PubMed

Alqahtani, Moteb M; Ali, Atif M; Harraz, Farid A; Faisal, M; Ismail, Adel A; Sayed, Mahmoud A; Al-Assiri, M S

2018-05-21

Mesoporous α-Fe 2 O 3 has been synthesized via a simple sol-gel procedure in the presence of Pluronic (F-127) triblock copolymer as structure directing agent. Silver (Ag) nanoparticles were deposited onto α-Fe 2 O 3 matrix by the photochemical reduction approach. Morphological analysis revealed the formation of Ag nanoparticles with small sizes < 20 nm onto the mesoporous structure of α-Fe 2 O 3 possessing < 50 nm semi-spherical shape. The XRD, FTIR, Raman, UV-vis, PL, and N 2 sorption isotherm studies confirmed the high crystallinity, mesoporosity, and optical characteristics of the synthesized product. The electrochemical sensing toward liquid ethanol has been performed using the current devolved Ag/α-Fe 2 O 3 -modified glassy carbon electrode (GCE) by cyclic voltammetry (CV) and current potential (I-V) techniques, and the obtained results were compared with bare GCE or pure α-Fe 2 O 3 . Mesoporous Ag/α-Fe 2 O 3 was found to largely enhance the sensor sensitivity and it exhibited excellent sensing characteristics during the precision detection of low concentrations of ethanol. High and reproducible sensitivity of 41.27 μAmM - 1  cm - 2 at lower ethanol concentration region (0.05 to 0.8 mM) and 2.93 μAmM - 1  cm - 2 at higher concentration zone (0.8 to 15 mM), with a limit of detection (LOD) of 15.4 μM have been achieved. Investigation on reaction kinetics revealed a characteristic behavior of mixed surface and diffusion-controlled processes. Detailed sensing studies revealed also that the sensitivity toward ethanol was higher than that of methanol or isopropanol. With further effort in developing the synthesis and fabrication approaches, a proper utility for the current proposed protocol for fabricating a better sensor device performance is possible.

Highly Sensitive Ethanol Chemical Sensor Based on Novel Ag-Doped Mesoporous α-Fe2O3 Prepared by Modified Sol-Gel Process

NASA Astrophysics Data System (ADS)

Alqahtani, Moteb M.; Ali, Atif M.; Harraz, Farid A.; Faisal, M.; Ismail, Adel A.; Sayed, Mahmoud A.; Al-Assiri, M. S.

2018-05-01

Mesoporous α-Fe2O3 has been synthesized via a simple sol-gel procedure in the presence of Pluronic (F-127) triblock copolymer as structure directing agent. Silver (Ag) nanoparticles were deposited onto α-Fe2O3 matrix by the photochemical reduction approach. Morphological analysis revealed the formation of Ag nanoparticles with small sizes < 20 nm onto the mesoporous structure of α-Fe2O3 possessing < 50 nm semi-spherical shape. The XRD, FTIR, Raman, UV-vis, PL, and N2 sorption isotherm studies confirmed the high crystallinity, mesoporosity, and optical characteristics of the synthesized product. The electrochemical sensing toward liquid ethanol has been performed using the current devolved Ag/α-Fe2O3-modified glassy carbon electrode (GCE) by cyclic voltammetry ( CV) and current potential ( I-V) techniques, and the obtained results were compared with bare GCE or pure α-Fe2O3. Mesoporous Ag/α-Fe2O3 was found to largely enhance the sensor sensitivity and it exhibited excellent sensing characteristics during the precision detection of low concentrations of ethanol. High and reproducible sensitivity of 41.27 μAmM- 1 cm- 2 at lower ethanol concentration region (0.05 to 0.8 mM) and 2.93 μAmM- 1 cm- 2 at higher concentration zone (0.8 to 15 mM), with a limit of detection (LOD) of 15.4 μM have been achieved. Investigation on reaction kinetics revealed a characteristic behavior of mixed surface and diffusion-controlled processes. Detailed sensing studies revealed also that the sensitivity toward ethanol was higher than that of methanol or isopropanol. With further effort in developing the synthesis and fabrication approaches, a proper utility for the current proposed protocol for fabricating a better sensor device performance is possible.

Carbothermic Reduction Kinetics of Phosphorous Vaporization from Tri-calcium Phosphate (TCP) Under Microwave Rapid Heating With/Without the Presence of Fe3O4

NASA Astrophysics Data System (ADS)

Yoshikawa, Noboru; Sunako, Manami; Kawahira, Keita; Suzuki, Koki; Miyamoto, Kazunori; Taniguchi, Shoji

2018-06-01

The kinetics of vapor phase dephosphorization from tri-calcium phosphate (TCP) by carbothermic reduction was studied with and without the presence of Fe3O4. Microwave heating was utilized to obtain large variations in the heating rate (HR). In the reduction of TCP alone, the phosphorous removal fraction (RF; equal to ΔP2O5/P2O 5 0 , where ΔP2O5 is the weight change and P2O 5 0 is the P2O5 weight before heating) decreased as the HR increased. In other words, a shorter residence time at a high temperature resulted in a smaller reduction fraction of TCP. An apparently third-order reaction was postulated to account for the kinetics using a fitting simulation based on the additive law of the reaction progress. On the other hand, the phosphorous removal (dephosphorization) rate (RR; equal to ΔP2O3/ t MW, where tMW is the microwave heating time period) increased as the HR increased above 1200 °C. The reduction ratio of Fe3O4 above 1100 °C is higher than 97 pct regardless of the heating rate. The reduction of TCP in the presence of Fe3O4 showed that RF increased slightly with increasing HR despite a shorter residence time at a high temperature. The RR also increased with the HR even though RF decreased to half of the values observed in the cases without Fe3O4 for temperatures above 1200 °C. The practicality and optimal operation conditions of phosphorus vapor removal were discussed.

Novel electrochemical process for coal conversion

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

Farooque, M.

1989-07-01

The feasibility of two distinctly different routes to coal conversion at low severity conditions was investigated. An electrochemical approach utilizing both the electro-oxidation and electro-reduction routes was employed. The electro-oxidation route consists of an electrochemical reaction involving H{sub 2}O and coal, leading to the breakup of coal molecules. The observed reaction rate has been explained as a combination of the coal and pyrite electro-oxidation currents. Organic sulfur has been identified as the contributing factor for the observation of more than 100% H{sub 2} production current efficiency with several coal samples. Also, an attractive coal pre-treatment process has been identified whichmore » results in production of useful products and simultaneous upgrading of the coal. Electrochemical oxidation of coal with H{sub 2}O leads to the production of hydrogen, CO{sub 2}, simultaneous removal of pyritic sulfur, and significant reduction of ash content. There is also indirect evidence that the organic sulfur may be removed in the process. A preliminary economic evaluation of this process has projected a cost advantage of > $8 per ton of Illinois {number sign}2 coal. A lab-scale cell has been successfully employed in this study for generating process data useful for future design calculations. This study also explored the electro-reduction route of coal conversion and has successfully demonstrated production of liquid products from different coal types at low severity conditions. A variety of aliphatic and aromatic compounds have been identified in the products. Coal type appeared to be the most important parameter affecting the product spectrum. 32 refs., 26 figs., 19 tabs.« less

Resistive switching mechanism of ZnO/ZrO2-stacked resistive random access memory device annealed at 300 °C by sol-gel method with forming-free operation

NASA Astrophysics Data System (ADS)

Jian, Wen-Yi; You, Hsin-Chiang; Wu, Cheng-Yen

2018-01-01

In this work, we used a sol-gel process to fabricate a ZnO-ZrO2-stacked resistive switching random access memory (ReRAM) device and investigated its switching mechanism. The Gibbs free energy in ZnO, which is higher than that in ZrO2, facilitates the oxidation and reduction reactions of filaments in the ZnO layer. The current-voltage (I-V) characteristics of the device revealed a forming-free operation because of nonlattice oxygen in the oxide layer. In addition, the device can operate under bipolar or unipolar conditions with a reset voltage of 0 to ±2 V, indicating that in this device, Joule heating dominates at reset and the electric field dominates in the set process. Furthermore, the characteristics reveal why the fabricated device exhibits a greater discrete distribution phenomenon for the set voltage than for the reset voltage. These results will enable the fabrication of future ReRAM devices with double-layer oxide structures with improved characteristics.

Mass Spectrometric Studies of Oxides

NASA Technical Reports Server (NTRS)

Jacobson, Nathan S.

2012-01-01

Current studies at NASA Glenn on oxide thermodynamics are discussed. Previous studies on the vaporization of B2O3 in reducing atmospheres led to inconsistent studies when B was used as a reductant. It is shown that liquid B2O3 does not wet B and a clear phase separation was noted in the Knudsen cell. This problem was solved by using FeB and Fe2B to supply a different and constant activity of B. The thermodynamic data thus derived are compared to quantum chemical composite calculations. A major problem in high temperature mass spectrometry is the determination of accurate ionization cross sections, particularly for molecules. The method of Deutsch and Mark shows promise and some sample calculations are discussed. Finally current studies on the thermodynamics of rare earth silicates are discussed. Here the problems are obtaining a measurable signal from SiO2 vaporization and non-equilibrium vaporization. The use of a Ta reducing agent provides a stronger signal, which is related to silica activity. The Whitman-Motzfeld relation adapted to KEMS measurements is applied to obtain equilibrium pressures.

Photoelectrochemical Properties and Photostabilities of High Surface Area CuBi 2O 4 and Ag-Doped CuBi 2O 4 Photocathodes

DOE PAGES

Kang, Donghyeon; Hill, James C.; Park, Yiseul; ...

2016-06-09

Here, electrochemical synthesis methods were developed to produce CuBi 2O 4, a promising p-type oxide for use in solar water splitting, as high surface area electrodes with uniform coverage. These methods involved electrodepositing nanoporous Cu/Bi films with a Cu:Bi ratio of 1:2 from dimethyl sulfoxide or ethylene glycol solutions, and thermally oxidizing them to CuBi 2O 4 at 450°C in air. Ag-doped CuBi 2O 4 electrodes were also prepared by adding a trace amount of Ag+ in the plating medium and codepositing Ag with the Cu/Bi films. In the Ag-doped CuBi 2O 4, Ag+ ions substitutionally replaced Bi3+ ions andmore » increased the hole concentration in CuBi 2O 4. As a result, photocurrent enhancements for both O 2 reduction and water reduction were achieved. Furthermore, while undoped CuBi 2O 4 electrodes suffered from anodic photocorrosion during O 2 reduction due to poor hole transport, Ag-doped CuBiO 4 effectively suppressed anodic photocorrosion. The flat-band potentials of CuBi 2O 4 and Ag-doped CuBi 2O 4 electrodes prepared in this study were found to be more positive than 1.3 V vs RHE in a 0.1 M NaOH solution (pH 12.8), which make these photocathodes highly attractive for use in solar hydrogen production. The optimized CuBi 2O 4/Ag-doped CuBi 2O 4 photocathode showed a photocurrent onset for water reduction at 1.1 V vs RHE, achieving a photovoltage higher than 1 V for water reduction. The thermodynamic feasibility of photoexcited electrons in the conduction band of CuBi 2O 4 to reduce water was also confirmed by detection of H 2 during photocurrent generation. This study provides new understanding for constructing improved CuBi 2O 4 photocathodes by systematically investigating photocorrosion as well as photoelectrochemical properties of high-quality CuBi 2O 4 and Ag-doped CuBi 2O 4 photoelectrodes for photoreduction of both O 2 and water.« less

Photoelectrochemical Properties and Photostabilities of High Surface Area CuBi 2O 4 and Ag-Doped CuBi 2O 4 Photocathodes

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

Kang, Donghyeon; Hill, James C.; Park, Yiseul

Here, electrochemical synthesis methods were developed to produce CuBi 2O 4, a promising p-type oxide for use in solar water splitting, as high surface area electrodes with uniform coverage. These methods involved electrodepositing nanoporous Cu/Bi films with a Cu:Bi ratio of 1:2 from dimethyl sulfoxide or ethylene glycol solutions, and thermally oxidizing them to CuBi 2O 4 at 450°C in air. Ag-doped CuBi 2O 4 electrodes were also prepared by adding a trace amount of Ag+ in the plating medium and codepositing Ag with the Cu/Bi films. In the Ag-doped CuBi 2O 4, Ag+ ions substitutionally replaced Bi3+ ions andmore » increased the hole concentration in CuBi 2O 4. As a result, photocurrent enhancements for both O 2 reduction and water reduction were achieved. Furthermore, while undoped CuBi 2O 4 electrodes suffered from anodic photocorrosion during O 2 reduction due to poor hole transport, Ag-doped CuBiO 4 effectively suppressed anodic photocorrosion. The flat-band potentials of CuBi 2O 4 and Ag-doped CuBi 2O 4 electrodes prepared in this study were found to be more positive than 1.3 V vs RHE in a 0.1 M NaOH solution (pH 12.8), which make these photocathodes highly attractive for use in solar hydrogen production. The optimized CuBi 2O 4/Ag-doped CuBi 2O 4 photocathode showed a photocurrent onset for water reduction at 1.1 V vs RHE, achieving a photovoltage higher than 1 V for water reduction. The thermodynamic feasibility of photoexcited electrons in the conduction band of CuBi 2O 4 to reduce water was also confirmed by detection of H 2 during photocurrent generation. This study provides new understanding for constructing improved CuBi 2O 4 photocathodes by systematically investigating photocorrosion as well as photoelectrochemical properties of high-quality CuBi 2O 4 and Ag-doped CuBi 2O 4 photoelectrodes for photoreduction of both O 2 and water.« less

Recent advances in mathematical modeling of nitrous oxides emissions from wastewater treatment processes.

PubMed

Ni, Bing-Jie; Yuan, Zhiguo

2015-12-15

Nitrous oxide (N2O) can be emitted from wastewater treatment contributing to its greenhouse gas footprint significantly. Mathematical modeling of N2O emissions is of great importance toward the understanding and reduction of the environmental impact of wastewater treatment systems. This article reviews the current status of the modeling of N2O emissions from wastewater treatment. The existing mathematical models describing all the known microbial pathways for N2O production are reviewed and discussed. These included N2O production by ammonia-oxidizing bacteria (AOB) through the hydroxylamine oxidation pathway and the AOB denitrification pathway, N2O production by heterotrophic denitrifiers through the denitrification pathway, and the integration of these pathways in single N2O models. The calibration and validation of these models using lab-scale and full-scale experimental data is also reviewed. We conclude that the mathematical modeling of N2O production, while is still being enhanced supported by new knowledge development, has reached a maturity that facilitates the estimation of site-specific N2O emissions and the development of mitigation strategies for a wastewater treatment plant taking into the specific design and operational conditions of the plant. Copyright © 2015 Elsevier Ltd. All rights reserved.

A membrane-free baffled microbial fuel cell for cathodic reduction of Cu(II) with electricity generation.

PubMed

Tao, Hu-Chun; Li, Wei; Liang, Min; Xu, Nan; Ni, Jin-Ren; Wu, Wei-Min

2011-04-01

A membrane-free baffled microbial fuel cell (MFC) was developed to treat synthetic Cu(II) sulfate containing wastewater in cathode chamber and synthetic glucose-containing wastewater fed to anode chamber. Maximum power density of 314 mW/m(3) with columbic efficiency of 5.3% was obtained using initial Cu(2+) concentration of 6400 mg/L. Higher current density favored the cathodic reduction of Cu(2+), and removal of Cu(2+) by 70% was observed within 144 h using initial concentration of 500 mg/L. Powder X-ray diffraction (XRD) analysis indicated that the Cu(2+) was reduced to Cu(2)O or Cu(2)O plus Cu which deposited on the cathode, and the deficient cathodic reducibility resulted in the formation of Cu(4)(OH)(6)SO(4) at high initial Cu(2+) concentration (500-6400 mg/L). This study suggested a novel low-cost approach to remove and recover Cu(II) from Cu(2+)-containing wastewater using MFC-type reactor. Copyright © 2011 Elsevier Ltd. All rights reserved.

Are dual isotope and isotopomer ratios of N2O useful indicators for N2O turnover during denitrification in nitrate-contaminated aquifers?

NASA Astrophysics Data System (ADS)

Well, Reinhard; Eschenbach, Wolfram; Flessa, Heinz; von der Heide, Carolin; Weymann, Daniel

2012-08-01

Denitrifying aquifers are sources of the greenhouse gas N2O. Isotopic signatures reflect processes of production and reduction of N2O, but it is not clear to which extent these can be used to quantify those processes. We investigated the spatial distribution of isotopologue values of N2O (δ18O, average δ15N, and 15N site preference, SP) in two denitrifying sandy aquifers to study N2O production and reduction and associated isotope effects in groundwater. For the first time, we combined this approach with direct estimation of N2O reduction from excess-N2 analysis. Groundwater samples were collected from 15 monitoring wells and four multilevel sampling wells and analysed for NO3-, dissolved N2O, dissolved O2, excess N2 from denitrification and isotopic signatures of NO3- and N2O. Both aquifers exhibited high NO3- concentrations with average concentrations of 22 and 15 mg N L-1, respectively. Evidence of intense denitrification with associated N2O formation was obtained from mean excess-N2 of 3.5 and 4.3 mg N L-1, respectively. Isotopic signatures of N2O were highly variable with ranges of 17.6-113.2‰ (δ18O), -55.4 to 89.4‰ (δ15Nbulk) and 1.8-97.9‰ (SP). δ15N and δ18O of NO3- ranged from -2.1‰ to 65.5‰ and from -5‰ to 33.5‰, respectively. The relationships between δ15N of NO3-, δ15Nbulk and SP were not in good agreement with the distribution predicted by a Rayleigh-model of isotope fractionation. The large ranges of δ18O and SP of N2O as well as the close correlation between these values could be explained by the fact that N2O reduction to N2 was strongly progressed but variable. We confirm and explain that a large range in SP and δ18O is typical for N2O from denitrifying aquifers, showing that this source signature can be distinguished from the isotopic fingerprint of N2O emitted from soils without water-logging. We conclude that isotopologue values of N2O in our sites were not suitable to quantify production or reduction of N2O or the contribution of different processes to the total N2O flux, apparently because these values were not only governed by individual pathways but eventually also by the spatial distribution of substrates and activity within the aquifers. These observations could be explained by the dynamics of N2O production, reduction and transport in water-saturated systems with heterogenic distribution of microbial activity and by a combination of diffusive and enzymatic isotope effects.

A High Performance H2-Cl2 Fuel Cell for Space Power Applications

NASA Technical Reports Server (NTRS)

Anderson, Everett B.; Taylor, E. Jennings; Wilemski, Gerald; Gelb, Alan

1993-01-01

NASA has numerous airborne/spaceborne applications for which high power and energy density power sources are needed. The proton exchange membrane fuel cell (PEMFC) is an attractive candidate for such a power source. PEMFC's offer many advantages for airborne/spaceborne applications. They have high power and energy densities, convert fuel to electrical power with high efficiency at both part and full load, and can rapidly startup and shutdown. In addition, PEMFC's are lightweight and operate silently. A significant impediment to the attainment of very high power and energy densities by PEMFC's is their current exclusive reliance on oxygen as the oxidant. Conventional PEMFC's oxidize hydrogen at the anode and reduce oxygen at the cathode. The electrode kinetics of oxygen reduction are known to be highly irreversible, incurring large overpotential losses. In addition, the modest open circuit potential of 1.2V for the H2-O2 fuel cell is unattainable due to mixed potential effects at the oxygen electrode. Because of the high overpotential losses, cells using H2 and O2 are capable of achieving high current densities only at very low cell voltages, greatly curtailing their power output. Based on experimental work on chlorine reduction in a gas diffusion electrode, we believe significant increases in both the energy and power densities of PEMFC systems can be achieved by employing chlorine as an alternative oxidant.

Kinetics of nitrous oxide (N2O) formation and reduction by Paracoccus pantotrophus.

PubMed

Read-Daily, B L; Sabba, F; Pavissich, J P; Nerenberg, R

2016-12-01

Nitrous oxide (N 2 O) is a powerful greenhouse gas emitted from wastewater treatment, as well as natural systems, as a result of biological nitrification and denitrification. While denitrifying bacteria can be a significant source of N 2 O, they can also reduce N 2 O to N 2 . More information on the kinetics of N 2 O formation and reduction by denitrifying bacteria is needed to predict and quantify their impact on N 2 O emissions. In this study, kinetic parameters were determined for Paracoccus pantotrophus, a common denitrifying bacterium. Parameters included the maximum specific reduction rates, [Formula: see text], growth rates, [Formula: see text], and yields, Y, for reduction of NO 3 - (nitrate) to nitrite (NO 2 - ), NO 2 - to N 2 O, and N 2 O to N 2 , with acetate as the electron donor. The [Formula: see text] values were 2.9 gN gCOD -1 d -1 for NO 3 - to NO 2 - , 1.4 gN gCOD -1  d -1 for NO 2 - to N 2 O, and 5.3 gN gCOD -1  d -1 for N 2 O to N 2 . The [Formula: see text] values were 2.7, 0.93, and 1.5 d -1 , respectively. When N 2 O and NO 3 - were added concurrently, the apparent (extant) kinetics, [Formula: see text], assuming reduction to N 2 , were 6.3 gCOD gCOD -1  d -1 , compared to 5.4 gCOD gCOD -1  d -1 for NO 3 - as the sole added acceptor. The [Formula: see text] was 1.6 d -1 , compared to 2.5 d -1 for NO 3 - alone. These results suggest that NO 3 - and N 2 O were reduced concurrently. Based on this research, denitrifying bacteria like P. pantotrophus may serve as a significant sink for N 2 O. With careful design and operation, treatment plants can use denitrifying bacteria to minimize N 2 O emissions.

Reduction of selenite to elemental selenium by Enterobacter cloacae SLD1a-1

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

Dungan, R.S.; Frankenberger, W.T. Jr.

1998-11-01

The facultative anaerobic bacterium Enterobacter cloacae strain SLD1a-1 was studied in washed cell suspensions to assess optimal conditions required for the reduction of selenite (SeO{sub 3}{sup 2{minus}}) to elemental selenium (Se{sup 0}). Enterobacter cloacae using glucose (1.4 mM) as an electron donor removed 79% of the added SeO{sub 3}{sup 2{minus}} from solution in 2.5 h. Optimal SeO{sub 3}{sup 2{minus}} reduction occurred at a pH of 6.5 and a temperature of 40 C. Carbohydrate sources arabinose, xylose, and sorbose were found to significantly enhance SeO{sub 3}{sup 2{minus}} reduction over that of glucose. The reduction of SeO{sub 3}{sup 2{minus}} at 7.9 {micro}Mmore » was inhibited by nitrate of levels 1 to 100 times greater, nitrite at levels 5 and 10 times greater, while sulfite at levels of two to four times greater was found to stimulate the reduction of SeO{sub 3}{sup 2{minus}}. Enterobacter cloacae grows on anaerobically incubated plates containing NO{sub 3}{sup {minus}} as the sole terminal electron acceptor and acetate as the electron donor. Use of SeO{sub 3}{sup 2{minus}} as the terminal electron acceptor during anaerobic respiration did not support growth and could only be reduced to Se{sup 0} when NO{sub 3}{sup {minus}} was present.« less

O 2 Activation by Non-Heme Iron Enzymes

DOE PAGES

Solomon, Edward I.; Goudarzi, Serra; Sutherlin, Kyle D.

2016-10-28

The non-heme Fe enzymes are ubiquitous in nature and perform a wide range of functions involving O 2 activation. These had been difficult to study relative to heme enzymes; however, spectroscopic methods have now been developed that provide significant insight into the correlation of structure with function. This Current Topics article summarizes both the molecular mechanism these enzymes use to control O 2 activation in the presence of cosubstrates and the oxygen intermediates these reactions generate. Three types of O 2 activation are observed. First, non-heme reactivity is shown to be different from heme chemistry where a low-spin Fe III-OOHmore » non-heme intermediate directly reacts with substrate. Also, two subclasses of non-heme Fe enzymes generate high-spin Fe IV=O intermediates that provide both σ and π frontier molecular orbitals that can control selectivity. Lastly, for several subclasses of non-heme Fe enzymes, substrate binding to the Fe II site leads to the one electron reductive activation of O 2 to an Fe III-superoxide capable of H-atom abstraction and electrophilic attack.« less

O 2 Activation by Non-Heme Iron Enzymes

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

Solomon, Edward I.; Goudarzi, Serra; Sutherlin, Kyle D.

The non-heme Fe enzymes are ubiquitous in nature and perform a wide range of functions involving O 2 activation. These had been difficult to study relative to heme enzymes; however, spectroscopic methods have now been developed that provide significant insight into the correlation of structure with function. This Current Topics article summarizes both the molecular mechanism these enzymes use to control O 2 activation in the presence of cosubstrates and the oxygen intermediates these reactions generate. Three types of O 2 activation are observed. First, non-heme reactivity is shown to be different from heme chemistry where a low-spin Fe III-OOHmore » non-heme intermediate directly reacts with substrate. Also, two subclasses of non-heme Fe enzymes generate high-spin Fe IV=O intermediates that provide both σ and π frontier molecular orbitals that can control selectivity. Lastly, for several subclasses of non-heme Fe enzymes, substrate binding to the Fe II site leads to the one electron reductive activation of O 2 to an Fe III-superoxide capable of H-atom abstraction and electrophilic attack.« less

Controlling the Interfacial Environment in the Electrosynthesis of MnOx Nanostructures for High-Performance Oxygen Reduction/Evolution Electrocatalysis.

PubMed

Hosseini-Benhangi, Pooya; Kung, Chun Haow; Alfantazi, Akram; Gyenge, Elöd L

2017-08-16

High-performance, nonprecious metal bifunctional electrocatalysts for the oxygen reduction and evolution reactions (ORR and OER, respectively) are of great importance for rechargeable metal-air batteries and regenerative fuel cells. A comprehensive study based on statistical design of experiments is presented to investigate and optimize the surfactant-assisted structure and the resultant bifunctional ORR/OER activity of anodically deposited manganese oxide (MnO x ) catalysts. Three classes of surfactants are studied: anionic (sodium dodecyl sulfate, SDS), non-ionic (t-octylphenoxypolyethoxyethanol, Triton X-100), and cationic (cetyltrimethylammonium bromide, CTAB). The adsorption of surfactants has two main effects: increased deposition current density due to higher Mn 2+ and Mn 3+ concentrations at the outer Helmholtz plane (Frumkin effect on the electrodeposition kinetics) and templating of the MnO x nanostructure. CTAB produces MnO x with nanoneedle (1D) morphology, whereas nanospherical- and nanopetal-like morphologies are obtained with SDS and Triton, respectively. The bifunctional performance is assessed based on three criteria: OER/ORR onset potential window (defined at 2 and -2 mA cm -2 ) and separately the ORR and OER mass activities. The best compromise among these three criteria is obtained either with Triton X-100 deposited catalyst composed of MnOOH and Mn 3 O 4 or SDS deposited catalyst containing a combination of α- and β-MnO 2 , MnOOH, and Mn 3 O 4 .The interaction effects among the deposition variables (surfactant type and concentration, anode potential, Mn 2+ concentration, and temperature) reveal the optimal strategy for high-activity bifunctional MnO x catalyst synthesis. Mass activities for OER and ORR up to 49 A g -1 (at 1556 mV RHE ) and -1.36 A g -1 (at 656 mV RHE ) are obtained, respectively.

Recovery of cobalt from spent lithium-ion batteries using supercritical carbon dioxide extraction.

PubMed

Bertuol, Daniel A; Machado, Caroline M; Silva, Mariana L; Calgaro, Camila O; Dotto, Guilherme L; Tanabe, Eduardo H

2016-05-01

Continuing technological development decreases the useful lifetime of electronic equipment, resulting in the generation of waste and the need for new and more efficient recycling processes. The objective of this work is to study the effectiveness of supercritical fluids for the leaching of cobalt contained in lithium-ion batteries (LIBs). For comparative purposes, leaching tests are performed with supercritical CO2 and co-solvents, as well as under conventional conditions. In both cases, sulfuric acid and H2O2 are used as reagents. The solution obtained from the supercritical leaching is processed using electrowinning in order to recover the cobalt. The results show that at atmospheric pressure, cobalt leaching is favored by increasing the amount of H2O2 (from 0 to 8% v/v). The use of supercritical conditions enable extraction of more than 95wt% of the cobalt, with reduction of the reaction time from 60min (the time employed in leaching at atmospheric pressure) to 5min, and a reduction in the concentration of H2O2 required from 8 to 4% (v/v). Electrowinning using a leach solution achieve a current efficiency of 96% and a deposit with cobalt concentration of 99.5wt%. Copyright © 2016 Elsevier Ltd. All rights reserved.

Chemical oxygen demand reduction in coffee wastewater through chemical flocculation and advanced oxidation processes.

PubMed

Zayas Pérez, Teresa; Geissler, Gunther; Hernandez, Fernando

2007-01-01

The removal of the natural organic matter present in coffee processing wastewater through chemical coagulation-flocculation and advanced oxidation processes (AOP) had been studied. The effectiveness of the removal of natural organic matter using commercial flocculants and UV/H2O2, UV/O3 and UV/H2O2/O3 processes was determined under acidic conditions. For each of these processes, different operational conditions were explored to optimize the treatment efficiency of the coffee wastewater. Coffee wastewater is characterized by a high chemical oxygen demand (COD) and low total suspended solids. The outcomes of coffee wastewater treatment using coagulation-flocculation and photodegradation processes were assessed in terms of reduction of COD, color, and turbidity. It was found that a reduction in COD of 67% could be realized when the coffee wastewater was treated by chemical coagulation-flocculation with lime and coagulant T-1. When coffee wastewater was treated by coagulation-flocculation in combination with UV/H2O2, a COD reduction of 86% was achieved, although only after prolonged UV irradiation. Of the three advanced oxidation processes considered, UV/H2O2, UV/O3 and UV/H2O2/O3, we found that the treatment with UV/H2O2/O3 was the most effective, with an efficiency of color, turbidity and further COD removal of 87%, when applied to the flocculated coffee wastewater.

Formation and Stabilization of Combustion-Generated, Environmentally Persistent Radicals on Ni(II)O Supported on a Silica Surface

PubMed Central

Vejerano, Eric; Lomnicki, Slawomir M.; Dellinger, Barry

2013-01-01

Previous studies have indicated Environmentally Persistent Free Radicals (EPFRs) are formed when hydroxyl- and chlorine-substituted aromatics chemisorbed on Cu(II)O and Fe(III)2O3 surfaces and were stabilized through their interactions with the surface metal cation. The current study reports our laboratory investigation on the formation and stabilization of EPFRs on an Ni(II)O surface. The EPFRs were produced by the chemisorption of adsorbates on the supported metal oxide surface and transfer of an electron from the adsorbate to the metal center, resulting in reduction of the metal cation. Depending on the temperature and the nature of the adsorbate, more than one type of organic radical was formed. A phenoxyl-type radical, with g-value between 2.0029 and 2.0044, and a semiquinone-type radical, with g-value from 2.0050 to as high as 2.0081, were observed. The half-lives on Ni(II)O were long and ranged from 1.5 to 5.2 days, which were similar to what were observed on Fe(III)2O3,. The yields of the EPFRs formed on Ni(II)O was ~ 8x higher than on Cu(II)O and ~50x higher than on Fe(III)2O3. PMID:22831558

Application of a TiO2 nanocomposite in earplugs, a case study of noise reduction.

PubMed

Ibrahimi Ghavamabadi, Leila; Fouladi Dehaghi, Behzad; Hesampour, Morteza; Ahmadi Angali, Kambiz

2018-03-13

Use of hearing protection devices (HPDs) has become necessary when other control measures cannot reduce noise to a safe and standard level. In most countries, more effective hearing protection devices are in demand. The aim of this study was to examine the effects of titanium dioxide (TiO 2 ) nanoparticles on noise reduction efficiency in a polyvinyl chloride (PVC) earplug. An S-60 type PVC polymer as main matrix and TiO 2 with 30 nm size were used. PVC/TiO 2 nanocomposite was mixed at a temperature of 160 °C and 40 rounds per minute (rpm) and the samples were prepared with 0, 0.2 and 0.5 wt% of TiO 2 nanoparticle concentrations. Earplug samples with PVC/TiO 2 (0.2, 0.5 wt%) nanoparticles, when compared with raw earplugs, showed almost equal noise attenuation at low frequencies (500- 125 Hz). However, at high frequencies (2-8 kHz), the power of noise reduction of earplugs containing TiO 2 nanoparticles was significantly increased. The results of the present study showed that samples containing nanoparticles of TiO 2 had more noticeable noise reduction abilities at higher frequencies in comparison with samples without the nanoparticles.

Manganese Recovery by Silicothermic Reduction of MnO in BaO-MnO-MgO-CaF2 (-SiO2) Slags

NASA Astrophysics Data System (ADS)

Heo, Jung Ho; Park, Joo Hyun

2018-04-01

The effects of reducing agent, CaF2 content, and reaction temperature upon the silicothermic reduction of MnO in the BaO-MnO-MgO-CaF2 (-SiO2) slags were investigated. Mn recovery was proportional to Si activity in the molten alloy. Moreover, 90 pct yield of Mn recovery was obtained under 5 mass pct CaF2 content and 1873 K (1600 °C) reaction temperature. Increasing CaF2 content above 5 pct yielded little or no further increase in Mn recovery, because it was accompanied by increased slag viscosity owing to the precipitation of high melting point compounds such as Ba2SiO4.

Processing, structure, and characterizaton of nickel-alumina composites obtained by the partial reduction of zirconia-doped nickel-aluminum oxide and application to the tempering of ceramics

NASA Astrophysics Data System (ADS)

Barbieri, Thomas John

1999-11-01

Partial reduction of the spinel compound NiAl2O4 results in a two phase composite mixture of Ni + Al2O3. The reduction reaction has a volume decrease associated with it, which theoretically could generate large residual stresses, which have the potential to "temper" a ceramic, i.e. to place the surface of a ceramic component into a state of residual compression. As the first step towards tempering a ceramic, it is necessary to demonstrate that appreciable stresses can be generated by this volume change, since they may be relieved by either cracking or diffusional relaxation processes at the high temperature of the reduction reaction. It was necessary to determine the best processing methods to use for producing the tempered specimens. Results are presented from a systematic study on the effect of the variation of processing parameters on the reduction behavior of NiAl2O4 doped with ZrO2. Specimen characteristics of interest were time required for reduction, microstructural development, volume contraction achieved and porosity generated during reduction, and the ability to survive the reduction process without fracturing. These results were applied to the tempering process. A simple specimen geometry was used for tempering which involved an Al 2O3 cylinder bonded to an outer NiAl2O4 ring. Finite element calculations were performed to predict the residual stresses generated by the volume contraction of the ring and the coefficient of thermal expansion, (CTE) mismatch between the Al2O3 core and the reduced composite ring. Stress measurements performed on the Al2 O3 core of each specimen using the "d vs. Sin 2Psi" method of X-ray diffraction indicate that only the CTE-induced stresses remain in the specimens after completion of the tempering process. Microstructural analysis of the tempered specimens was performed to determine if residual stresses were developed during reduction, and what processes occurred to relieve these stresses. The results indicate that stresses are generated during the reduction process, but they are dissipated through catastrophic fracture, cation rearrangement in the lattice, and creep. Further evidence of the presence of residual stresses during reduction was found in a decrease in coarsening rate in tempered specimens.

Electrocatalytic performances of LaNi1-xMgxO3 perovskite oxides as bi-functional catalysts for lithium air batteries

NASA Astrophysics Data System (ADS)

Du, Zhenzhen; Yang, Peng; Wang, Long; Lu, Yuhao; Goodenough, J. B.; Zhang, Jian; Zhang, Dawei

2014-11-01

Mg-doped perovskite oxides LaNi1-xMgxO3 (x = 0, 0.08, 0.15) electrocatalysts are synthesized by a sol-gel method using citric acid as complex agent and ethylene glycol as thickening agent. The intrinsic oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) activity of as-prepared perovskite oxides in aqueous electrolyte are examined on a rotating disk electrode (RDE) set up. Li-air primary batteries on the basis of Mg-doped perovskite oxides LaNi1-xMgxO3 (x = 0, 0.08, 0.15) and nonaqueous electrolyte are also fabricated and tested. In terms of the ORR current densities and OER current densities, the performance is enhanced in the order of LaNiO3, LaNi0.92Mg0.08O3 and LaNi0.85Mg0.15O3. Most notably, partially substituting nickel with magnesium suppresses formation of Ni2+ and ensures high concentration of both OER and ORR reaction energy favorable Ni3+ (eg = 1) on the surface of perovskite catalysts. Nonaqueous Li-air primary battery using LaNi0.92Mg0.08O3 and LaNi0.85Mg0.15O3 as the cathode catalysts exhibit improved performances compared with LaNiO3 catalyst, which are consistent with the ORR current densities.

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

Liu, Shizhong; White, Michael G.; Liu, Ping

Here, we report a detailed mechanistic study of the oxygen reduction reaction (ORR) on Pt(111) in alkaline solution, combining density functional theory and kinetic Monte Carlo simulations. A complex reaction network including four possible pathways via either 2e – or 4e – transfer is established and is able to reproduce the experimental measured polarization curve at both low- and high-potential regions. Our results show that it is essential to account for solvation by water and the dynamic coverage of *OH to describe the reaction kinetics well. In addition, a chemisorbed water (*H 2O)-mediated mechanism including 4e – transfers is identified,more » where the reduction steps via *H 2O on the surface are potential-independent and only the final removal of *OH from the surface in the form of OH –(aq) contributes to the current. For the ORR in alkaline solutions, such a mechanism is more competitive than the associative and dissociative mechanisms typically used to describe the ORR in acid solution. Finally, *OH and **O 2 intermediates are found to be critically important for tuning the ORR activity of Pt in alkaline solution. To enhance the activity, the binding of Pt should be tuned in such a way that *OH binding is weak enough to release more surface sites under working conditions, while **O 2 binding is strong enough to enable the ORR via the 4e – transfer mechanism.« less

Effect of Selective Heart Rate Slowing in Heart Failure With Preserved Ejection Fraction.

PubMed

Pal, Nikhil; Sivaswamy, Nadiya; Mahmod, Masliza; Yavari, Arash; Rudd, Amelia; Singh, Satnam; Dawson, Dana K; Francis, Jane M; Dwight, Jeremy S; Watkins, Hugh; Neubauer, Stefan; Frenneaux, Michael; Ashrafian, Houman

2015-11-03

Heart failure with preserved ejection fraction (HFpEF) is associated with significant morbidity and mortality but is currently refractory to therapy. Despite limited evidence, heart rate reduction has been advocated, on the basis of physiological considerations, as a therapeutic strategy in HFpEF. We tested the hypothesis that heart rate reduction improves exercise capacity in HFpEF. We conducted a randomized, crossover study comparing selective heart rate reduction with the If blocker ivabradine at 7.5 mg twice daily versus placebo for 2 weeks each in 22 symptomatic patients with HFpEF who had objective evidence of exercise limitation (peak oxygen consumption at maximal exercise [o2 peak] <80% predicted for age and sex). The result was compared with 22 similarly treated matched asymptomatic hypertensive volunteers. The primary end point was the change in o2 peak. Secondary outcomes included tissue Doppler-derived E/e' at echocardiography, plasma brain natriuretic peptide, and quality-of-life scores. Ivabradine significantly reduced peak heart rate compared with placebo in the HFpEF (107 versus 129 bpm; P<0.0001) and hypertensive (127 versus 145 bpm; P=0.003) cohorts. Ivabradine compared with placebo significantly worsened the change in o2 peak in the HFpEF cohort (-2.1 versus 0.9 mL·kg(-1)·min(-1); P=0.003) and significantly reduced submaximal exercise capacity, as determined by the oxygen uptake efficiency slope. No significant effects on the secondary end points were discernable. Our observations bring into question the value of heart rate reduction with ivabradine for improving symptoms in a HFpEF population characterized by exercise limitation. URL: http://www.clinicaltrials.gov. Unique identifier: NCT02354573. © 2015 The Authors.

Electrochemical Reduction of Protic Supercritical CO2 on Copper Electrodes.

PubMed

Melchaeva, Olga; Voyame, Patrick; Bassetto, Victor Costa; Prokein, Michael; Renner, Manfred; Weidner, Eckhard; Petermann, Marcus; Battistel, Alberto

2017-09-22

The electrochemical reduction of carbon dioxide is usually studied in aqueous solutions under ambient conditions. However, the main disadvantages of this method are high hydrogen evolution and low faradaic efficiencies of carbon-based products. Supercritical CO 2 (scCO 2 ) can be used as a solvent itself to suppresses hydrogen evolution and tune the carbon-based product yield; however, it has received little attention for this purpose. Therefore, the focus of this study was on the electrochemical reduction of scCO 2 . The conductivity of scCO 2 was increased through the addition of supporting electrolyte and a cosolvent (acetonitrile). Furthermore, the addition of protic solutions of different pH to scCO 2 was investigated. 1 m H 2 SO 4 , trifluoroethanol, H 2 O, KOH, and CsHCO 3 solutions were used to determine the effect on current density, faradaic efficiency, and selectivity of the scCO 2 reduction. The reduction of scCO 2 to methanol and ethanol are reported for the first time. However, methane and ethylene were not observed. Additionally, corrosion of the Cu electrode was noticed. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis of Copper-Based Nanostructured Catalysts on SiO2-Al2O3, SiO2-TiO2, and SiO2-ZrO2 Supports for NO Reduction.

PubMed

Namkhang, Pornpan; Kongkachuichay, Paisan

2015-07-01

The selective catalytic reduction of NO over a series of Cu-based catalysts supported on modified silica including SiO2-Al2O3, SiO2-TiO2, and SiO2-ZrO2 prepared via a sol-gel process and a flame spray pyrolysis (FSP) was studied. The prepared catalysts were characterized by means of TEM, XRD, XRF, TPR, and nitrogen physisorption measurement techniques, to determine particle diameter, morphology, crystallinity, phase composition, copper reducibility, surface area, and pore size of catalysts. The particles obtained from sol-gel method were almost spherical while the particles obtained from the FSP were clearly spherical and non-porous nanosized particles. The effects of Si:Al, Si:Ti, and Si:Zr molar ratio of precursor were identified as the domain for different crystalline phase of materials. It was clearly seen that a high SiO2 content inhibited the crystallization of materials. The BET surface area of catalysts obtained from sol-gel method was higher than that from the FSP and it shows that surface area increased with increasing SiO2 molar ratio due to high surface area from SiO2. The catalyst performances were tested for the selective catalytic reduction of NO with H2. It was found that the catalyst prepared over 7 wt% Cu on Si02-Al2O3 support was the most active compared with the others which converted NO as more than 70%. Moreover, the excess copper decreased the performance of NO reduction, due to the formation of CuO agglomeration covered on the porous silica as well as the alumina surface, preventing the direct contact of CO2 and AL2O3.

Co@Co3 O4 @PPD Core@bishell Nanoparticle-Based Composite as an Efficient Electrocatalyst for Oxygen Reduction Reaction.

PubMed

Wang, Zhijuan; Li, Bing; Ge, Xiaoming; Goh, F W Thomas; Zhang, Xiao; Du, Guojun; Wuu, Delvin; Liu, Zhaolin; Andy Hor, T S; Zhang, Hua; Zong, Yun

2016-05-01

Durable electrocatalysts with high catalytic activity toward oxygen reduction reaction (ORR) are crucial to high-performance primary zinc-air batteries (ZnABs) and direct methanol fuel cells (DMFCs). An efficient composite electrocatalyst, Co@Co3 O4 core@shell nanoparticles (NPs) embedded in pyrolyzed polydopamine (PPD) is reported, i.e., in Co@Co3 O4 @PPD core@bishell structure, obtained via a three-step sequential process involving hydrothermal synthesis, high temperature calcination under nitrogen atmosphere, and gentle heating in air. With Co@Co3 O4 NPs encapsulated by ultrathin highly graphitized N-doped carbon, the catalyst exhibits excellent stability in aqueous alkaline solution over extended period and good tolerance to methanol crossover effect. The integration of N-doped graphitic carbon outer shell and ultrathin nanocrystalline Co3 O4 inner shell enable high ORR activity of the core@bishell NPs, as evidenced by ZnABs using catalyst of Co@Co3 O4 @PPD in air-cathode which delivers a stable voltage profile over 40 h at a discharge current density of as high as 20 mA cm(-2) . © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Improved oxygen reduction reaction catalyzed by Pt/Clay/Nafion nanocomposite for PEM fuel cells.

PubMed

Narayanamoorthy, B; Datta, K K R; Eswaramoorthy, M; Balaji, S

2012-07-25

A novel Pt nanoparticle (Pt NP) embedded aminoclay/Nafion (Pt/AC/N) nanocomposite catalyst film was prepared for oxygen reduction reaction by sol-gel method. The prepared nanocomposite films were surface characterized using XRD and TEM and thermal stability was studied by TGA. The prepared film has firmly bound Pt NP and could exhibit an improved electro-reduction activity compared to vulcan carbon/Nafion supported Pt NP (Pt/VC/N). Moreover, the Pt/AC/N film possessed good stability in the acidic environment. The limiting current density of the Pt/AC/N film with 35.4 μg/cm(2) of Pt loading was found to be 4.2 mA/cm(2), which is 30% higher than that of the Pt/VC/N. The maximum H2O2 intermediate formation was found to be ∼1.6% and the reaction found to follow a four electron transfer mechanism. Accelerated durability test for 2000 potential cycles showed that ca. 78% of initial limiting current was retained. The results are encouraging for possible use of the Pt/AC/N as the free-standing electrocatalyst layer for polymer electrolyte membrane fuel cells.

Comparing the efficacy of hyper-pure chlorine-dioxide with other oral antiseptics on oral pathogen microorganisms and biofilm in vitro.

PubMed

Herczegh, Anna; Gyurkovics, Milán; Agababyan, Hayk; Ghidán, Agoston; Lohinai, Zsolt

2013-09-01

This study examines the antibacterial properties of sodium hypochlorite (NaOCl), chlorhexidine gluconate (CHX), Listerine®, and high purity chlorine dioxide (Solumium, ClO2) on selected common oral pathogen microorganisms and on dental biofilm in vitro. Antimicrobial activity of oral antiseptics was compared to the gold standard phenol. We investigated Streptococcus mutans, Lactobacillus acidophilus, Enterococcus faecalis, Veillonella alcalescens, Eikenella corrodens, Actinobacillus actinomycetemcomitans and Candida albicans as some important representatives of the oral pathogens. Furthermore, we collected dental plaque from the upper first molars of healthy young students. Massive biofilm was formed in vitro and its reduction was measured after treating it with mouthrinses: CHX, Listerine® or hyper pure ClO2. Their biofilm disrupting effect was measured after dissolving the crystal violet stain from biofilm by photometer. The results have showed that hyper pure ClO2 solution is more effective than other currently used disinfectants in case of aerobic bacteria and Candida yeast. In case of anaerobes its efficiency is similar to CHX solution. The biofilm dissolving effect of hyper pure ClO2 is significantly stronger compared to CHX and Listerine® after 5 min treatment. In conclusion, hyper pure ClO2 has a potent disinfectant efficacy on oral pathogenic microorganisms and a powerful biofilm dissolving effect compared to the current antiseptics, therefore high purity ClO2 may be a new promising preventive and therapeutic adjuvant in home oral care and in dental or oral surgery practice.

Reduction of O2 slow component by priming exercise: novel mechanistic insights from time-resolved near-infrared spectroscopy

PubMed Central

Fukuoka, Yoshiyuki; Poole, David C; Barstow, Thomas J; Kondo, Narihiko; Nishiwaki, Masato; Okushima, Dai; Koga, Shunsaku

2015-01-01

Novel time-resolved near-infrared spectroscopy (TR-NIRS), with adipose tissue thickness correction, was used to test the hypotheses that heavy priming exercise reduces the V̇O2 slow component (V̇O2SC) (1) by elevating microvascular [Hb] volume at multiple sites within the quadriceps femoris (2) rather than reducing the heterogeneity of muscle deoxygenation kinetics. Twelve subjects completed two 6-min bouts of heavy work rate exercise, separated by 6 min of unloaded cycling. Priming exercise induced faster overall V̇O2 kinetics consequent to a substantial reduction in the V̇O2SC (0.27 ± 0.12 vs. 0.11 ± 0.09 L·min−1, P < 0.05) with an unchanged primary V̇O2 time constant. An increased baseline for the primed bout [total (Hb + Mb)] (197.5 ± 21.6 vs. 210.7 ± 22.5 μmol L−1, P < 0.01), reflecting increased microvascular [Hb] volume, correlated significantly with the V̇O2SC reduction. At multiple sites within the quadriceps femoris, priming exercise reduced the baseline and slowed the increase in [deoxy (Hb + Mb)]. Changes in the intersite coefficient of variation in the time delay and time constant of [deoxy (Hb + Mb)] during the second bout were not correlated with the V̇O2SC reduction. These results support a mechanistic link between priming exercise-induced increase in muscle [Hb] volume and the reduced V̇O2SC that serves to speed overall V̇O2 kinetics. However, reduction in the heterogeneity of muscle deoxygenation kinetics does not appear to be an obligatory feature of the priming response. PMID:26109190

Improving the photovoltaic performance of the all-solid-state TiO2 NR/CuInS2 solar cell by hydrogen plasma treatment.

PubMed

Chen, Bingfeng; Niu, Wenzhe; Lou, Zirui; Ye, Zhizhen; Zhu, Liping

2018-07-06

The interfacial properties of the heterojunction between p-type and n-type materials play an important role in the performance of the solar cell. In this paper, a p-type CuInS 2 film was deposited on TiO 2 nanorod arrays by spin coating to fabricate an all-solid-state solar cell and the TiO 2 nanorod arrays were treated with hydrogen plasma(H:TiO 2 ) to ameliorate the interfacial properties. The influence of the hydrogen plasma treatment on the performance of the solar cell was investigated. The short-circuit current density was obviously raised and the power conversion efficiency of the solar cell improved to 0.30%, which is three times that of solar cells without hydrogen plasma treatment. The enhancement of the performance is attributed to not only the enhancement of carrier separation and transport, but the reduction of the recombination of electrons and holes, which is caused by hydrogen plasma treatment.

Improving the photovoltaic performance of the all-solid-state TiO2 NR/CuInS2 solar cell by hydrogen plasma treatment

NASA Astrophysics Data System (ADS)

Chen, Bingfeng; Niu, Wenzhe; Lou, Zirui; Ye, Zhizhen; Zhu, Liping

2018-07-01

The interfacial properties of the heterojunction between p-type and n-type materials play an important role in the performance of the solar cell. In this paper, a p-type CuInS2 film was deposited on TiO2 nanorod arrays by spin coating to fabricate an all-solid-state solar cell and the TiO2 nanorod arrays were treated with hydrogen plasma(H:TiO2) to ameliorate the interfacial properties. The influence of the hydrogen plasma treatment on the performance of the solar cell was investigated. The short-circuit current density was obviously raised and the power conversion efficiency of the solar cell improved to 0.30%, which is three times that of solar cells without hydrogen plasma treatment. The enhancement of the performance is attributed to not only the enhancement of carrier separation and transport, but the reduction of the recombination of electrons and holes, which is caused by hydrogen plasma treatment.

MnO2 nanorods/SiO2 sphere coated on single-wall carbon nanotubes as supercapacitor electrode for high energy storage applications

NASA Astrophysics Data System (ADS)

Iro, Zaharaddeen S.; Subramani, C.; Kesavan, T.; Dash, S. S.; Sasidharan, M.; Sundramoorthy, Ashok K.

2017-12-01

A composite of MnO2/SiO2 sphere was coated on single-wall carbon nanotubes (MnO2/SiO2/SWCNT) using one-pot hydrothermal synthesis method. KMnO4 was used as an oxidizing agent for mild functionalization of single-wall carbon nanotubes (SWCNT), and also as a precursor of MnO2. A comparative study in the presence of SiO2 and SWCNT was carried out using bare MnO2 as a reference. After addition of SiO2, the composite obtained showed an increase in both the specific capacitance and cycle life which can be associated with spherical shape of SiO2 which offered reduction sites for MnO2. With the addition of SWCNT less than 5%, the composite further showed an increase in capacitance and cycle life, this is because of the good conductive nature, excellent mechanical property and chemical stability of SWCNT. The electrochemical behaviour was studied using cyclic voltammetry and galvanostatic charge/discharge method in 1 M Na2SO4 electrolyte. The specific capacitance of MnO2, MnO2/SiO2 and MnO2/SiO2/SWCNT composite is 73.6 F g-1, 108.7 F g-1 and 136 F g-1 at a current density of 1 A g-1, respectively. The MnO2/SiO2/SWCNT energy density was 68 Wh kg-1 with power density of 444.4 W kg-1. The MnO2/SiO2/SWCNT composite retained 88% of its specific capacitance after 500 cycles. We envisage that this hybrid material could be applied for preparation of supercapacitor electrode.

Solution processed transition metal oxide anode buffer layers for efficiency and stability enhancement of polymer solar cells

NASA Astrophysics Data System (ADS)

Ameen, M. Yoosuf; Shamjid, P.; Abhijith, T.; Reddy, V. S.

2018-01-01

Polymer solar cells were fabricated with solution-processed transition metal oxides, MoO3 and V2O5 as anode buffer layers (ABLs). The optimized device with V2O5 ABL exhibited considerably higher power conversion efficiency (PCE) compared to the devices based on MoO3 and poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) ABLs. The space charge limited current measurements and impedance spectroscopy results of hole-only devices revealed that V2O5 provided a very low charge transfer resistance and high hole mobility, facilitating efficient hole transfer from the active layer to the ITO anode. More importantly, incorporation of V2O5 as ABL resulted in substantial improvement in device stability compared to MoO3 and PEDOT:PSS based devices. Unencapsulated PEDOT:PSS-based devices stored at a relative humidity of 45% have shown complete failure within 96 h. Whereas, MoO3 and V2O5 based devices stored in similar conditions retained 22% and 80% of their initial PCEs after 96 h. Significantly higher stability of the V2O5-based device is ascribed to the reduction in degradation of the anode/active layer interface, as evident from the electrical measurements.

Moessbauer spectra of ferrite catalysts used in oxidative dehydrogenation

NASA Technical Reports Server (NTRS)

Cares, W. R.; Hightower, J. W.

1971-01-01

Room temperature Mossbauer spectroscopy was used to examine bulk changes which occur in low surface area CoFe2O4 and CuFe2O4 catalysts as a result of contact with various mixtures of trans-2-butene and O2 during oxidative dehydrogenation reactions at about 420 C. So long as there was at least some O2 in the gas phase, the CoFe2O4 spectrum was essentially unchanged. However, the spectrum changed from a random spinel in the oxidized state to an inverse spinel as it was reduced by oxide ion removal. The steady state catalyst lies very near the fully oxidized state. More dramatic solid state changes occurred as the CuFe2O4 underwent reduction. Under severe reduction, the ferrite was transformed into Cu and Fe3O4, but it could be reversibly recovered by oxidation. An intense doublet located near zero velocity persisted in all spectra of CuFe2O4 regardless of the state of reduction.

Oxidase catalysis via aerobically generated hypervalent iodine intermediates

NASA Astrophysics Data System (ADS)

Maity, Asim; Hyun, Sung-Min; Powers, David C.

2018-02-01

The development of sustainable oxidation chemistry demands strategies to harness O2 as a terminal oxidant. Oxidase catalysis, in which O2 serves as a chemical oxidant without necessitating incorporation of oxygen into reaction products, would allow diverse substrate functionalization chemistry to be coupled to O2 reduction. Direct O2 utilization suffers from intrinsic challenges imposed by the triplet ground state of O2 and the disparate electron inventories of four-electron O2 reduction and two-electron substrate oxidation. Here, we generate hypervalent iodine reagents—a broadly useful class of selective two-electron oxidants—from O2. This is achieved by intercepting reactive intermediates of aldehyde autoxidation to aerobically generate hypervalent iodine reagents for a broad array of substrate oxidation reactions. The use of aryl iodides as mediators of aerobic oxidation underpins an oxidase catalysis platform that couples substrate oxidation directly to O2 reduction. We anticipate that aerobically generated hypervalent iodine reagents will expand the scope of aerobic oxidation chemistry in chemical synthesis.

Scalable cross-point resistive switching memory and mechanism through an understanding of H2O2/glucose sensing using an IrOx/Al2O3/W structure.

PubMed

Chakrabarti, Somsubhra; Maikap, Siddheswar; Samanta, Subhranu; Jana, Surajit; Roy, Anisha; Qiu, Jian-Tai

2017-10-04

The resistive switching characteristics of a scalable IrO x /Al 2 O 3 /W cross-point structure and its mechanism for pH/H 2 O 2 sensing along with glucose detection have been investigated for the first time. Porous IrO x and Ir 3+ /Ir 4+ oxidation states are observed via high-resolution transmission electron microscope, field-emission scanning electron spectroscopy, and X-ray photo-electron spectroscopy. The 20 nm-thick IrO x devices in sidewall contact show consecutive long dc cycles at a low current compliance (CC) of 10 μA, multi-level operation with CC varying from 10 μA to 100 μA, and long program/erase endurance of >10 9 cycles with 100 ns pulse width. IrO x with a thickness of 2 nm in the IrO x /Al 2 O 3 /SiO 2 /p-Si structure has shown super-Nernstian pH sensitivity of 115 mV per pH, and detection of H 2 O 2 over the range of 1-100 nM is also achieved owing to the porous and reduction-oxidation (redox) characteristics of the IrO x membrane, whereas a pure Al 2 O 3 /SiO 2 membrane does not show H 2 O 2 sensing. A simulation based on Schottky, hopping, and Fowler-Nordheim tunneling conduction, and a redox reaction, is proposed. The experimental I-V curve matches very well with simulation. The resistive switching mechanism is owing to O 2- ion migration, and the redox reaction of Ir 3+ /Ir 4+ at the IrO x /Al 2 O 3 interface through H 2 O 2 sensing as well as Schottky barrier height modulation is responsible. Glucose at a low concentration of 10 pM is detected using a completely new process in the IrO x /Al 2 O 3 /W cross-point structure. Therefore, this cross-point memory shows a method for low cost, scalable, memory with low current, multi-level operation, which will be useful for future highly dense three-dimensional (3D) memory and as a bio-sensor for the future diagnosis of human diseases.

Characterization of PZT Capacitor Structures with Various Electrode Materials Processed In-Situ Using AN Automated, Rotating Elemental Target, Ion Beam Deposition System

NASA Astrophysics Data System (ADS)

Gifford, Kenneth Douglas

Ferroelectric thin film capacitor structures containing lead zirconate titanate (PZT) as the dielectric, with the chemical formula Pb(rm Zr_{x }Ti_{1-x})O_3, were synthesized in-situ with an automated ion beam sputter deposition system. Platinum (Pt), conductive ruthenium oxide (RuO_2), and two types of Pt-RuO_2 hybrid electrodes were used as the electrode materials. The capacitor structures are characterized in terms of microstructure and electrical characteristics. Reduction or elimination of non-ferroelectric phases, that nucleate during PZT processing on Pt/TiO _2/MgO and RuO_2/MgO substrates, is achieved by reducing the thickness of the individually deposited layers and by interposing a buffer layer (~100-200A) of PbTiO _3 (PT) between the bottom electrode and the PZT film. Capacitor structures containing a Pt electrode exhibit poor fatigue resistance, irregardless of the PZT microstructure or the use of a PT buffer layer. From these results, and results from similar capacitors synthesized with sol-gel and laser ablation, PZT-based capacitor structures containing Pt electrodes are considered to be unsuitable for use in memory devices. Using a PT buffer layer, in capacitor structures containing RuO_2 top and bottom electrodes and polycrystalline, highly (101) oriented PZT, reduces or eliminates the nucleation of zirconium-titanium oxide, non-ferroelectric species at the bottom electrode interface during processing. This results in good fatigue resistance up to ~2times10^ {10} switching cycles. DC leakage current density vs. time measurements follow the Curie-von Schweidler law, J(t) ~ t^ {rm -n}. Identification of the high electric field current conduction mechanism is inconclusive. The good fatigue resistance, low dc leakage current, and excellent retention, qualifies the use of these capacitor structures in non-volatile random access (NVRAM) and dynamic random access (DRAM) memory devices. Excellent fatigue resistance (10% loss in remanent polarization up to ~2times10^ {10} switching cycles), low dc leakage current, and excellent retention are observed in capacitor structures containing polycrystalline PZT (exhibiting dominant (001) and (100) XRD reflections), a Pt-RuO_2 hybrid bottom electrode (Type IA), and an RuO _2 top electrode. These results, and electrical characterization results on capacitors containing co-deposited Pt-RuO_2 hybrid electrodes (Type II), show potential for application of these capacitor structures in NVRAM and DRAM memory devices.

A new V-doped Bi2(O,S)3 oxysulfide catalyst for highly efficient catalytic reduction of 2-nitroaniline and organic dyes.

PubMed

Abay, Angaw Kelemework; Kuo, Dong-Hau; Chen, Xiaoyun; Saragih, Albert Daniel

2017-12-01

A new type of convenient, and environmentally friendly, Vanadium (V)-doped Bi 2 (O,S) 3 oxysulfide catalyst with different V contents was successfully synthesized via a simple and facile method. The obtained V-doped Bi 2 (O,S) 3 solid solution catalysts were fully characterized by conventional methods. The catalytic performance of the samples was tested by using the reduction of 2-nitroaniline (2-NA) in aqueous solution. The reduction/decolorization of methylene blue (MB) and rhodamine B (RhB) was also chosen to evaluate the universality of catalysts. It was observed that the introduction of V can improve the catalytic performance, and 20%V-Bi 2 (O,S) 3 was found to be the optimal V doping concentration for the reduction of 2-NA, MB, and RhB dyes. For comparative purposes, a related V-free Bi 2 (O, S) 3 oxysulfide material was synthesized and tested as the catalyst. The superior activity of V-doped Bi 2 (O,S) 3 over pure Bi 2 (O,S) 3 was ascribed mainly to an increase in active sites of the material and also due to the presence of synergistic effects. The presence of V 5+ as found from XPS analysis may interact with Bi atoms and enhancing the catalytic activity of the sample. In the catalytic reduction of 2-NA, MB and RhB, the obtained V-doped Bi 2 (O,S) 3 oxysulfide catalyst exhibited excellent catalytic activity as compared with other reported catalysts. Furthermore this highly efficient, low-cost and easily reusable V-doped Bi 2 (O,S) 3 catalyst is anticipated to be of great potential in catalysis in the future. Copyright © 2017 Elsevier Ltd. All rights reserved.

The rate of nitrite reduction in leaves as indicated by O2 and CO2 exchange during photosynthesis

PubMed Central

Eichelmann, H.; Oja, V.; Peterson, R.B.; Laisk, A.

2011-01-01

Light response (at 300 ppm CO2 and 10–50 ppm O2 in N2) and CO2 response curves [at absorbed photon fluence rate (PAD) of 550 μmol m−2 s−1] of O2 evolution and CO2 uptake were measured in tobacco (Nicotiana tabacum L.) leaves grown on either NO3− or NH4+ as N source and in potato (Solanum tuberosum L.), sorghum (Sorghum bicolor L. Moench), and amaranth (Amaranthus cruentus L.) leaves grown on NH4NO3. Photosynthetic O2 evolution in excess of CO2 uptake was measured with a stabilized zirconia O2 electrode and an infrared CO2 analyser, respectively, and the difference assumed to represent the rate of electron flow to acceptors alternative to CO2, mainly NO2−, SO42−, and oxaloacetate. In NO3−-grown tobacco, as well as in sorghum, amaranth, and young potato, the photosynthetic O2–CO2 flux difference rapidly increased to about 1 μmol m−2 s−1 at very low PADs and the process was saturated at 50 μmol quanta m−2 s−1. At higher PADs the O2–CO2 flux difference continued to increase proportionally with the photosynthetic rate to a maximum of about 2 μmol m−2 s−1. In NH4+-grown tobacco, as well as in potato during tuber filling, the low-PAD component of surplus O2 evolution was virtually absent. The low-PAD phase was ascribed to photoreduction of NO2− which successfully competes with CO2 reduction and saturates at a rate of about 1 μmol O2 m−2 s−1 (9% of the maximum O2 evolution rate). The high-PAD component of about 1 μmol O2 m−2 s−1, superimposed on NO2− reduction, may represent oxaloacetate reduction. The roles of NO2−, oxaloacetate, and O2 reduction in the regulation of ATP/NADPH balance are discussed. PMID:21239375

Betavoltaic Enhancement Using Defect-Engineered TiO2 Nanotube Arrays through Electrochemical Reduction in Organic Electrolytes.

PubMed

Ma, Yang; Wang, Na; Chen, Jiang; Chen, Changsong; San, Haisheng; Chen, Jige; Cheng, Zhengdong

2018-06-19

Utilizing high-energy beta particles emitted from radioisotopes for long-lifetime betavoltaic cells is a great challenge due to low energy conversion efficiency. Here, we report a betavoltaic cell fabricated using TiO 2 nanotube arrays (TNTAs) electrochemically reduced in ethylene glycol electrolyte (EGECR-TNTAs) for the enhancement of the betavoltaic effect. The electrochemical reduction of TNTAs using high cathodic bias in organic electrolytes is indeed a facile and effective strategy to induce in situ self-doping of oxygen vacancy (OV) and Ti 3+ defects. The black EGECR-TNTAs are highly stable with a significantly narrower band gap and higher electrical conductivity as well as UV-vis-NIR light absorption. A 20 mCi of 63 Ni betavoltaic cell based on the reduced TNTAs exhibits a maximum ECE of 3.79% with open-circuit voltage of 1.04 V, short-circuit current density of 117.5 nA cm -2 , and a maximum power density of 39.2 nW cm -2 . The betavoltaic enhancement can be attributed to the enhanced charge carrier transport and separation as well as multiple exciton generation of electron-hole pairs due the generation of OV and Ti 3+ interstitial bands below the conductive band of TiO 2.

Enhanced Nitrobenzene reduction by zero valent iron pretreated with H2O2/HCl.

PubMed

Yang, Zhe; Ma, Xiaowen; Shan, Chao; Fang, Zhuoyao; Pan, Bingcai

2018-04-01

In this study a novel iron-based reducing agent of highly effective reduction toward nitrobenzene (NB) was obtained by pretreating zero valent iron (ZVI) with H 2 O 2 /HCl. During the H 2 O 2 /HCl pretreatment, ZVI undergoes an intensive corrosion process with formation of various reducing corrosion products (e.g., Fe 2+ , ferrous oxides/hydroxides, Fe 3 O 4 ), yielding a synergetic system (prtZVI) including liquid, suspensions and solid phase. The pretreatment process remarkably enhances the reductive performance of ZVI, where a rapid reduction of NB (200 mg L -1 ) in the prtZVI suspension was accomplished in a broad pH range (3-9) and at low dosage. Nitrosobenzene and phenylhydroxylamine are identified as the intermediates for NB reduction with the end-product of aniline. Compared with the virgin ZVI as well as another nanosized ZVI, the prtZVI system exhibits much higher electron efficiency for NB reduction as well as higher utilization ratio of Fe 0 . A rapid reduction of various nitroaromatics in an actual pharmaceutical wastewater further demonstrated the feasibility of the prtZVI system in real wastewater treatment. Copyright © 2018 Elsevier Ltd. All rights reserved.

Si/Ti2O3/Reduced Graphene Oxide Nanocomposite Anodes for Lithium-Ion Batteries with Highly Enhanced Cyclic Stability.

PubMed

Park, A Reum; Son, Dae-Yong; Kim, Jung Sub; Lee, Jun Young; Park, Nam-Gyu; Park, Juhyun; Lee, Joong Kee; Yoo, Pil J

2015-08-26

Silicon (Si) has attracted tremendous attention as a high-capacity anode material for next generation Li-ion batteries (LIBs); unfortunately, it suffers from poor cyclic stability due to excessive volume expansion and reduced electrical conductivity after repeated cycles. To circumvent these issues, we propose that Si can be complexed with electrically conductive Ti2O3 to significantly enhance the reversible capacity and cyclic stability of Si-based anodes. We prepared a ternary nanocomposite of Si/Ti2O3/reduced graphene oxide (rGO) using mechanical blending and subsequent thermal reduction of the Si, TiO2 nanoparticles, and rGO nanosheets. As a result, the obtained ternary nanocomposite exhibited a specific capacity of 985 mAh/g and a Coulombic efficiency of 98.4% after 100 cycles at a current density of 100 mA/g. Furthermore, these ternary nanocomposite anodes exhibited outstanding rate capability characteristics, even with an increased current density of 10 A/g. This excellent electrochemical performance can be ascribed to the improved electron and ion transport provided by the Ti2O3 phase within the Si domains and the structurally reinforced conductive framework comprised of the rGO nanosheets. Therefore, it is expected that our approach can also be applied to other anode materials to enable large reversible capacity, excellent cyclic stability, and good rate capability for high-performance LIBs.

Oxidative degradation and toxicity reduction of trichloroethylene (TCE) in water using TiO2/solar light: comparative study of TiO2 slurry and immobilized systems.

PubMed

Cho, Il-Hyoung; Park, Jae-Hong; Kim, Young-Gyu

2005-01-01

A solar-driven, photocatalyzed degradation system using TiO2 slurry and immobilized systems was constructed and applied to the degradation of trichloroethylene (TCE) contaminated water using TiO2 with solar light. The experiments were carried out under constant weather conditions on a sunny day. Solar photocatalytic treatment efficiency of the solar light/TiO2 slurry system was compared with that of the solar light/TiO2 immobilized system. The operation of the solar light/TiO2 slurry and immobilized systems showed 100% (TiO2 slurry system), 80% (TiO2 immobilized system) degradation of the TCE after 6 h, with a chloride production yield of approximately 89% (TiO2 slurry system), 72% (TiO2 immobilized system). The oxidants such as H2O2 and S2O8(2-) in the TiO2 slurry and immobilized systems increased TCE degradation rate by suppressing the electron/hole recombination process. The degradation rate and relative toxicity reduction of TCE followed the order of solar light/TiO2 slurry + S2O8(2-) > solar light/TiO2 slurry + H2O2 > solar light/TiO2 immobilized + S2O8(2-) > solar light/TiO2 slurry > solar light/TiO2 immobilized + H2O2 > solar light/TiO2 immobilized. Finally, following to the toxicity result, the acute toxicity was reduced by below toxicity endpoint (EC50 concentration) following the treatment. It means that many of the metabolites of TCE reduction are less toxic to Vibrio fischeri than the parent compound. Based on these results, TCE can be efficiently and safely treated in a solar-driven, photocatalyzed degradation system.

Effect of 1.5 MeV electron irradiation on β-Ga2O3 carrier lifetime and diffusion length

NASA Astrophysics Data System (ADS)

Lee, Jonathan; Flitsiyan, Elena; Chernyak, Leonid; Yang, Jiancheng; Ren, Fan; Pearton, Stephen J.; Meyler, Boris; Salzman, Y. Joseph

2018-02-01

The influence of 1.5 MeV electron irradiation on minority transport properties of Si doped β-Ga2O3 vertical Schottky rectifiers was observed for fluences up to 1.43 × 1016 cm-2. The Electron Beam-Induced Current technique was used to determine the minority hole diffusion length as a function of temperature for each irradiation dose. This revealed activation energies related to shallow donors at 40.9 meV and radiation-induced defects with energies at 18.1 and 13.6 meV. Time-resolved cathodoluminescence measurements showed an ultrafast 210 ps decay lifetime and reduction in carrier lifetime with increased irradiation.

Enhanced catalyst activity by decorating of Au on Ag@Cu2O nanoshell

NASA Astrophysics Data System (ADS)

Chen, Lei; Liu, Maomao; Zhao, Yue; Kou, Qiangwei; Wang, Yaxin; Liu, Yang; Zhang, Yongjun; Yang, Jinghai; Jung, Young Mee

2018-03-01

We successfully synthesized Au-decorated Ag@Cu2O heterostructures via a simple galvanic replacement method. As the Au precursor concentration increased, the density of the Au nanoparticles (NPs) on the Ag@Cu2O surface increased, which changed the catalytic activity of the Ag@Cu2O-Au structure. The combination of Au, Ag, and Cu2O exhibited excellent catalytic properties, which can further effect on the catalyst activity of the Ag@Cu2O-Au structure. In addition, the proposed Ag@Cu2O-Au nanocomposite was used to transform the organic, toxic pollutant, 4-nitrophenol (4-NP), into its nontoxic and medicinally important amino derivative via a catalytic reduction to optimize the material performance. The proposed Au-decorated Ag@Cu2O exhibited excellent catalytic activity, and the catalytic reduction time greatly decreased (5 min). Thus, three novel properties of Ag@Cu2O-Au, i.e., charge redistribution and transfer, adsorption, and catalytic reduction of organic pollutants, were ascertained for water remediation. The proposed catalytic properties have potential applications for photocatalysis and localized surface plasmon resonance (LSPR)- and peroxidase-like catalysis.

Enhancing the performance of single-chambered microbial fuel cell using manganese/palladium and zirconium/palladium composite cathode catalysts.

PubMed

Jadhav, Dipak A; Deshpande, Parag A; Ghangrekar, Makarand M

2017-08-01

Application of ZrO 2 , MnO 2 , palladium, palladium-substituted-zirconium oxide (Zr 0.98 Pd 0.02 O 2 ) and palladium-substituted-manganese oxide (Mn 0.98 Pd 0.02 O 2 ) cathode catalysts in a single-chambered microbial fuel cell (MFC) was explored. The highest power generation (1.28W/m 3 ) was achieved in MFC with Mn 0.98 Pd 0.02 O 2 catalyst, which was higher than that with MnO 2 (0.58W/m 3 ) alone; whereas, MFC having Zr 0.98 Pd 0.02 O 2 catalyzed cathode and non-catalyzed cathode produced powers of 1.02 and 0.23W/m 3 , respectively. Also, low-cost zirconium-palladium-composite showed better catalytic activity and capacitance over ZrO 2 with 20A/m 3 current production and demonstrated its suitability for MFC applications. Cyclic voltammetry analyses showed higher well-defined redox peaks in composite catalysts (Mn/Zr-Pd-C) over other catalyzed MFCs containing MnO 2 or ZrO 2 . Electrochemical behaviour of composite catalysts on cathode showed higher availability of adsorption sites for oxygen reduction and, hence, enhanced the rate of cathodic reactions. Thus, Mn/Zr-Pd-C-based composite catalysts exhibited superior cathodic performance and could be proposed as alternatives to costly Pd-catalyst for field applications. Copyright © 2017 Elsevier Ltd. All rights reserved.

Investigation of the electrocatalytic oxygen reduction and evolution reactions in lithium–oxygen batteries

DOE PAGES

Zheng, Dong; Zhang, Xuran; Qu, Deyu; ...

2015-04-21

Oxygen reduction and oxygen evolution reactions were examined on graphite electrodes with different crystal orientations. The kinetics for the redox couple O 2/O 2 •- are very fast, therefore no catalyst seems necessary to assist the charge transfer process. Apparently, the main source of the overpotential for the O 2 reduction reaction is from mass diffusion. Li 2O 2 becomes soluble in non-aqueous electrolytes in the presence of the tetraethylammonium tetrafluoroborate additive. The soluble B-O 2 2- ions can be oxidized electro-catalytically. The edge orientation of graphite demonstrates superior catalytic activity for the oxidation over basal orientation. The findings revealmore » an opportunity for recharging Li-air batteries efficiently and a new strategy of developing the catalyst for oxygen evolution reaction.« less

Shape-selective synthesis of Sn(MoO4)2 nanomaterials for catalysis and supercapacitor applications.

PubMed

Sakthikumar, K; Ede, Sivasankara Rao; Mishra, Soumyaranjan; Kundu, Subrata

2016-06-07

Size and shape-selective Sn(MoO4)2 nanomaterials have been synthesized for the first time using a simple hydrothermal route by the reaction of Sn(ii) chloride salt with sodium molybdate in CTAB micellar media under stirring at 60 °C temperature for about three hours. Needle-like and flake-like Sn(MoO4)2 nanomaterials were synthesized by optimizing the CTAB to metal salt molar ratio and by controlling other reaction parameters. The eventual diameter and length of the nanoneedles are ∼100 ± 10 nm and ∼850 ± 100 nm respectively. The average diameter of the flakes is ∼250 ± 50 nm. The synthesized Sn(MoO4)2 nanomaterials can be used in two potential applications, namely, catalytic reduction of nitroarenes and as an anodic material in electrochemical supercapacitors. From the catalysis study, it was observed that the Sn(MoO4)2 nanomaterials could act as a potential catalyst for the successful photochemical reduction of nitroarenes into their respective aminoarenes within a short reaction time. From the supercapacitor study, it was observed that the Sn(MoO4)2 nanomaterials of different shapes show different specific capacitance (Cs) values and the highest Cs value was observed for Sn(MoO4)2 nanomaterials having a flake-like morphology. The highest Cs value observed was 109 F g(-1) at a scan rate of 5 mV s(-1) for the flake-like Sn(MoO4)2 nanomaterials. The capacitor shows an excellent long cycle life along with 70% retention of the Cs value, even after 4000 consecutive cycles at a current density of 8 mA cm(-2). Other than the applications in catalysis and supercapacitors, the synthesized nanomaterials can find further applications in photoluminescence, sensor and other energy-related devices.

Crystallographic origin of cycle decay of the high-voltage LiNi0.5Mn1.5O4 spinel lithium-ion battery electrode.

PubMed

Pang, Wei Kong; Lu, Cheng-Zhang; Liu, Chia-Erh; Peterson, Vanessa K; Lin, Hsiu-Fen; Liao, Shih-Chieh; Chen, Jin-Ming

2016-06-29

High-voltage spinel LiNi0.5Mn1.5O4 (LNMO) is considered a potential high-power-density positive electrode for lithium-ion batteries, however, it suffers from capacity decay after extended charge-discharge cycling, severely hindering commercial application. Capacity fade is thought to occur through the significant volume change of the LNMO electrode occurring on cycling, and in this work we use operando neutron powder diffraction to compare the structural evolution of the LNMO electrode in an as-assembled 18650-type battery containing a Li4Ti5O12 negative electrode with that in an identical battery following 1000 cycles at high-current. We reveal that the capacity reduction in the battery post cycling is directly proportional to the reduction in the maximum change of the LNMO lattice parameter during its evolution. This is correlated to a corresponding reduction in the MnO6 octahedral distortion in the spinel structure in the cycled battery. Further, we find that the rate of lattice evolution, which reflects the rate of lithium insertion and removal, is ∼9 and ∼10% slower in the cycled than in the as-assembled battery during the Ni(2+)/Ni(3+) and Ni(3+)/Ni(4+) transitions, respectively.

A facile strategy to fabricate plasmonic Cu modified TiO{sub 2} nano-flower films for photocatalytic reduction of CO{sub 2} to methanol

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

Liu, Enzhou; Qi, Lulu; Bian, Juanjuan

Graphical abstract: Photoreduction of CO{sub 2} to CH{sub 3}OH over plasmonic Cu/TiO{sub 2} film. - Highlights: • Cu nanoparticles modified TiO{sub 2} nano-flower film was prepared by a facile strategy. • Cu nanoparticles can enhance the light absorption and the Raman scattering of TiO{sub 2}. • Cu nanoparticles can effectively restrain the recombination of the charge carriers. • A synergistic mechanism is proposed for photocatalytic reduction of CO{sub 2} on Cu/TiO{sub 2} film. - Abstract: Cu nanoparticles (NPs) deposited TiO{sub 2} nano-flower films were fabricated using a combination of a hydrothermal method and a microwave-assisted reduction process. The investigations indicatedmore » that Cu NPs and TiO{sub 2} film both exhibit visible light harvesting properties based on localized surface plasmon resonance (LSPR) of Cu NPs and unique nanostructures of TiO{sub 2} film. Fluorescence quenching was observed because the recombination of charge carriers was effectively suppressed by Cu NPs deposition. The experimental results indicate that Cu/TiO{sub 2} films exhibit better activity for the photocatalytic reduction of CO{sub 2} due to the charge transfer property and LSPR effect of Cu NPs. The CH{sub 3}OH production rate reached 1.8 μmol cm{sup −2} h{sup −1} (energy efficiency was 0.8%) over 0.5 Cu/TiO{sub 2} film under UV and visible light irradiation, which was 6.0 times higher than that observed over pure TiO{sub 2} film. In addition, a tentative photocatalytic mechanism is proposed to understand the experimental results over the Cu modified TiO{sub 2} nano-flower films.« less

High-Potential Electrocatalytic O2 Reduction with Nitroxyl / NOx Mediators: Implications for Fuel Cells and Aerobic Oxidation Catalysis

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

Gerken, James B.; Stahl, Shannon S.

2015-07-15

Efficient reduction of O2 to water is a central challenge in energy conversion and aerobic oxidation catalysis. In the present study, we investigate the electrochemical reduction of O2 with soluble organic nitroxyl and nitrogen oxide (NOx) mediators. When used alone, neither organic nitroxyls, such as TEMPO (2,2,6,6-tetramethyl-1-piperidinyl-N-oxyl), nor NOx species, such as sodium nitrite, are effective mediators of electrochemical O2 reduction. The combination of nitroxyl/NOx species, however, mediates sustained O2 reduction at electrochemical potentials of 0.19–0.33 V (vs. Fc/Fc+) in acetonitrile containing trifluoroacetic acid. Mechanistic analysis of the coupled redox reactions supports a process in which the nitrogen oxide catalystmore » drives aerobic oxidation of a nitroxyl mediator to an oxoammonium species, which then is reduced back to the nitroxyl at the cathode. The electrolysis potential is dictated by the oxoammonium/nitroxyl reduction potential. The high potentials observed with this ORR system benefit from the mechanism-based specificity for four-electron reduction of oxygen to water mediated by NOx species, together with kinetically efficient reduction of oxidized NOx species by TEMPO and other organic nitroxyls. This research was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center, funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences.« less

Preparation, patterning, and properties of thin YBa2Cu3O(7-delta) films

NASA Astrophysics Data System (ADS)

de Vries, J. W. C.; Dam, B.; Heijman, M. G. J.; Stollman, G. M.; Gijs, M. A. M.

1988-05-01

High T(c) superconducting thin films were prepared on (100) SrTiO3 substrates by dc triode sputtering and subsequent annealing. In these films Hall-bar structures having a width down to 5 microns were patterned using a reactive ion-etching technique. Superconductivity above 77 K was observed. When compared with the original film there is only a small reduction in T(c). The critical current density determined by electrical measurements is substantially reduced. On the other hand, the critical current density in the bulk of the grains as measured by the torque on a film is not reduced by the patterning process. It is suggested that superconductor-normal metal-superconductor junctions between the grains account for this difference.

A simple way to prepare Au@polypyrrole/Fe3O4 hollow capsules with high stability and their application in catalytic reduction of methylene blue dye

NASA Astrophysics Data System (ADS)

Yao, Tongjie; Cui, Tieyu; Wang, Hao; Xu, Linxu; Cui, Fang; Wu, Jie

2014-06-01

Metal nanoparticles are promising catalysts for dye degradation in treating wastewater despite the challenges of recycling and stability. In this study, we have introduced a simple way to prepare Au@polypyrrole (PPy)/Fe3O4 catalysts with Au nanoparticles embedded in a PPy/Fe3O4 capsule shell. The PPy/Fe3O4 capsule shell used as a support was constructed in one-step, which not only dramatically simplified the preparation process, but also easily controlled the magnetic properties of the catalysts through adjusting the dosage of FeCl2.4H2O. The component Au nanoparticles could catalyze the reduction of methylene blue dye with NaBH4 as a reducing agent and the reaction rate constant was calculated through the pseudo-first-order reaction equation. The Fe3O4 nanoparticles permitted quick recycling of the catalysts with a magnet due to their room-temperature superparamagnetic properties; therefore, the catalysts exhibited good reusability. In addition to catalytic activity and reusability, stability is also an important property for catalysts. Because both Au and Fe3O4 nanoparticles were wrapped in the PPy shell, compared with precursor polystyrene/Au composites and bare Fe3O4 nanoparticles, the stability of Au@PPy/Fe3O4 hollow capsules was greatly enhanced. Since the current method is simple and flexible to create recyclable catalysts with high stability, it would promote the practicability of metal nanoparticle catalysts in industrial polluted water treatment.Metal nanoparticles are promising catalysts for dye degradation in treating wastewater despite the challenges of recycling and stability. In this study, we have introduced a simple way to prepare Au@polypyrrole (PPy)/Fe3O4 catalysts with Au nanoparticles embedded in a PPy/Fe3O4 capsule shell. The PPy/Fe3O4 capsule shell used as a support was constructed in one-step, which not only dramatically simplified the preparation process, but also easily controlled the magnetic properties of the catalysts through adjusting the dosage of FeCl2.4H2O. The component Au nanoparticles could catalyze the reduction of methylene blue dye with NaBH4 as a reducing agent and the reaction rate constant was calculated through the pseudo-first-order reaction equation. The Fe3O4 nanoparticles permitted quick recycling of the catalysts with a magnet due to their room-temperature superparamagnetic properties; therefore, the catalysts exhibited good reusability. In addition to catalytic activity and reusability, stability is also an important property for catalysts. Because both Au and Fe3O4 nanoparticles were wrapped in the PPy shell, compared with precursor polystyrene/Au composites and bare Fe3O4 nanoparticles, the stability of Au@PPy/Fe3O4 hollow capsules was greatly enhanced. Since the current method is simple and flexible to create recyclable catalysts with high stability, it would promote the practicability of metal nanoparticle catalysts in industrial polluted water treatment. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr00023d

Electrochemical Corrosion and In Vitro Bioactivity of SiO2:ZrO2-Coated 316L Stainless Steel in Simulated Body Fluid

NASA Astrophysics Data System (ADS)

Srinivasan, A.; Rajendran, N.

2015-08-01

The effect of Si:Zr ratio on the in vitro bioactivity and electrochemical corrosion behavior of SiO2:ZrO2-mixed oxide-coated 316L stainless steel (SS) was evaluated in simulated body fluid (SBF) solution for 72, 120, and 168 h. Growth of Hydroxyapatite (HAp) was accelerated when Si content in the coating was increased. The Zr content in the coating improved the corrosion resistance of 316L SS rather than accelerating the HAp growth. When the Si:Zr ratio was 50:50, the coating exhibited significant improvement in corrosion resistance as well as HAp growth. The mechanism of HAp growth was proposed based on the change in surface zeta potential values of the coatings. Potentiodynamic polarization studies revealed about 10 and 5 times reduction in corrosion current density ( i corr) values for SiO2:ZrO2 (50:50)-coated 316L SS after 168 h of immersion compared to SiO2, ZrO2, and Si:Zr (70:30) coatings in SBF solutions thus confirming the superior corrosion resistance. The equivalent circuit parameters derived from electrochemical impedance spectroscopy studies further confirmed significant improvement in charge transfer resistance value even after 168 h of exposure.

Interhemispheric differences in polar stratospheric HNO3, H2O, ClO, and O3

NASA Technical Reports Server (NTRS)

Santee, M. L.; Read, W. G.; Waters, J. W.; Froidevaux, L.; Manney, G. L.; Flower, D. A.; Jarnot, R. F.; Harwood, R. S.; Peckham, G. E.

1995-01-01

Simultaneous global measurements of nitric acid (HNO3), water (H2O), chlorine monoxide (ClO), and ozone (O3) in the stratosphere have been obtained over complete annual cycles in both hemispheres by the Microwave Limb Sounder on the Upper Atmosphere Research Satellite. A sizeable decrease in gas-phase HNO3 was evident in the lower stratospheric vortex over Antarctica by early June 1992, followed by a significant reduction in gas-phase H2O after mid-July. By mid-August, near the time of peak ClO, abundances of gas-phase HNO3 and H2O were extremely low. The concentrations of HNO3 and H2O over Antarctica remained depressed into November, well after temperatures in the lower stratosphere had risen above the evaporation threshold for polar stratospheric clouds, implying that denitrification and dehydration had occurred. No large decreases in either gas-phase HNO3 or H2O were observed in the 1992-1993 Arctic winter vortex. Although ClO was enhanced over the Arctic as it was over the Antarctic, Arctic O3 depletion was substantially smaller than that over Antarctica. A major factor currently limiting the formation of an Arctic ozone 'hole' is the lack of denitrification in the northern polar vortex, but future cooling of the lower stratosphere could lead to more intense denitrification and consequently larger losses of Arctic ozone.

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

PubMed

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

2010-11-01

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

Facile synthesis of electrospun MFe2O4 (M = Co, Ni, Cu, Mn) spinel nanofibers with excellent electrocatalytic properties for oxygen evolution and hydrogen peroxide reduction

NASA Astrophysics Data System (ADS)

Li, Mian; Xiong, Yueping; Liu, Xiaotian; Bo, Xiangjie; Zhang, Yufan; Han, Ce; Guo, Liping

2015-05-01

Designing and preparing porous transition metal ferrites without using any template, shape-directing agent, and surfactant is a challenge. Herein, heterojunction MFe2O4 (M = Co, Ni, Cu, Mn) nanofiber (NF) based films with three-dimensional configurations were synthesized by electrospinning and the subsequent thermal treatment processes. Characterization results indeed show the 3D net-like textural structures of the electrospun spinel-type MFe2O4 NFs. In particular, the resulting MFe2O4 NFs have lengths up to several dozens of micrometers with an average diameter size of about 150 nm and possess abundant micro/meso/macropores on both the surface and within the films. The hierarchically porous structures and high surface areas of these MFe2O4 NFs (for example, the CoFe2O4 NFs possess a larger BET specific surface area (61.48 m2 g-1) than those of the CoFe2O4 NPs (5.93 m2 g-1)) can afford accessible transport channels for effectively decreasing the mass transport resistances, enhancing the electrical conductivity, and increasing the density and reactivity of the exposed catalytic active sites. All these advantages will be responsible for the better electrocatalytic performances of these MFe2O4 NFs compared with their structural isomers (i.e. the MFe2O4 NPs) for the oxygen evolution reaction (OER) and H2O2 reduction in alkaline solution. Meanwhile, both the OER and H2O2 reduction catalytic activities for these MFe2O4 NFs obey the order of CoFe2O4 NFs > CuFe2O4 NFs > NiFe2O4 NFs > MnFe2O4 NFs > Fe2O3 NFs. The CoFe2O4 NFs represent a new class of highly efficient non-noble-metal catalysts for both OER and H2O2 reduction/detection in alkaline media.Designing and preparing porous transition metal ferrites without using any template, shape-directing agent, and surfactant is a challenge. Herein, heterojunction MFe2O4 (M = Co, Ni, Cu, Mn) nanofiber (NF) based films with three-dimensional configurations were synthesized by electrospinning and the subsequent thermal treatment processes. Characterization results indeed show the 3D net-like textural structures of the electrospun spinel-type MFe2O4 NFs. In particular, the resulting MFe2O4 NFs have lengths up to several dozens of micrometers with an average diameter size of about 150 nm and possess abundant micro/meso/macropores on both the surface and within the films. The hierarchically porous structures and high surface areas of these MFe2O4 NFs (for example, the CoFe2O4 NFs possess a larger BET specific surface area (61.48 m2 g-1) than those of the CoFe2O4 NPs (5.93 m2 g-1)) can afford accessible transport channels for effectively decreasing the mass transport resistances, enhancing the electrical conductivity, and increasing the density and reactivity of the exposed catalytic active sites. All these advantages will be responsible for the better electrocatalytic performances of these MFe2O4 NFs compared with their structural isomers (i.e. the MFe2O4 NPs) for the oxygen evolution reaction (OER) and H2O2 reduction in alkaline solution. Meanwhile, both the OER and H2O2 reduction catalytic activities for these MFe2O4 NFs obey the order of CoFe2O4 NFs > CuFe2O4 NFs > NiFe2O4 NFs > MnFe2O4 NFs > Fe2O3 NFs. The CoFe2O4 NFs represent a new class of highly efficient non-noble-metal catalysts for both OER and H2O2 reduction/detection in alkaline media. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr07243j

Fabrication of Amine-Modified Magnetite-Electrochemically Reduced Graphene Oxide Nanocomposite Modified Glassy Carbon Electrode for Sensitive Dopamine Determination

PubMed Central

He, Quanguo; Liu, Jun; Liu, Xiaopeng; Li, Guangli; Chen, Dongchu; Deng, Peihong; Liang, Jing

2018-01-01

Amine-modified magnetite (NH2–Fe3O4)/reduced graphene oxide nanocomposite modified glassy carbon electrodes (NH2–Fe3O4/RGO/GCEs) were developed for the sensitive detection of dopamine (DA). The NH2-Fe3O4/RGO/GCEs were fabricated using a drop-casting method followed by an electrochemical reduction process. The surface morphologies, microstructure and chemical compositions of the NH2–Fe3O4 nanoparticles (NPs), reduced graphene oxide (RGO) sheets and NH2–Fe3O4/RGO nanocomposites were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-Ray diffraction (XRD) and Fourier-transform infrared (FTIR) spectroscopy. The electrochemical behaviors of DA on the bare and modified GCEs were investigated in phosphate buffer solution (PBS) by cyclic voltammetry (CV). Compared with bare electrode and RGO/GCE, the oxidation peak current (ipa) on the NH2–Fe3O4/RGO/GCE increase significantly, owing to the synergistic effect between NH2–Fe3O4 NPs and RGO sheets. The oxidation peak currents (ipa) increase linearly with the concentrations of DA in the range of 1 × 10−8 mol/L – 1 × 10−7 mol/L, 1 × 10−7 mol/L – 1 × 10−6 mol/L and 1 × 10−6 mol/L – 1 × 10−5 mol/L. The detection limit is (4.0 ± 0.36) ×10−9 mol/L (S/N = 3). Moreover, the response peak currents of DA were hardly interfered with the coexistence of ascorbic acid (AA) and uric acid (UA). The proposed NH2–Fe3O4/RGO/GCE is successfully applied to the detection of dopamine hydrochloride injections with satisfactory results. Together with low cost, facile operation, good selectivity and high sensitivity, the NH2–Fe3O4/RGO/GCEs have tremendous prospects for the detection of DA in various real samples. PMID:29584682

A mechanistic study of hydrogen gas sensing by PdO nanoflake thin films at temperatures below 250 °C.

PubMed

Chiang, Yu-Ju; Li, Kuang-Chung; Lin, Yi-Chieh; Pan, Fu-Ming

2015-02-07

We prepared PdO nanoflake thin films on the SiO2 substrate by reactive sputter deposition, and studied their sensing response to H2 at temperatures between 25 and 250 °C. In addition to the oxygen ionosorption model, which is used to describe the early H2 sensing response over the temperature range studied, the H2 sensing kinetics of the PdO thin films can be separated into three temperature regimes: temperatures below 100 °C, around 150 °C and above 200 °C. At temperatures below 100 °C, PdO reduction is the dominant reaction affecting the H2 sensing behavior. At temperatures around 150 °C, Pd reoxidation kinetically competes with PdO reduction leading to a complicated sensing characteristic. Active PdO reduction by H2 promotes the continuing growth of Pd nanoislands, facilitating dissociative oxygen adsorption and thus the subsequent Pd reoxidation in the H2-dry air gas mixture. The kinetic competition between the PdO reduction and reoxidation at 150 °C leads to the observation of an inverse of the increase in the sensor conductivity. At temperatures above 200 °C, the PdO sensor exhibits a sensor signal monotonically increasing with the H2 concentration, and the H2 sensing behavior is consistent with the Mars-van-Krevelen redox mechanism.

Reduction of adsorbed As(V) on nano-TiO2 by sulfate-reducing bacteria.

PubMed

Luo, Ting; Ye, Li; Ding, Cheng; Yan, Jinlong; Jing, Chuanyong

2017-11-15

Reduction of surface-bound arsenate [As(V)] and subsequent release into the aqueous phase contribute to elevated As in groundwater. However, this natural process is not fully understood, especially in the presence of sulfate-reducing bacteria (SRB). Gaining mechanistic insights into solid-As(V)-SRB interactions motivated our molecular level study on the fate of nano-TiO 2 bound As(V) in the presence of Desulfovibrio vulgaris DP4, a strain of SRB, using incubation and in situ ATR-FTIR experiments. The incubation results clearly revealed the reduction of As(V), either adsorbed on nano-TiO 2 or dissolved, in the presence of SRB. In contrast, this As(V) reduction was not observed in abiotic control experiments where sulfide was used as the reductant. Moreover, the reduction was faster for surface-bound As(V) than for dissolved As(V), as evidenced by the appearance of As(III) at 45h and 75h, respectively. ATR-FTIR results provided direct evidence that the surface-bound As(V) was reduced to As(III) on TiO 2 surfaces in the presence of SRB. In addition, the As(V) desorption from nano-TiO 2 was promoted by SRB relative to abiotic sulfide, due to the competition between As(V) and bacterial phosphate groups for TiO 2 surface sites. This competition was corroborated by the ATR-FTIR analysis, which showed inner-sphere surface complex formation by bacterial phosphate groups on TiO 2 surfaces. The results from this study highlight the importance of indirect bacteria-mediated As(V) reduction and release in geochemical systems. Copyright © 2017 Elsevier B.V. All rights reserved.

Phases of LiMn1.84V0.06Ti0.1O4 cathode material

NASA Astrophysics Data System (ADS)

Zainol, N. H.; Kamarulzaman, N.; Osman, Z.; Fadzil, A. F. M.; Yahya, N. F.

2017-09-01

In this work, LiMn1.84V0.06Ti0.1O4 was prepared via a combustion method using citric acid as a reductant. The precursor obtained was annealed at 700 °C for 24h in a furnace. The thermal profile of the precursor was obtained by simultaneous thermogravimetric analysis (STA). The observed material was characterized by X-ray Diffraction (XRD) and found to be pure and single-phase of cubic structure. The electrochemical performance of LiMn1.84V0.06Ti0.1O4 cathode material was studied by applying a constant current of 1.0 mA at a voltage range of 4.2 to 2.5 V. The specific capacity of LiMn1.84V0.06Ti0.1O4 cathode material at the 1st cycle shows the value of 95mAh/g which is less than the specific capacity of LiMn2O4, which is 117 mAh/g.

Polymer Electrolyte Fuel Cells Employing Heteropolyacids as Redox Mediators for Oxygen Reduction Reactions: Pt-Free Cathode Systems.

PubMed

Matsui, Toshiaki; Morikawa, Eri; Nakada, Shintaro; Okanishi, Takeou; Muroyama, Hiroki; Hirao, Yoshifumi; Takahashi, Tsuyoshi; Eguchi, Koichi

2016-07-20

In this study, the heteropolyacids of H3+xPVxMO12-xO40 (x = 0, 2, and 3) were applied as redox mediators for the oxygen reduction reaction in polymer electrolyte fuel cells, of which the cathode is free from the usage of noble metals such as Pt/C. In this system, the electrochemical reduction of heteropolyacid over the carbon cathode and the subsequent reoxidation of the partially reduced heteropolyacid by exposure to the dissolved oxygen in the regenerator are important processes for continuous power generation. Thus, the redox properties of catholytes containing these heteropolyacids were investigated in detail. The substitution quantity of V in the heteropolyacid affected the onset reduction potential as well as the reduction current density, resulting in a difference in cell performance. The chemical composition of heteropolyacid also had a significant impact on the reoxidation property. Among the three compounds, H6PV3Mo9O40 was the most suitable redox mediator. Furthermore, the pH of the catholyte was found to be the crucial factor in determining the reoxidation rate of partially reduced heteropolyacid as well as cell performance.

Reduction of mixed Mn-Zr oxides: in situ XPS and XRD studies.

PubMed

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

2015-09-21

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

Carbon supported MnO2-CoFe2O4 with enhanced electrocatalytic activity for oxygen reduction and oxygen evolution

NASA Astrophysics Data System (ADS)

Wang, Ying; Liu, Qing; Hu, Tianjun; Zhang, Limin; Deng, Youquan

2017-05-01

The catalyst MnO2-CoFe2O4/C was firstly synthesized via a two-step process and applied as a bifunctional electrocatalyst for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) in alkaline media. The composite exhibits better bifunctional activity than CoFe2O4/C and MnO2/C. Moreover, superior durability and high methanol tolerance in alkaline media outperforms the commercial Pt/C electrocatalyst, which signifying its excellent potential for applications in metal-air batteries and alkaline fuel cells.

Electrochemical H2O2 biosensor composed of myoglobin on MoS2 nanoparticle-graphene oxide hybrid structure.

PubMed

Yoon, Jinho; Lee, Taek; Bapurao G, Bharate; Jo, Jinhee; Oh, Byung-Keun; Choi, Jeong-Woo

2017-07-15

In this research, the electrochemical biosensor composed of myoglobin (Mb) on molybdenum disulfide nanoparticles (MoS 2 NP) encapsulated with graphene oxide (GO) was fabricated for the detection of hydrogen peroxide (H 2 O 2 ). Hybrid structure composed of MoS 2 NP and GO (GO@MoS 2 ) was fabricated for the first time to enhance the electrochemical signal of the biosensor. As a sensing material, Mb was introduced to fabricate the biosensor for H 2 O 2 detection. Formation and immobilization of GO@MoS 2 was confirmed by transmission electron microscopy, ultraviolet-visible spectroscopy, scanning electron microscopy, and scanning tunneling microscopy. Immobilization of Mb, and electrochemical property of biosensor were investigated by cyclic voltammetry and amperometric i-t measurements. Fabricated biosensor showed the electrochemical signal enhanced redox current as -1.86μA at an oxidation potential and 1.95μA at a reduction potential that were enhanced relative to those of electrode prepared without GO@MoS 2 . Also, this biosensor showed the reproducibility of electrochemical signal, and retained the property until 9 days from fabrication. Upon addition of H 2 O 2 , the biosensor showed enhanced amperometric response current with selectivity relative to that of the biosensor prepared without GO@MoS 2 . This novel hybrid material-based biosensor can suggest a milestone in the development of a highly sensitive detecting platform for biosensor fabrication with highly sensitive detection of target molecules other than H 2 O 2 . Copyright © 2016 Elsevier B.V. All rights reserved.

Ag/α-Fe2O3 hollow microspheres: Preparation and application for hydrogen peroxide detection

NASA Astrophysics Data System (ADS)

Kang, Xinyuan; Wu, Zhiping; Liao, Fang; Zhang, Tingting; Guo, Tingting

2015-09-01

In this paper, we demonstrated a simple approach for preparing α-Fe2O3 hollow spheres by mixing ferric nitrate aqueous and glucose in 180 °C. The glucose was found to act as a soft template in the process of α-Fe2O3 hollow spheres formation. Ag/α-Fe2O3 hollow nanocomposite was obtained under UV irradiation without additional reducing agents or initiators. Synthesized Ag/α-Fe2O3 hollow composites exhibited remarkable catalytic performance toward H2O2 reduction. The electrocatalytic activity mechanism of Ag/α-Fe2O3/GCE were discussed toward the reduction of H2O2 in this paper.

Facile synthesis of electrospun MFe2O4 (M = Co, Ni, Cu, Mn) spinel nanofibers with excellent electrocatalytic properties for oxygen evolution and hydrogen peroxide reduction.

PubMed

Li, Mian; Xiong, Yueping; Liu, Xiaotian; Bo, Xiangjie; Zhang, Yufan; Han, Ce; Guo, Liping

2015-05-21

Designing and preparing porous transition metal ferrites without using any template, shape-directing agent, and surfactant is a challenge. Herein, heterojunction MFe2O4 (M = Co, Ni, Cu, Mn) nanofiber (NF) based films with three-dimensional configurations were synthesized by electrospinning and the subsequent thermal treatment processes. Characterization results indeed show the 3D net-like textural structures of the electrospun spinel-type MFe2O4 NFs. In particular, the resulting MFe2O4 NFs have lengths up to several dozens of micrometers with an average diameter size of about 150 nm and possess abundant micro/meso/macropores on both the surface and within the films. The hierarchically porous structures and high surface areas of these MFe2O4 NFs (for example, the CoFe2O4 NFs possess a larger BET specific surface area (61.48 m(2) g(-1)) than those of the CoFe2O4 NPs (5.93 m(2) g(-1))) can afford accessible transport channels for effectively decreasing the mass transport resistances, enhancing the electrical conductivity, and increasing the density and reactivity of the exposed catalytic active sites. All these advantages will be responsible for the better electrocatalytic performances of these MFe2O4 NFs compared with their structural isomers (i.e. the MFe2O4 NPs) for the oxygen evolution reaction (OER) and H2O2 reduction in alkaline solution. Meanwhile, both the OER and H2O2 reduction catalytic activities for these MFe2O4 NFs obey the order of CoFe2O4 NFs > CuFe2O4 NFs > NiFe2O4 NFs > MnFe2O4 NFs > Fe2O3 NFs. The CoFe2O4 NFs represent a new class of highly efficient non-noble-metal catalysts for both OER and H2O2 reduction/detection in alkaline media.

Effects of a TiC substrate on the catalytic activity of Pt for NO reduction.

PubMed

Chu, Xingli; Fu, Zhaoming; Li, Shasha; Zhang, Xilin; Yang, Zongxian

2016-05-11

Density functional theory calculations are used to elucidate the catalytic properties of a Pt monolayer supported on a TiC(001) substrate (Pt/TiC) toward NO reduction. It is found that the compound system of Pt/TiC has a good stability due to the strong Pt-TiC interaction. The diverse dissociation paths (namely the direct dissociation mechanism and the dimeric mechanism) are investigated. The transition state searching calculations suggest that NO has strong diffusion ability and small activation energy for dissociation on the Pt/TiC. For NO reduction on the Pt/TiC surface, we have found that the direct dissociation mechanisms (NO + N + O → NO2 + N and NO + N + O → N2 + O + O) are easier with a smaller dissociation barrier than those on the Pt(111) surface; and the dimeric process (NO + NO → (NO)2 → N2O + O → N2 + O + O) is considered to be dominant or significant with even a lower energy barrier than that of the direct dissociation. The results show that Pt/TiC can serve as an efficient catalyst for NO reduction.

The Effect of Titanium Dioxide (TiO2) Nanoparticles on Hydroxyapatite (HA)/TiO2 Composite Coating Fabricated by Electrophoretic Deposition (EPD)

NASA Astrophysics Data System (ADS)

Amirnejad, M.; Afshar, A.; Salehi, S.

2018-05-01

Composite coatings of Hydroxyapatite (HA) with ceramics, polymers and metals are used to modify the surface structure of implants. In this research, HA/TiO2 composite coating was fabricated by electrophoretic deposition (EPD) on 316 stainless steel substrate. HA/TiO2 composite coatings with 5, 10 and 20 wt.% of TiO2, deposited at 40 V and 90 s as an optimum condition. The samples coated at this condition led to an adherent, continuous and crack-free coating. The influence of TiO2 content was studied by performing different characterization methods such as scanning electron microscopy (SEM), energy dispersive x-ray spectroscopy (EDS), corrosion resistance in simulated body fluid (SBF), coating's dissolution rate in physiological solution and bond strength to the substrate. The results showed that the higher amount of TiO2 in the composite coating led to increase in bond strength of coating to stainless steel substrate from 3 MPa for HA coating to 5.5 MPa for HA-20 wt.% TiO2 composite coating. In addition, it caused to reduction of corrosion current density of samples in the SBF solution from 18.92 μA/cm2 for HA coating to 6.35 μA/cm2 for HA-20 wt.% TiO2 composite coating.

The Effect of Titanium Dioxide (TiO2) Nanoparticles on Hydroxyapatite (HA)/TiO2 Composite Coating Fabricated by Electrophoretic Deposition (EPD)

NASA Astrophysics Data System (ADS)

Amirnejad, M.; Afshar, A.; Salehi, S.

2018-04-01

Composite coatings of Hydroxyapatite (HA) with ceramics, polymers and metals are used to modify the surface structure of implants. In this research, HA/TiO2 composite coating was fabricated by electrophoretic deposition (EPD) on 316 stainless steel substrate. HA/TiO2 composite coatings with 5, 10 and 20 wt.% of TiO2, deposited at 40 V and 90 s as an optimum condition. The samples coated at this condition led to an adherent, continuous and crack-free coating. The influence of TiO2 content was studied by performing different characterization methods such as scanning electron microscopy (SEM), energy dispersive x-ray spectroscopy (EDS), corrosion resistance in simulated body fluid (SBF), coating's dissolution rate in physiological solution and bond strength to the substrate. The results showed that the higher amount of TiO2 in the composite coating led to increase in bond strength of coating to stainless steel substrate from 3 MPa for HA coating to 5.5 MPa for HA-20 wt.% TiO2 composite coating. In addition, it caused to reduction of corrosion current density of samples in the SBF solution from 18.92 μA/cm2 for HA coating to 6.35 μA/cm2 for HA-20 wt.% TiO2 composite coating.

Nitrous oxide emissions from soils: how well do we understand the processes and their controls?

PubMed Central

Butterbach-Bahl, Klaus; Baggs, Elizabeth M.; Dannenmann, Michael; Kiese, Ralf; Zechmeister-Boltenstern, Sophie

2013-01-01

Although it is well established that soils are the dominating source for atmospheric nitrous oxide (N2O), we are still struggling to fully understand the complexity of the underlying microbial production and consumption processes and the links to biotic (e.g. inter- and intraspecies competition, food webs, plant–microbe interaction) and abiotic (e.g. soil climate, physics and chemistry) factors. Recent work shows that a better understanding of the composition and diversity of the microbial community across a variety of soils in different climates and under different land use, as well as plant–microbe interactions in the rhizosphere, may provide a key to better understand the variability of N2O fluxes at the soil–atmosphere interface. Moreover, recent insights into the regulation of the reduction of N2O to dinitrogen (N2) have increased our understanding of N2O exchange. This improved process understanding, building on the increased use of isotope tracing techniques and metagenomics, needs to go along with improvements in measurement techniques for N2O (and N2) emission in order to obtain robust field and laboratory datasets for different ecosystem types. Advances in both fields are currently used to improve process descriptions in biogeochemical models, which may eventually be used not only to test our current process understanding from the microsite to the field level, but also used as tools for up-scaling emissions to landscapes and regions and to explore feedbacks of soil N2O emissions to changes in environmental conditions, land management and land use. PMID:23713120

Factors that control catalytic two- versus four-electron reduction of dioxygen by copper complexes.

PubMed

Fukuzumi, Shunichi; Tahsini, Laleh; Lee, Yong-Min; Ohkubo, Kei; Nam, Wonwoo; Karlin, Kenneth D

2012-04-25

The selective two-electron reduction of O(2) by one-electron reductants such as decamethylferrocene (Fc*) and octamethylferrocene (Me(8)Fc) is efficiently catalyzed by a binuclear Cu(II) complex [Cu(II)(2)(LO)(OH)](2+) (D1) {LO is a binucleating ligand with copper-bridging phenolate moiety} in the presence of trifluoroacetic acid (HOTF) in acetone. The protonation of the hydroxide group of [Cu(II)(2)(LO)(OH)](2+) with HOTF to produce [Cu(II)(2)(LO)(OTF)](2+) (D1-OTF) makes it possible for this to be reduced by 2 equiv of Fc* via a two-step electron-transfer sequence. Reactions of the fully reduced complex [Cu(I)(2)(LO)](+) (D3) with O(2) in the presence of HOTF led to the low-temperature detection of the absorption spectra due to the peroxo complex [Cu(II)(2)(LO)(OO)] (D) and the protonated hydroperoxo complex [Cu(II)(2)(LO)(OOH)](2+) (D4). No further Fc* reduction of D4 occurs, and it is instead further protonated by HOTF to yield H(2)O(2) accompanied by regeneration of [Cu(II)(2)(LO)(OTF)](2+) (D1-OTF), thus completing the catalytic cycle for the two-electron reduction of O(2) by Fc*. Kinetic studies on the formation of Fc*(+) under catalytic conditions as well as for separate examination of the electron transfer from Fc* to D1-OTF reveal there are two important reaction pathways operating. One is a rate-determining second reduction of D1-OTF, thus electron transfer from Fc* to a mixed-valent intermediate [Cu(II)Cu(I)(LO)](2+) (D2), which leads to [Cu(I)(2)(LO)](+) that is coupled with O(2) binding to produce [Cu(II)(2)(LO)(OO)](+) (D). The other involves direct reaction of O(2) with the mixed-valent compound D2 followed by rapid Fc* reduction of a putative superoxo-dicopper(II) species thus formed, producing D.

Characterization and application of the hetero-junction ZnFe2O4/TiO2 for Cr(VI) reduction under visible light

NASA Astrophysics Data System (ADS)

Rekhila, G.; Trari, M.; Bessekhouad, Y.

2017-06-01

The spinel ZnFe2O4 prepared by nitrate route is used as dispersed photons collector capable to sensitize TiO2 under visible light and to reduce Cr(VI) into trivalent state. The transport properties, optical and photo-electrochemical characterizations are correlated, to build the energetic diagram of the hetero-system ZnFe2O4/TiO2/CrO4 - solution. A gap of 1.97 eV is obtained for the spinel from the diffuse reflectance. The conduction band of ZnFe2O4 (-1.47 V SCE) favors the electrons injection into TiO2, permitting a physical separation of the charge carriers. The oxidation of oxalic acid by photoholes prevents the corrosion of the spinel. The best configuration ZnFe2O4 (75 %)/TiO2 (25 %) is used to catalyze the downhill reaction (2HCrO4 - + 3C2H4O4 + 1.5O2 + 8H+ → 2Cr3+ + 6CO2 + 11 H2O, Δ G° = -557 kcal mol-1). 60 % of Cr(VI) are reduced after 3 h of visible light illumination and the photoactivity follows a first-order kinetic with a half-life of 70 min. The water reduction competes with the HCrO4 - reduction which is the reason in the regression of the photoactivity; a hydrogen evolution rate of 24 µmol mg-1 h-1 is obtained.

Self-doped Ti(3+)-TiO2 as a photocatalyst for the reduction of CO2 into a hydrocarbon fuel under visible light irradiation.

PubMed

Sasan, Koroush; Zuo, Fan; Wang, Yuan; Feng, Pingyun

2015-08-28

Self-doped TiO2 shows visible light photocatalytic activity, while commercial TiO2 (P25) is only UV responsive. The incorporation of Ti(3+) into TiO2 structures narrows the band gap (2.90 eV), leading to significantly increased photocatalytic activity for the reduction of CO2 into a renewable hydrocarbon fuel (CH4) in the presence of water vapour under visible light irradiation.

A mitigation strategy for commercial aviation impact on NOx-related O3 change

NASA Astrophysics Data System (ADS)

Wasiuk, D. K.; Khan, M. A. H.; Shallcross, D. E.; Derwent, R. G.; Lowenberg, M. H.

2016-07-01

An operational mitigation strategy for commercial aircraft impact on atmospheric composition, referred to as the turboprop replacement strategy (TRS), is described in this paper. The global air traffic between 2005 and 2011 was modeled with the TRS in which turbofan powered aircraft were replaced with nine chosen turboprop powered aircraft on all routes up to 1700 nautical miles (NM) in range. The results of this TRS double the global number of departures, as well as global mission distance, while global mission time grows by nearly a factor of 3. However, the global mission fuel and the emissions of aviation CO2, H2O, and SOx remain approximately unchanged, and the total global aviation CO, hydrocarbons (HC), and NOx emissions are reduced by 79%, 21%, and 11% on average between 2005 and 2011. The TRS lowers the global mean cruise altitude of flights up to 1700 NM by 2.7 km which leads to a significant decrease in global mission fuel burn, mission time, distance flown, and the aircraft emissions of CO2, CO, H2O, NOx, SOx, and HC above 9.2 km. The replacement of turbofans with turboprops in regional fleets on a global scale leads to an overall reduction in levels of tropospheric O3 at the current estimated mean cruise altitude near the tropopause where the radiative forcing of O3 is strongest. Further, the replacement strategy results in a reduction of ground-level aviation CO and NOx emissions by 33 and 29%, respectively, between 2005 and 2011.

Enhanced nitrogen selectivity for nitrate reduction on Cu-nZVI by TiO2 photocatalysts under UV irradiation

NASA Astrophysics Data System (ADS)

Krasae, Nalinee; Wantala, Kitirote

2016-09-01

The aims of this work were to study the effect of Cu-nZVI with and without TiO2 on nitrate reduction and to study the pathway of nitrate reduction utilizing to nitrogen gas. The chemical and physical properties of Cu-nZVI and Cu-nZVI/TiO2 such as specific surface area, crystalline phase, oxidation state of Cu and Fe and morphology were determined by N2 adsorption-desorption Brunauer-Emmett-Teller (BET) analytical technique, X-ray diffraction (XRD), X-ray Absorption Near Edge Structure (XANES) technique and Transmittance Electron Microscopy (TEM). The full factorial design (FFD) was used in this experiment for the effect of Cu-nZVI with and without TiO2, where the initial solution pH was varied at 4, 5.5, and 7 and initial nitrate concentration was varied at 50, 75, and 100 ppm. Finally, the pathway of nitrate reduction was examined to calculate the nitrogen gas selectivity. The specific area of Cu-nZVI and Cu-nZVI/TiO2 was found to be about 4 and 36 m2/g, respectively. The XRD pattern of Fe0 in Cu-nZVI was found at 45° (2θ), whereas Cu-nZVI/TiO2 cannot be observed. TEM images can confirm the position of the core and the shell of nZVI for Fe0 and ferric oxide. Cu-nZVI/TiO2 proved to have higher activity in nitrogen reduction performance than that without TiO2 and nitrate can be completely degraded in both of solution pH of 4 and 7 in 75 ppm of initial nitrate concentration. It can be highlighted that the nitrogen gas selectivity of Cu-nZVI/TiO2 greater than 82% was found at an initial solution pH of 4 and 7. The main effects of Cu-nZVI with and without TiO2 and the initial nitrate concentration on nitrate reduction were significant. The interaction between solution pH and initial nitrate concentration and the interaction of all effects at a reaction time of 15 min on nitrate reduction were also significant.

Enhanced pH sensitivity of AlGaN/GaN ion-sensitive field effect transistor with Al2O3 synthesized by atomic layer deposition

NASA Astrophysics Data System (ADS)

Wang, Lei; Li, Liuan; Zhang, Tong; Liu, Xinke; Ao, Jin-Ping

2018-01-01

In this study, we evaluated the pH sensitivity enhancement of AlGaN/GaN ion-sensitive field-effect transistor (ISFET) coated by Al2O3 film on the sensing area utilizing atomic layer deposition (ALD). The presence of the Al2O3 film leads to an obvious reduction of surface state density as well as leakage current in the solution, which is beneficial for improving the stability of the ISFET. Furthermore, the sensitivity of the ISFET was improved to 57.8 mV/pH, which is very close to the Nernstian limit at room temperature. The pH sensitivity enhancement can be explained by the higher density of sensing site as well as better surface hydrophilicity.

Estimating N2O processes during grassland renewal and grassland conversion to maize cropping using N2O isotopocules

NASA Astrophysics Data System (ADS)

Buchen, Caroline; Well, Reinhard; Flessa, Heinz; Fuß, Roland; Helfrich, Mirjam; Lewicka-Szczebak, Dominika

2017-04-01

Grassland break-up due to grassland renewal and grassland conversion to cropland can lead to a flush of mineral nitrogen from decomposition of the old grass sward and the decomposition of soil organic matter. Moreover, increased carbon and nitrogen mineralisation can result in enhanced nitrous oxide (N2O) emissions. As N2O is known to be an important greenhouse gas and a major precursor for ozone depletion, its emissions need to be mitigated by adjusting agricultural management practices. Therefore, it is necessary to understand the N2O processes involved, as well as the contribution of N2O reduction to N2. Apart from the widely used 15N gas flux method, natural abundance isotopic analysis of the four most abundant isotopocules of N2O species is a promising alternative to assess N2O production pathways. We used stable isotope analyses of soil-emitted N2O (δ18ON2O, δ15NN2Obulk and δ15NN2OSP= intramolecular distribution of 15N within the linear N2O molecule) with an isotopocule mapping approach to simultaneously estimate the magnitude of N2O reduction to N2 and the fraction of N2O originating from the bacterial denitrification pathway or fungal denitrification and/or nitrification. This approach is based on endmember areas of isotopic values for the N2O produced from different sources reported in the literature. For this purpose, we calculated two main scenarios with different assumptions for N2O produced: N2O is reduced to N2 before residual N2O is mixed with N2O of various sources (Scenario a) and vice versa (Scenario b). Based on this, we applied seven different scenario variations, where we evaluated the range of possible values for the potential N2O production pathways (heterotrophic bacterial denitrification and/or nitrifier denitrification and fungal denitrification and/or nitrification). This was done by using a range of isotopic endmember values and assuming different fractionation factors of N2O reduction in order to find the most reliable scenario. Investigations were carried out over a study period of one year following grassland renewal and grassland conversion to maize cropping on two different soil sites (Plaggic Anthrosol and Histic Gleysol) near Oldenburg, Lower Saxony Germany. Our observations indicate heterotrophic bacterial denitrification and/or nitrifier denitrification as the main source of N2O production, with a significant contribution of N2O reduction to N2 rather than nitrification (i.e. hydroxylamine oxidation) and fungal denitrification throughout the entire study period. A tendency to a higher contribution of N2O reduction to N2 was observed for the often water-saturated Histic Gleysol, while lower N2O reduction was found for the Plaggic Anthrosol. For two samples, we attempt to validate our results from the isotopocule mapping approach with a parallel 15N labelling study at the field scale (Buchen et al., 2016), as conditions of soil moisture, nitrate availability and N2O flux were similar. References: Buchen, C., Lewicka-Szczebak, D., Fuß, R., Helfrich, M., Flessa, H., Well, R., 2016. Fluxes of N2 and N2O and contributing processes in summer after grassland renewal and grassland conversion to maize cropping on a Plaggic Anthrosol and a Histic Gleysol. Soil Biology and Biochemistry 101, 6-19.

Manganese oxide/poly(3,4-ethylenedioxythiophene) hybrid electrocatalysts for the oxygen reduction reaction in alkaline fuel cells

DOE PAGES

Lambert, Timothy N.; Vigil, Julian A.

2016-08-22

Manganese oxide/poly(3,4-ethylene-dioxythiophene) (MnO x/ PEDOT) nanostructured hybrid thin films were prepared using a simple anodic electrodeposition process from aqueous solution, and then tested for oxygen reduction reaction (ORR) activity in alkaline electrolyte using rotating disk electrode and rotating ring disk electrode methods. MnO x/PEDOT provided improvements over MnO x-only and PEDOT-only control films, with > 0.2 V decrease in onset and half-wave overpotentials, and > 1.5 times increase in terminal current density. The MnO x/PEDOT film exhibited only a slightly lower n value (n = 3.86-3.92) than the 20% Pt/C benchmark electrocatalyst (n = 3.98) across all potentials. MnO x/PEDOTmore » also displayed a more positive half-wave potential and superior electrocatalytic selectivity for the ORR upon methanol exposure than 20% Pt/C. Here, the high activity and synergism of MnO x/PEDOT towards the ORR is attributed to effective intermixing/dispersion of the two materials, intimate substrate contact with improved charge transfer processes attained by co-electrodepositing MnO x with PEDOT and due to the increase in Mn 3+ content at the surface of the oxide.« less

Manganese oxide/poly(3,4-ethylenedioxythiophene) hybrid electrocatalysts for the oxygen reduction reaction in alkaline fuel cells

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

Lambert, Timothy N.; Vigil, Julian A.

Manganese oxide/poly(3,4-ethylene-dioxythiophene) (MnO x/ PEDOT) nanostructured hybrid thin films were prepared using a simple anodic electrodeposition process from aqueous solution, and then tested for oxygen reduction reaction (ORR) activity in alkaline electrolyte using rotating disk electrode and rotating ring disk electrode methods. MnO x/PEDOT provided improvements over MnO x-only and PEDOT-only control films, with > 0.2 V decrease in onset and half-wave overpotentials, and > 1.5 times increase in terminal current density. The MnO x/PEDOT film exhibited only a slightly lower n value (n = 3.86-3.92) than the 20% Pt/C benchmark electrocatalyst (n = 3.98) across all potentials. MnO x/PEDOTmore » also displayed a more positive half-wave potential and superior electrocatalytic selectivity for the ORR upon methanol exposure than 20% Pt/C. Here, the high activity and synergism of MnO x/PEDOT towards the ORR is attributed to effective intermixing/dispersion of the two materials, intimate substrate contact with improved charge transfer processes attained by co-electrodepositing MnO x with PEDOT and due to the increase in Mn 3+ content at the surface of the oxide.« less

The kinetics of ulvoespinel reduction - Synthetic study and applications to lunar rocks.

NASA Technical Reports Server (NTRS)

Mccallister, R. H.; Taylor, L. A.

1973-01-01

The kinetics of Fe2TiO4 reduction to FeTiO3 + Fe were studied using CO-CO2 gas mixtures with fO2 measured by a solid ceramic (calcia-zirconia) oxygen electrolyte cell. Isothermal rate studies at 900 C suggest that the mechanism of Fe2TiO4 reduction is one of nucleation and growth, where the growth stage may be controlled by the diffusion of the reactant through the product layer or volume diffusion. The activation energy for the growth stage of the process was determined to be 46 plus or minus 4 kcal/mole.

Pulse oximeter saturation target limits for preterm infants: a survey among European neonatal intensive care units.

PubMed

Huizing, Maurice J; Villamor-Martínez, Eduardo; Vento, Máximo; Villamor, Eduardo

2017-01-01

The optimum range of pulse oximeter oxygen saturation (SpO 2 ) for preterm infants remains controversial. Between November 2015 and February 2016, we conducted a web-based survey aimed to investigate the current and former practices on SpO 2 targets in European neonatal intensive care units (NICUs). We obtained valid responses from 193 NICUs, treating 8590 newborns ≤28 weeks per year, across 27 countries. Forty different saturation ranges were reported, ranging from 82-93 to 94-99%. The most frequently utilized SpO 2 ranges were 90-95% (28%), 88-95% (12%), 90-94% (5%), and 91-95% (5%). A total of 156 NICUs (81%) changed their SpO 2 limits over the last 10 years. The most frequently reported former limits were 88-92% (18%), 85-95% (9%), 88-93 (7%), and 85-92% (6%). The NICUs that increased their SpO 2 ranges expected to obtain a reduction in mortality. A 54% of the NICUs found the scientific evidence supporting their SpO 2 targeting policy strong or very strong. We detected a high degree of heterogeneity in pulse oximeter SpO 2 target limits across European NICUs. The currently used limits are 3 to 5% higher than the former limits, and the most extreme limits, such as lower below 85% or upper above 96%, have almost been abandoned. What is Known: • For preterm infants requiring supplemental oxygen, the optimum range of pulse oximeter oxygen saturation (SpO 2 ) to minimize organ damage, without causing hypoxic injury, remains controversial. What is New: • This survey highlights the lack of consensus regarding SpO 2 target limits for preterm infants among European neonatal intensive care units (NICUs). We detected 40 different SpO 2 ranges, and even the most frequently reported range (i.e., 90-95%) was used in only 28% of the 193 respondent NICUs. • A total of 156 NICUs (81%) changed their SpO 2 limits over the last 10 years. The currently used limits are 3 to 5% higher than the former limits, and the most extreme limits, such as lower below 85% or upper above 96%, have almost been abandoned.

Probing the Active Surface Sites for CO Reduction on Oxide-Derived Copper Electrocatalysts

DOE PAGES

Verdaguer-Casadevall, Arnau; Li, Christina W.; Johansson, Tobias P.; ...

2015-07-30

CO electroreduction activity on oxide-derived Cu (OD-Cu) was found to correlate with metastable surface features that bind CO strongly. OD-Cu electrodes prepared by H 2 reduction of Cu 2O precursors reduce CO to acetate and ethanol with nearly 50% Faradaic efficiency at moderate overpotential. Temperature-programmed desorption of CO on OD-Cu revealed the presence of surface sites with strong CO binding that are distinct from the terraces and stepped sites found on polycrystalline Cu foil. After annealing at 350 °C, the surface-area corrected current density for CO reduction is 44-fold lower and the Faradaic efficiency is less than 5%. These changesmore » are accompanied by a reduction in the proportion of strong CO binding sites. Here, we propose that the active sites for CO reduction on OD-Cu surfaces are strong CO binding sites that are supported by grain boundaries. Uncovering these sites is a first step toward understanding the surface chemistry necessary for efficient CO electroreduction.« less

N2O + CO reaction over single Ga or Ge atom embedded graphene: A DFT study

NASA Astrophysics Data System (ADS)

Esrafili, Mehdi D.; Vessally, Esmail

2018-01-01

The possibility of using a single Ga or Ge atom embedded graphene as an efficient catalyst for the reduction of N2O molecule by CO is examined. We perform density functional theory calculations to calculate adsorption energies as well as analysis of the structural and electronic properties of different species involved in the N2O + CO reaction. The large activation energy for the diffusion of the single Ga or Ge atom on the C vacancy site of graphene shows the high stability of both Ga- and Ge-embedded graphene sheets in the N2O reduction. The activation energy needed for the decomposition of N2O is calculated to be 18.4 and 14.1 kcal/mol over Ga- and Ge-embedded graphene, respectively. The results indicate that the Ge-embedded graphene may serve as an effective catalyst for the N2O reduction. Moreover, the activation energy for the disproportionation of N2O molecules that generates N2 and O2 is relatively high; so, the generation of these side products may be hindered by decreasing the temperature.

Integrated Solid/Nanoporous Copper/Oxide Hybrid Bulk Electrodes for High-performance Lithium-Ion Batteries

PubMed Central

Hou, Chao; Lang, Xing-You; Han, Gao-Feng; Li, Ying-Qi; Zhao, Lei; Wen, Zi; Zhu, Yong-Fu; Zhao, Ming; Li, Jian-Chen; Lian, Jian-She; Jiang, Qing

2013-01-01

Nanoarchitectured electroactive materials can boost rates of Li insertion/extraction, showing genuine potential to increase power output of Li-ion batteries. However, electrodes assembled with low-dimensional nanostructured transition metal oxides by conventional approach suffer from dramatic reductions in energy capacities owing to sluggish ion and electron transport kinetics. Here we report that flexible bulk electrodes, made of three-dimensional bicontinuous nanoporous Cu/MnO2 hybrid and seamlessly integrated with Cu solid current collector, substantially optimizes Li storage behavior of the constituent MnO2. As a result of the unique integration of solid/nanoporous hybrid architecture that simultaneously enhances the electron transport of MnO2, facilitates fast ion diffusion and accommodates large volume changes on Li insertion/extraction of MnO2, the supported MnO2 exhibits a stable capacity of as high as ~1100 mA h g−1 for 1000 cycles, and ultrahigh charge/discharge rates. It makes the environmentally friendly and low-cost electrode as a promising anode for high-performance Li-ion battery applications. PMID:24096928

Enhanced critical currents in (Gd,Y)Ba2Cu3Ox superconducting tapes with high levels of Zr addition

NASA Astrophysics Data System (ADS)

Selvamanickam, V.; Chen, Y.; Shi, T.; Liu, Y.; Khatri, N. D.; Liu, J.; Yao, Y.; Xiong, X.; Lei, C.; Soloveichik, S.; Galstyan, E.; Majkic, G.

2013-03-01

The critical current and structural properties of (Gd,Y)BaCuO tapes made by metal organic chemical vapor deposition (MOCVD) with Zr addition levels up to 30 at.% have been investigated. The reduction in critical current beyond the previously optimized Zr addition level of 7.5 at.% was found to be due to structural deterioration of the (Gd,Y)Ba2Cu3Ox film. By a modified MOCVD process, enhanced critical current densities have been achieved with high levels of Zr addition, including 3.83 MA cm-2 in 15 at.% Zr-added 1.1 μm thick film at 77 K in zero magnetic field. Critical currents as high as 1072 A/12 mm have been reached in (Gd,Y)BaCuO tapes with 15 at.% Zr addition at 30 K in a field of 3 T applied perpendicular to the tape, corresponding to a pinning force value of 268 GN m-3. The enhanced critical currents achievable with a high density of nanoscale defects by employing high levels of second-phase additions enable the performance targets needed for the use of HTS tapes in coil applications involving high magnetic fields at temperatures below 50 K to be met.

Redox reaction between graphene oxide and In powder to prepare In2O3/reduced graphene oxide hybrids for supercapacitors

NASA Astrophysics Data System (ADS)

Xu, Xiaoyang; Wu, Tao; Xia, Fengling; Li, Yi; Zhang, Congcong; Zhang, Lei; Chen, Mingxi; Li, Xichuan; Zhang, Li; Liu, Yu; Gao, Jianping

2014-11-01

A facile and quick route for the chemical reduction of graphene oxide (GO) using In powder as a reductant has been established. The reduction of GO by In powder is traced by UV-visible absorption spectroscopy, and the obtained reduced graphene oxide (rGO) is analyzed. The In3+ ions produced during the reaction between the GO and the In powder are chemically transformed to In2O3 and then form In2O3/rGO hybrids. The In2O3/rGO hybrids are used as electrode materials and their electrochemical performance are studied using cyclic voltammetry and galvanostatic charge/discharge. The In2O3/rGO hybrids demonstrate excellent electrochemical performance and their highest specific capacitance is 178.8 F g-1 which is much higher than that of either In2O3 or rGO. In addition, the In2O3/rGO hybrids are also very stable.

UV Absorption Cross Sections of Nitrous Oxide (N2O) and Carbon Tetrachloride (CCl4) Between 210 and 350 K and the Atmospheric Implications

NASA Technical Reports Server (NTRS)

Carlon, Nabilah Rontu; Papanastasiou, Dimitrios K.; Fleming, Eric L.; Jackman, Charles H.; Newman, Paul A.; Burkholder, James B.

2010-01-01

Absorption cross sections of nitrous oxide (N2O) and carbon tetrachloride (CCl4) are reported at five atomic UV lines (184.95, 202.548, 206.200, 213.857, and 228.8 nm) at 27 temperatures in the range 210-350 K. In addition, UV absorption spectra of CCl4 are reported between 200-235 nm as a function of temperature (225-350 K). The results from this work are critically compared with results from earlier studies. For N2O, the present results are in good agreement with the current JPL recommendation enabling a reduction in the estimated uncertainty in the N2O atmospheric photolysis rate. For CCl4, the present cross section results are systematically greater than the current recommendation at the reduced temperatures most relevant to stratospheric photolysis. The new cross sections result in a 5-7% increase in the modeled CCl4 photolysis loss, and a slight decrease in the stratospheric lifetime, from 51 to 50 years, for present day conditions. The corresponding changes in modeled inorganic chlorine and ozone in the stratosphere are quite small. A CCl4 cross section parameterization for use in 37 atmospheric model calculations is presented.

The effect of milling time and sintering temperature on Mn, Ti substituted barium hexaferrite nanoparticle

NASA Astrophysics Data System (ADS)

Yustanti, Erlina; Manaf, Azwar

2018-04-01

Barium hexaferrite (BaO.6Fe2O3/BaFe12O19) is a permanent magnetic material and microwave absorbing material. The value of microwave absorption can be increased through the engineering of the material structure, while the reduction of crystallite and particle size up to nanometer results device performance improvement to be superior. In this research, the structural engineering through mechanical alloying and crystallite size reduction through high power ultrasonic irradiation will be explained. Mixing and alloying of Sigma Aldrich BaCO3, Fe2O3, MnCO3, TiO2 p.a 99% precursor material used ball mill with powder ratio of vial at 1:10. Mechanical alloying for 60 hours at 160 rpm produced amorphous material. The process of the crystalline embryo nucleation for 4 hours produced multicrystalline material at a sinter temperature of 1100°C. Phase analysis of the mechanical alloying result using x-ray diffractometer was confirmed either the formation of BaO.6Fe2-xMnx/2Tix/2O3 (x=0.5) single phase. Multicrystalline powder of BaO.6Fe2-xMnx/2Tix/2O3 (x=0.5) was obtained through 20 hours hand grinding and re-milling to bulk sample. Crystallite size reduction in the analysis was conducted through particle density variation in ultrasonic reactor and variation of the increase in ultrasonic time. Increase in milling time up to 60 hours produced fragmenting so that particle size reduction from 18.8 µm to 0.9 µm was occurred. The 12-h ultrasonic irradiation at a frequency of 20 kHz amplitude of 60 µm produced a crystallite-size reduction up to 18 nm at a 10 g/L particle density.

Modification of pH Conferring Virucidal Activity on Dental Alginates

PubMed Central

Nallamuthu, Navina; Braden, Michael; Oxford, John; Williams, David; Patel, Mangala

2015-01-01

To formulate an alginate dental impression material with virucidal properties, experimental alginate dental impression materials were developed and the formulations adjusted in order to study the effect on pH profiles during setting. Commercially available materials served as a comparison. Eight experimental materials were tested for antiviral activity against Herpes Simplex Virus type 1 (HSV-1). Changing the amount of magnesium oxide (MgO) used in the experimental formulations had a marked effect on pH. Increasing MgO concentration corresponded with increased pH values. All experimental materials brought about viral log reductions ranging between 0.5 and 4.0 over a period of 4 h. The material with the lowest pH was the most effective. The current work highlights the very important role of MgO in controlling pH profiles. This knowledge has been applied to the formulation of experimental alginates; where materials with pH values of approximately 4.2–4.4 are able to achieve a significant log reduction when assayed against HSV-1. PMID:28788042

Dual path mechanism in the thermal reduction of graphene oxide.

PubMed

Larciprete, Rosanna; Fabris, Stefano; Sun, Tao; Lacovig, Paolo; Baraldi, Alessandro; Lizzit, Silvano

2011-11-02

Graphene is easily produced by thermally reducing graphene oxide. However, defect formation in the C network during deoxygenation compromises the charge carrier mobility in the reduced material. Understanding the mechanisms of the thermal reactions is essential for defining alternative routes able to limit the density of defects generated by carbon evolution. Here, we identify a dual path mechanism in the thermal reduction of graphene oxide driven by the oxygen coverage: at low surface density, the O atoms adsorbed as epoxy groups evolve as O(2) leaving the C network unmodified. At higher coverage, the formation of other O-containing species opens competing reaction channels, which consume the C backbone. We combined spectroscopic tools and ab initio calculations to probe the species residing on the surface and those released in the gas phase during heating and to identify reaction pathways and rate-limiting steps. Our results illuminate the current puzzling scenario of the low temperature gasification of graphene oxide.

CuO based catalysts on modified acidic silica supports tested in the de-NOx reduction.

PubMed

Bennici, Simona; Gervasini, Antonella; Lazzarin, Marta; Ragaini, Vittorio

2005-03-01

A series of dispersed CuO catalysts supported on modified silica supports with Al2O3 (SA), TiO2 (ST), and ZrO2 (SZ) were prepared optimising the adsorption method of copper deposition assisted by ultrasound treatment, already reported in a previous paper (S. Bennici, A. Gervasini, V. Ragaini, Ultrason. Sonochem. 10 (2003) 61). The obtained catalysts were characterized in their bulk (atomic absorption, X-ray diffraction, temperature programmed reduction) and surface (N2 adsorption, X-ray photoelectron spectroscopy, scanning electron microscopy) properties. The morphology of the finished materials was not deeply modified compared with that of the relevant supports. The employed complemented techniques evidenced a well dispersed CuO phase with a copper-support interaction on the most acidic supports (SA and SZ). The catalyst performances were studied in the reaction of selective catalytic reduction of NOx with ethene in oxidizing atmosphere in a flow apparatus under variable times (0.360-0.072 s) and temperatures (200-450 degrees C). The catalysts prepared on the most acidic supports (SA and SZ) were the most active and selective towards N2 formation. They showed a particular interesting activity in the reaction of NO2 reduction besides that of NO reduction.

Reoxidation of uranium metal immersed in a Li2O-LiCl molten salt after electrolytic reduction of uranium oxide

NASA Astrophysics Data System (ADS)

Choi, Eun-Young; Jeon, Min Ku; Lee, Jeong; Kim, Sung-Wook; Lee, Sang Kwon; Lee, Sung-Jai; Heo, Dong Hyun; Kang, Hyun Woo; Jeon, Sang-Chae; Hur, Jin-Mok

2017-03-01

We present our findings that uranium (U) metal prepared by using the electrolytic reduction process for U oxide (UO2) in a Li2O-LiCl salt can be reoxidized into UO2 through the reaction between the U metal and Li2O in LiCl. Two salt types were used for immersion of the U metal: one was the salt used for electrolytic reduction, and the other was applied to the unused LiCl salts with various concentrations of Li2O and Li metal. Our results revealed that the degree of reoxidation increases with the increasing Li2O concentration in LiCl and that the presence of the Li metal in LiCl suppresses the reoxidation of the U metal.

Electrical and carrier transport properties of the Au/Y2O3/n-GaN metal-insulator-semiconductor (MIS) diode with rare-earth oxide interlayer

NASA Astrophysics Data System (ADS)

Venkata Prasad, C.; Rajagopal Reddy, V.; Choi, Chel-Jong

2017-04-01

The electrical and transport properties of rare-earth Y2O3 on n-type GaN with Au electrode have been investigated by current-voltage and capacitance-voltage techniques at room temperature. The Au/Y2O3/n-GaN metal-insulator-semiconductor (MIS) diode shows a good rectification behavior compared to the Au/n-GaN metal-semiconductor (MS) diode. Statistical analysis showed that a mean barrier height (BH) and ideality factor are 0.78 eV and 1.93, and 0.96 eV and 2.09 for the Au/n-GaN MS and Au/Y2O3/n-GaN MIS diodes, respectively. Results indicate that the high BH is obtained for the MIS diode compared to the MS diode. The BH, ideality factor and series resistance are also estimated by Cheung's function and Norde method. From the forward current-voltage data, the interface state density ( N SS) is estimated for both the MS and MIS Schottky diodes, and found that the estimated N SS is lower for the MIS diode compared to the MS diode. The results reveal that the introduction of Y2O3 interlayer facilitated the reduction of N SS of the Au/n-GaN interface. Experimental results suggest that the Poole-Frenkel emission is a dominant conduction mechanism in the reverse bias region of both Au/n-GaN MS and Au/Y2O3/n-GaN MIS diodes.

Increased reactive oxygen species production during reductive stress: The roles of mitochondrial glutathione and thioredoxin reductases.

PubMed

Korge, Paavo; Calmettes, Guillaume; Weiss, James N

2015-01-01

Both extremes of redox balance are known to cause cardiac injury, with mounting evidence revealing that the injury induced by both oxidative and reductive stress is oxidative in nature. During reductive stress, when electron acceptors are expected to be mostly reduced, some redox proteins can donate electrons to O2 instead, which increases reactive oxygen species (ROS) production. However, the high level of reducing equivalents also concomitantly enhances ROS scavenging systems involving redox couples such as NADPH/NADP+ and GSH/GSSG. Here our objective was to explore how reductive stress paradoxically increases net mitochondrial ROS production despite the concomitant enhancement of ROS scavenging systems. Using recombinant enzymes and isolated permeabilized cardiac mitochondria, we show that two normally antioxidant matrix NADPH reductases, glutathione reductase and thioredoxin reductase, generate H2O2 by leaking electrons from their reduced flavoprotein to O2 when electron flow is impaired by inhibitors or because of limited availability of their natural electron acceptors, GSSG and oxidized thioredoxin. The spillover of H2O2 under these conditions depends on H2O2 reduction by peroxiredoxin activity, which may regulate redox signaling in response to endogenous or exogenous factors. These findings may explain how ROS production during reductive stress overwhelms ROS scavenging capability, generating the net mitochondrial ROS spillover causing oxidative injury. These enzymes could potentially be targeted to increase cancer cell death or modulate H2O2-induced redox signaling to protect the heart against ischemia/reperfusion damage. Copyright © 2015 Elsevier B.V. All rights reserved.

Platinum-Coated Hollow Graphene Nanocages as Cathode Used in Lithium-Oxygen Batteries

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

Wu, Feng; Xing, Yi; Zeng, Xiaoqiao

2016-08-31

One of the formidable challenges facing aprotic lithium-oxygen (Li-O-2) batteries is the high charge overpotential, which induces the formation of byproducts, loss in efficiency, and poor cycling performance. Herein, the synthesis of the ultrasmall Pt-coated hollow graphene nano cages as cathode in Li-O-2 batteries is reported. The charge voltage plateau can reduce to 3.2 V at the current density of 100 mA g(-1), even maintain below 3.5 V when the current density increased to 500 mA g(-1). The unique hollow graphene nanocages matrix can not only provide numerous nanoscale tri-phase regions as active sites for efficient oxygen reduction, but alsomore » offer sufficient amount of mesoscale pores for rapid oxygen diffusion. Furthermore, with strong atomic-level oxygen absorption into its subsurface, ultrasmall Pt catalytically serves as the nucleation site for Li2O2 growth. The Li2O2 is subsequently induced into a favorable form with small size and amorphous state, decomposed more easily during recharge. Meanwhile, the conductive hollow graphene substrate can enhance the catalytic activity of noble metal Pt catalysts due to the graphene-metal interfacial interaction. Benefiting from the above synergistic effects between the hollow graphene nanocages and the nanosized Pt catalysts, the ultrasmall Pt-decorated graphene nanocage cathode exhibits enhanced electrochemical performances.« less

Visible light optical coherence tomography for microvascular oximetry in ocular circulation (Conference Presentation)

NASA Astrophysics Data System (ADS)

Chen, Siyu; Yi, Ji; Zhang, Hao F.

2016-03-01

Visible light optical coherence tomography (vis-OCT) is intrinsically capable of optical determination of blood oxygen saturation (sO2). Thanks to its 3D sectioning ability, confounding factors that plaque multi-wavelength fundus photography can be avoided. We further supplemented it with motion-enhanced angiography (vis-OCTA), which allowed us to resolve retinal micro vessels without losing spectral information. As a result, spectroscopic vis-OCTA can extract microvascular sO2 which are generally inaccessible. Here we extend the theoretical formulation of vis-OCTA oximetry to include optical attenuation, scattering and motion contrast. The model allows robust estimation of sO2, while also promising reduction of illuminating power to 1/3 of current value of ~1 mW. To demonstrate the capability of our approach, we performed oxygen challenge while taking vis-OCTA measurements on rat ocular circulation in vivo. We supplied the experiment animal with the following gas mixture: normal air, 5% CO2 air, pure O2 and 10% O2 air. For each inhalation gas, the OCTA measurements were compared with peripheral capillary sO2 (spO2) provided by a pulse oximeter. The retinal artery sO2 measurements corresponded well with spO2 reading as expected (R2 = 0.87). We found that both retinal and choroidal circulation sO2 moderately increased when we supplied 5% CO2 air. 100% O2 inhalation significantly increased both artery and vein oxygenation. On the contrary, 10% O2 air could deplete the oxygen reservoir in the circulation and lead to low sO2 readings.

Facile, low temperature synthesis of SnO2/reduced graphene oxide nanocomposite as anode material for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Hou, Chau-Chung; Brahma, Sanjaya; Weng, Shao-Chieh; Chang, Chia-Chin; Huang, Jow-Lay

2017-08-01

We demonstrate a facile, single step, low temperature and energy efficient strategy for the synthesis of SnO2-reduced graphene oxide (RGO) nanocomposite where the crystallization of SnO2 nanoparticles and the reduction of graphene oxide takes place simultaneously by an in situ chemical reduction process. The electrochemical property of the SnO2-RGO composite prepared by using low concentrations of reducing agent shows better Li storage performance, good rate capability (378 mAh g-1 at 3200 mA g-1) and stable capacitance (522 mAh g-1 after 50 cycles). Increasing the reductant concentration lead to crystallization of high concentration of SnO2 nanoparticle aggregation and degrade the Li ion storage property.

Recent Advances in TiO2 -Based Nanostructured Surfaces with Controllable Wettability and Adhesion.

PubMed

Lai, Yuekun; Huang, Jianying; Cui, Zequn; Ge, Mingzheng; Zhang, Ke-Qin; Chen, Zhong; Chi, Lifeng

2016-04-27

Bioinspired surfaces with special wettability and adhesion have attracted great interest in both fundamental research and industry applications. Various kinds of special wetting surfaces have been constructed by adjusting the topographical structure and chemical composition. Here, recent progress of the artificial superhydrophobic surfaces with high contrast in solid/liquid adhesion has been reviewed, with a focus on the bioinspired construction and applications of one-dimensional (1D) TiO2-based surfaces. In addition, the significant applications related to artificial super-wetting/antiwetting TiO2-based structure surfaces with controllable adhesion are summarized, e.g., self-cleaning, friction reduction, anti-fogging/icing, microfluidic manipulation, fog/water collection, oil/water separation, anti-bioadhesion, and micro-templates for patterning. Finally, the current challenges and future prospects of this renascent and rapidly developing field, especially with regard to 1D TiO2-based surfaces with special wettability and adhesion, are proposed and discussed. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Dissimilatory perchlorate reduction linked to aerobic methane oxidation via chlorite dismutase

NASA Astrophysics Data System (ADS)

Oremland, R. S.; Baesman, S. M.; Miller, L. G.

2013-12-01

The presence of methane (CH4) in the atmosphere of Mars is controversial yet the evidence has aroused scientific interest, as CH4 could be a harbinger of extant or extinct microbial life. There are various oxidized compounds present on the surface of Mars that could serve as electron acceptors for the anaerobic oxidation of CH4, including perchlorate (ClO4-). We examined the role of perchlorate, chlorate (ClO3-) and chlorite (ClO2-) as oxidants linked to CH4 oxidation. Dissimilatory perchlorate reduction begins with reduction of ClO4- to ClO2- and ends with dismutation of chlorite to yield chloride (Cl-) and molecular oxygen (O2). We explored the potential for aerobic CH4 oxidizing bacteria to couple with oxygen derived from chlorite dismutation during dissimilatory perchlorate reduction. Methane (0.2 kPa) was completely removed within several days from the N2-flushed headspace above cell suspensions of methanotrophs (Methylobacter albus strain BG8) and perchlorate reducing bacteria (Dechloromonas agitata strain CKB) in the presence of 5 mM ClO2-. Similar rates of CH4 consumption were observed for these mixed cultures whether they were co-mingled or segregated under a common headspace, indicating that direct contact of cells was not required for methane consumption to occur. We also observed complete removal of 0.2 kPa CH4 in bottles containing dried soil (enriched in methanotrophs by CH4 additions over several weeks) and D. agitata CKB and in the presence of 10 mM ClO2-. This soil (seasonally exposed sediment) collected from the shoreline of a freshwater lake (Searsville Lake, CA) demonstrated endogenous CH4 uptake as well as perchlorate, chlorate and chlorite reduction/dismutation. However, these experiments required physical separation of soil from the aqueous bacterial culture to allow for the partitioning of O2 liberated from chlorite dismutation into the shared headspace. Although dissimilatory reduction of ClO4- and ClO3- could be inferred from the accumulation of chloride ions either in spent media or in slurries prepared from Searsville Lake soil, neither of these oxyanions evoked methane oxidation when added to either anaerobic mixed cultures or soils enriched in methanotrophs. This result leads us to surmise that the release of O2 during enzymatic perchlorate reduction was low, and that the oxygen produced was unavailable to the aerobic methanotrophs. This was borne out by patterns of O2 and CO2 production during experiments with lake soil, growth media, and pure cultures of dissimilatory perchlorate reducing bacteria. We observed that O2 release during incubation of D. agitata CKB with 10 mM ClO4- or ClO3- was decoupled from metabolism. More O2 was released during incubations without added acetate than with 10 mM acetate and an even greater amount of O2 was released during incubation with heat-killed cells. This suggests a chemical mechanism of O2 production during reaction with ClO4- and ClO3-. Hence, perchlorate reducing bacteria need not be present to facilitate O2 release from the surface of Mars, in support of recent interpretations of Viking LR and GEx experiments.

H2S adsorption and decomposition on the gradually reduced α-Fe2O3(001) surface: A DFT study

NASA Astrophysics Data System (ADS)

Lin, Changfeng; Qin, Wu; Dong, Changqing

2016-11-01

Reduction of iron based desulfurizer occurs during hot gas desulfurization process, which will affect the interaction between H2S and the desulfurizer surface. In this work, a detailed adsorption behavior and dissociation mechanism of H2S on the perfect and reduced α-Fe2O3(001) surfaces, as well as the correlation between the interaction characteristic and reduction degree of iron oxide, have been studied by using periodic density functional theory (DFT) calculations. Results demonstrate that H2S firstly chemisorbs on surface at relatively higher oxidation state (reduction degree χ < 33%), then dissociative adsorption occurs and becomes the main adsorption type after χ > 33%. Reduction of iron oxide benefits the H2S adsorption. Further, dissociation processes of H2S via molecular and dissociative adsorption were investigated. Results show that after reduction of Fe2O3 into the oxidation state around FeO and Fe, the reduced surface exhibits very strong catalytic capacity for H2S decomposition into S species. Meanwhile, the overall dissociation process on all surfaces is exothermic. These results provide a fundamental understanding of reduction effect of iron oxide on the interaction mechanism between H2S and desulfurizer surface, and indicate that rational control of reduction degree of desulfurizer is essential for optimizing the hot gas desulfurization process.

Facile synthesis of morphology-controlled Co3O4 nanostructures through solvothermal method with enhanced catalytic activity for H2O2 electroreduction

NASA Astrophysics Data System (ADS)

Cheng, Kui; Cao, Dianxue; Yang, Fan; Xu, Yang; Sun, Gaohui; Ye, Ke; Yin, Jinling; Wang, Guiling

2014-05-01

Hydrogen peroxide (H2O2) replaced oxygen (O2) as oxidant has been widely investigated due to its faster reduction kinetics, easier storage and handling than gaseous oxygen. The main challenge of using H2O2 as oxidant is the chemical decomposition. In this article, by using different C2H5OH/H2O volume ratio as the solvent, Co3O4 with different morphologies (nanosheet, nanowire, ultrafine nanowire net, nanobelts, and honeycomb-like) direct growth on Ni foam are synthesized via a simple solvothermal method for the first time. Results show that the introduction of ethanol could obviously improve the catalytic performance toward H2O2 electroreduction. The sample prepared in the solution with the C2H5OH/H2O volume ratio of 1:2 shows the best catalytic performance among the five samples and a current density of 0.214 A cm-2 is observed in 3.0 mol L-1 KOH + 0.5 mol L-1 H2O2 at -0.4 V (vs. Ag/AgCl KCl), which is much larger than that on the other metal oxides reported previously, almost comparable with the precious metals. This electrode of Co3O4 directly grown on Ni foam has superior mass transport property, which combining with its low-cost and facile preparation, make it a promising electrode for fuel cell using H2O2 as the oxidant.

Electron-stimulated reactions in layered CO/H2O films: Hydrogen atom diffusion and the sequential hydrogenation of CO to methanol

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

Petrik, Nikolay G.; Monckton, Rhiannon J.; Koehler, Sven

Low-energy (100 eV) electron-stimulated reactions in layered H2O/CO/H2O ices are investigated. For CO trapped within approximately 50 ML of the vacuum interface in the amorphous solid water (ASW) films, both oxidation and reduction reactions are observed. However for CO buried more deeply in the film, only the reduction of CO to methanol is observed. Experiments with layered films of H2O and D2O show that the hydrogen atoms participating in the reduction of the buried CO originate in region from ~10 – 40 ML below the surface of the ASW films and subsequently diffuse through the film. For deeply buried COmore » layers, the CO reduction reactions quickly increase with temperature above ~60 K. We present a simple chemical kinetic model that treats the diffusion of hydrogen atoms in the ASW and sequential hydrogenation of the CO to methanol that accounts for the observations.« less

Lewis Acid Assisted Nitrate Reduction with Biomimetic Molybdenum Oxotransferase Complex.

PubMed

Elrod, Lee Taylor; Kim, Eunsuk

2018-03-05

The reduction of nitrate (NO 3 - ) to nitrite (NO 2 - ) is of significant biological and environmental importance. While Mo IV (O) and Mo VI (O) 2 complexes that mimic the active site structure of nitrate reducing enzymes are prevalent, few of these model complexes can reduce nitrate to nitrite through oxygen atom transfer (OAT) chemistry. We present a novel strategy to induce nitrate reduction chemistry of a previously known catalyst Mo IV (O)(SN) 2 (2), where SN = bis(4- tert-butylphenyl)-2-pyridylmethanethiolate, that is otherwise incapable of achieving OAT with nitrate. Addition of nitrate with the Lewis acid Sc(OTf) 3 (OTf = trifluoromethanesulfonate) to 2 results in an immediate and clean conversion of 2 to Mo VI (O) 2 (SN) 2 (1). The Lewis acid additive further reacts with the OAT product, nitrite, to form N 2 O and O 2 . This work highlights the ability of Sc 3+ additives to expand the reactivity scope of an existing Mo IV (O) complex together with which Sc 3+ can convert nitrate to stable gaseous molecules.

Entanglement of solid vortex matter: a boomerang-shaped reduction forced by disorder in interlayer phase coherence in Bi2Sr2CaCu2O8+y.

PubMed

Kato, T; Shibauchi, T; Matsuda, Y; Thompson, J R; Krusin-Elbaum, L

2008-07-11

We present evidence for entangled solid vortex matter in a glassy state in a layered superconductor Bi2Sr2CaCu2O8+y containing randomly splayed linear defects. The interlayer phase coherence--probed by the Josephson plasma resonance--is enhanced at high temperatures, reflecting the recoupling of vortex liquid by the defects. At low temperatures in the vortex solid state, the interlayer coherence follows a boomerang-shaped reentrant temperature path with an unusual low-field decrease in coherence, indicative of meandering vortices. We uncover a distinct temperature scaling between in-plane and out-of-plane critical currents with opposing dependencies on field and time, consistent with the theoretically proposed "splayed-glass" state.

Preparation of Ferrotitanium Alloys by Electrolysis-Assisted Calciothermic Reduction of Ilmenite in Equimolar CaCl2-NaCl Electrolyte: Effect of Calcium Oxide

NASA Astrophysics Data System (ADS)

Zhou, Zhongren; Zhang, Yingjie; Hua, Yixin; Xu, Cunying; Dong, Peng; Zhang, Qibo; Wang, Ding

2018-04-01

The effect of CaO content on the preparation of ferrotitanium alloys from ilmenite with the method of the electrolysis-assisted calciothermic reduction has been investigated by use of ilmenite powders as raw materials that positions them next to the cathodic molybdenum plate, equimolar CaCl2-NaCl molten salt with 2-7 mol.% CaO as electrolyte and graphite as anode at 700°C with cell voltage of 2.8 V under argon atmosphere. It is demonstrated that increasing the reactant CaO content is beneficial to the calciothermic reduction of ilmenite and the intermediate CaTiO3. Experimental results also show that after 14 h of calciothermic reduction process, the products are ferrotitanium alloys and the specific energy consumption is only about 10.21 kWh kg-1 when adding 5 mol.% CaO into equimolar CaCl2-NaCl molten salt and approximately 14.40 kWh kg-1 when CaO content is increased to 7 mol.%.

Constraining the role of iron in environmental nitrogen transformations. Dual stable isotope systematics of abiotic NO 2- reduction by Fe(II) and its production of N 2O

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

Johnston, David; Wankel, Scott David; Buchwald, Carolyn

Redox reactions involving nitrogen and iron have been shown to have important implications for mobilization of priority contaminants. Thus, an understanding of the linkages between their biogeochemical cycling is critical for predicting subsurface mobilization of radionuclides such as uranium. Despite mounting evidence for biogeochemical interactions between iron and nitrogen, our understanding of their environmental importance remains limited. Here we present an investigation of abiotic nitrite (NO 2 -) reduction by Fe(II) or ‘chemodenitrification,’ and its relevance to the production of nitrous oxide (N 2O), specifically focusing on dual (N and O) isotope systematics under a variety of environmentally relevant conditions.more » We observe a range of kinetic isotope effects that are regulated by reaction rates, with faster rates at higher pH (~8), higher concentrations of Fe(II) and in the presence of mineral surfaces. A clear non-linear relationship between rate constant and kinetic isotope effects of NO 2 - reduction was evident (with larger isotope effects at slower rates) and is interpreted as reflecting the dynamics of Fe(II)-N reaction intermediates. N and O isotopic composition of product N 2O also suggests a complex network of parallel and/or competing pathways. Our findings suggest that NO 2 - reduction by Fe(II) may represent an important abiotic source of environmental N 2O, especially in iron-rich environments experiencing dynamic redox variations. This study provides a multi-compound, multi-isotope framework for evaluating the environmental occurrence of abiotic NO 2 - reduction and N 2O formation, helping future studies constrain the relative roles of abiotic and biological N 2O production pathways.« less

Continuous flow reduction of artemisinic acid utilizing multi-injection strategies-closing the gap towards a fully continuous synthesis of antimalarial drugs.

PubMed

Pieber, Bartholomäus; Glasnov, Toma; Kappe, C Oliver

2015-03-09

One of the rare alternative reagents for the reduction of carbon-carbon double bonds is diimide (HN=NH), which can be generated in situ from hydrazine hydrate (N2H4⋅H2O) and O2. Although this selective method is extremely clean and powerful, it is rarely used, as the rate-determining oxidation of hydrazine in the absence of a catalyst is relatively slow using conventional batch protocols. A continuous high-temperature/high-pressure methodology dramatically enhances the initial oxidation step, at the same time allowing for a safe and scalable processing of the hazardous reaction mixture. Simple alkenes can be selectively reduced within 10-20 min at 100-120 °C and 20 bar O2 pressure. The development of a multi-injection reactor platform for the periodic addition of N2H4⋅H2O enables the reduction of less reactive olefins even at lower reaction temperatures. This concept was utilized for the highly selective reduction of artemisinic acid to dihydroartemisinic acid, the precursor molecule for the semisynthesis of the antimalarial drug artemisinin. The industrially relevant reduction was achieved by using four consecutive liquid feeds (of N2H4⋅H2O) and residence time units resulting in a highly selective reduction within approximately 40 min at 60 °C and 20 bar O2 pressure, providing dihydroartemisinic acid in ≥93% yield and ≥95% selectivity. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The Cost of a Military Person-Year. A Method for Computing Savings from Force Reductions

DTIC Science & Technology

2007-01-01

personnel FASAB Federal Accounting Standards Advisory Board FASB Financial Accounting Standards Board FERS Federal Employee Retirement System FG federal...an average prescribed SMCR of only $61,393, which is clearly problematic: Using the Comptroller’s own methods as mandated by DoD financial man... financial commitment the Figure 4.2 Probability-Adjusted Present Values of Retirement Benefits for Current Members by YOS RAND MG598-4.2 1,400 $ th o u

Formic acid acting as an efficient oxygen scavenger in four-electron reduction of oxygen catalyzed by a heterodinuclear iridium-ruthenium complex in water.

PubMed

Fukuzumi, Shunichi; Kobayashi, Takeshi; Suenobu, Tomoyoshi

2010-09-01

A heterodinuclear iridium-ruthenium complex [Ir(III)(Cp*)(H(2)O)(bpm)Ru(II)(bpy)(2)](SO(4))(2) (Cp* = eta(5)-pentamethyl-cyclopentadienyl, bpm = 2,2'-bipyrimidine, bpy = 2,2'-bipyridine) acts as an effective catalyst for removal of dissolved O(2) by the four-electron reduction of O(2) with formic acid in water at an ambient temperature.

Fischer-Tropsch Cobalt Catalyst Improvements with the Presence of TiO2, La2O3, and ZrO2 on an Alumina Support

NASA Technical Reports Server (NTRS)

Klettlinger, Jennifer Lindsey Suder

2012-01-01

The objective of this study was to evaluate the effect of titanium oxide, lanthanum oxide, and zirconium oxide on alumina supported cobalt catalysts. The hypothesis was that the presence of lanthanum oxide, titanium oxide, and zirconium oxide would reduce the interaction between cobalt and the alumina support. This was of interest because an optimized weakened interaction could lead to the most advantageous cobalt dispersion, particle size, and reducibility. The presence of these oxides on the support were investigated using a wide range of characterization techniques such as SEM, nitrogen adsorption, x-ray diffraction (XRD), temperature programmed reduction (TPR), temperature programmed reduction after reduction (TPR-AR), and hydrogen chemisorptions/pulse reoxidation. Results indicated that both La2O3 and TiO2 doped supports facilitated the reduction of cobalt oxide species in reference to pure alumina supported cobalt catalysts, however further investigation is needed to determine the effect of ZrO2 on the reduction profile. Results showed an increased corrected cluster size for all three doped supported catalysts in comparison to their reference catalysts. The increase in reduction and an increase in the cluster size led to the conclusion that the support-metal interaction weakened by the addition of TiO2 and La2O3. It is also likely that the interaction decreased upon presence of ZrO2 on the alumina, but further research is necessary. Preliminary results have indicated that the alumina-supported catalysts with titanium oxide and lanthanum oxide present are of interest because of the weakened cobalt support interaction. These catalysts showed an increased extent of reduction, therefore more metallic cobalt is present on the support. However, whether or not there is more cobalt available to participate in the Fischer-Tropsch synthesis reaction (cobalt surface atoms) depends also on the cluster size. On one hand, increasing cluster size alone tends to decrease the active site density; on the other hand, by increasing the size of the cobalt clusters, there is less likelihood of forming oxidized cobalt complexes (cobalt aluminate) during Fischer-Tropsch synthesis. Thus, from the standpoint of stability, improving the extent of reduction while increasing the particle size slightly may be beneficial for maintaining the sites, even if there is a slight decrease in overall initial active site density.

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

Kuhn, M., E-mail: kuhnm@mit.edu; Hashimoto, S.; Sato, K.

The oxygen nonstoichiometry of La{sub 0.6}Sr{sub 0.4}CoO{sub 3-{delta}} has been the topic of various reports in the literature, but has been exclusively measured at high oxygen partial pressures, pO{sub 2}, and/or elevated temperatures. For applications of La{sub 0.6}Sr{sub 0.4}CoO{sub 3-{delta}}, such as solid oxide fuel cell cathodes or oxygen permeation membranes, knowledge of the oxygen nonstoichiometry and thermo-chemical stability over a wide range of pO{sub 2} is crucial, as localized low pO{sub 2} could trigger failure of the material and device. By employing coulometric titration combined with thermogravimetry, the oxygen nonstoichiometry of La{sub 0.6}Sr{sub 0.4}CoO{sub 3-{delta}} was measured at highmore » and intermediate pO{sub 2} until the material decomposed (at log(pO{sub 2}/bar) Almost-Equal-To -4.5 at 1073 K). For a gradually reduced sample, an offset in oxygen content suggests that La{sub 0.6}Sr{sub 0.4}CoO{sub 3-{delta}} forms a 'super-reduced' solid solution before decomposing. When the sample underwent alternate reduction-oxidation, a hysteresis-like pO{sub 2} dependence of the oxygen content in the decomposition pO{sub 2} range was attributed to the reversible formation of ABO{sub 3} and A{sub 2}BO{sub 4} phases. Reduction enthalpy and entropy were determined for the single-phase region and confirmed interpolated values from the literature. - Graphical abstract: Oxygen nonstoichiometry (shown as 3-{delta}) of La{sub 0.6}Sr{sub 0.4}CoO{sub 3-{delta}} as a function of pO{sub 2} at 773-1173 K. The experimental data were obtained by thermogravimetric analysis (TG) and coulometric titration (measured either by a simple reduction (CT1) or a 'two-step-forward one-step-back' reduction-oxidation (CT2) procedure). D1 and D2 denote the decomposition pO{sub 2}. The solid lines are the fit to the thermogravimetry and CT1 data. The dashed lines represent the non-equilibrium region where the sample shows a super-reduced state. Highlights: Black-Right-Pointing-Pointer Oxygen nonstoichiometry of La{sub 0.6}Sr{sub 0.4}CoO{sub 3-{delta}} at intermediate temperatures and p(O2). Black-Right-Pointing-Pointer Experimental confirmation of previously interpolated reduction enthalpy. Black-Right-Pointing-Pointer Decomposition p(O2) assessed by coulometric titration. Black-Right-Pointing-Pointer Hysteresis-like p(O2) dependence of oxygen content at decomposition p(O2).« less

Electrocatalysis for oxygen electrodes in fuel cells and water electrolyzers for space applications

NASA Technical Reports Server (NTRS)

Prakash, Jai; Tryk, Donald; Yeager, Ernest

1990-01-01

The lead ruthenate pyrochlore Pb2Ru2O6.5, in both high- and low-area forms, has been characterized using thermogravimetric analysis, X-ray photoelectron spectroscopy, X-ray diffraction, cyclic voltammetry, and O2 reduction and generation kinetic-mechanistic studies. Mechanisms are proposed. Compounds in which part of the Ru is substituted with Ir have also been prepared. They exhibit somewhat better performance for O2 reduction in porous, gas-fed electrodes than the unsubstituted compound. The anodic corrosion resistance of pyrochlore-based porous electrodes was improved by using two different anionically conducting polymer overlayers, which slow down the diffusion of ruthenate and plumbate out of the electrode. The O2 generation performance was improved with both types of electrodes. With a hydrogel overlayer, the O2 reduction performance was also improved.

Thermal generation of spin current in epitaxial CoFe{sub 2}O{sub 4} thin films

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

Guo, Er-Jia, E-mail: ejguophysics@gmail.com, E-mail: klaeui@uni-mainz.de; Quantum Condensed Matter Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37830; Herklotz, Andreas

2016-01-11

The longitudinal spin Seebeck effect (LSSE) has been investigated in high-quality epitaxial CoFe{sub 2}O{sub 4} (CFO) thin films. The thermally excited spin currents in the CFO films are electrically detected in adjacent Pt layers due to the inverse spin Hall effect. The LSSE signal exhibits a linear increase with increasing temperature gradient, yielding a LSSE coefficient of ∼100 nV/K at room temperature. The temperature dependence of the LSSE is investigated from room temperature down to 30 K, showing a significant reduction at low temperatures, revealing that the total amount of thermally generated magnons decreases. Furthermore, we demonstrate that the spin Seebeck effectmore » is an effective tool to study the magnetic anisotropy induced by epitaxial strain, especially in ultrathin films with low magnetic moments.« less

Photocatalytic CO2 reduction over SrTiO3: Correlation between surface structure and activity

NASA Astrophysics Data System (ADS)

Luo, Chao; Zhao, Jie; Li, Yingxuan; Zhao, Wen; Zeng, Yubin; Wang, Chuanyi

2018-07-01

Perovskite oxide SrTiO3 is a promising semiconductor photocatalyst for CO2 reduction, which has two possible chemical surfaces-TiO2-terminated and SrO-terminated surfaces. Up to now, the effect of chemical surface and its modification on CO2 adsorption, activation and sequential photocatalytic reduction is not established. In the work, SrTiO3, surface-Ti-rich SrTiO3 and Sr(OH)2-decorated SrTiO3 were prepared and their structural, surface, and optical properties and photocatalytic activity were explored. It is found that the absorption edge of surface-Ti-rich SrTiO3 shifted toward visible-light region as compared with that of the other two photocatalysts, which is attributed to the decreased Ti 3d ground-state level at the surface. Bicarbonate- (HCO3-) and bidentate carbonate-like (b-CO3=) species are the main species for CO2 adsorption on the surface-Ti-rich SrTiO3, whereas, besides HCO3- and b-CO3=, plenty of monodentate carbonate-like species (m-CO3=) that has relatively low reactivity is present on the SrTiO3 and Sr(OH)2-decorated photocatalysts. As a result, the surface-Ti-rich SrTiO3 exhibits the highest activity for CO2 reduction. Furthermore, although Sr(OH)2-decoration and SrO-terminated surfaces facilitate CO2 fixing, the produced surface species are attached to the weakly active Sr ions, giving rise to the lower reactivity. The present work might supply a guide for designing highly active perovskite-type semiconductors for photocatalysis.

Contact resistance reduction of ZnO thin film transistors (TFTs) with saw-shaped electrode.

PubMed

Park, Woojin; Shaikh, Sohail F; Min, Jung-Wook; Lee, Sang Kyung; Lee, Byoung Hun; Hussain, Muhammad M

2018-08-10

We report on a saw-shaped electrode architecture ZnO thin film transistor (TFT), which effectively increases the channel width. The contact line of the saw-shaped electrode is almost twice as long at the contact metal/ZnO channel junction. We experimentally observed an enhancement in the output drive current by 50% and a reduction in the contact resistance by over 50%, when compared to a typically shaped electrode ZnO TFT consuming the same chip area. This performance enhancement is attributed to the extension of the channel width. This technique can contribute to device performance enhancement, and in particular reduce the contact resistance, which is a serious challenge.

The relationship between helminth infections and low haemoglobin levels in Ethiopian children with blood type A.

PubMed

Degarege, A; Yimam, Y; Madhivanan, P; Erko, B

2017-05-01

The current study was conducted to evaluate the nature of association of ABO blood type with helminth infection and related reduction in haemoglobin concentration. Stool samples were collected from 403 school-age children attending Tikur Wuha Elementary School from February to April 2011. Helminth infection was examined using formol-ether concentration and thick Kato-Katz (two slides per stool specimen) techniques. Haemoglobin level was determined using a HemoCue machine and ABO blood type was determined using the antisera haemagglutination test. Nutritional status was assessed using height and weight measurements. Out of 403 children examined, 169, 120, 96 and 18 had blood type O, A, B and AB, respectively. The prevalences of helminth infections were 46.9% for hookworm, 24.6% for Schistosoma mansoni, 4.2% for Ascaris lumbricoides, 1.7% for Trichuris trichiura and 58.3% for any helminth species. The relative odds of infection with at least one helminth species was significantly higher among children with blood type A (adjusted odds ratio (AOR), 2.10; 95% confidence interval (CI), 1.28-3.45) or blood type B (AOR, 2.08; 95% CI, 1.22-3.56) as compared to children with blood type O. Among children infected with helminths, mean haemoglobin concentration was lower in those with blood type A than those with blood type O (β, -0.36; 95% CI, -0.72 to -0.01). The relative odds of hookworm infection (AOR, 1.78; 95% CI, 1.08-2.92) and related reduction in haemogobin levels (β, -0.45; 95% CI, -0.84 to -0.04) was higher among children with blood type A as compared to those with blood type O. Although the difference was not significant, the relative odds of S. mansoni or A. lumbricoides infections and related reduction in haemoglobin levels was also higher in children with blood type A or B as compared to children with blood type O. In conclusion, children with blood type A are associated with an increased risk of helminth, particularly hookworm, infection and related reduction in haemoglobin level. The mechanisms by which blood type A makes children susceptible to helminth infection and a related reduction in haemoglobin level ought to be investigated.

Titanium dioxide-gold nanocomposite materials embedded in silicate sol-gel film catalyst for simultaneous photodegradation of hexavalent chromium and methylene blue.

PubMed

Pandikumar, Alagarsamy; Ramaraj, Ramasamy

2012-02-15

Aminosilicate sol-gel supported titanium dioxide-gold (EDAS/(TiO(2)-Au)(nps)) nanocomposite materials were synthesized by simple deposition-precipitation method and characterized. The photocatalytic oxidation and reduction activity of the EDAS/(TiO(2)-Au)(nps) film was evaluated using hexavalent chromium (Cr(VI)) and methylene blue (MB) dye under irradiation. The photocatalytic reduction of Cr(VI) to Cr(III) was studied in the presence of hole scavengers such as oxalic acid (OA) and methylene blue (MB). The photocatalytic degradation of MB was investigated in the presence and absence of Cr(VI). Presence of Au(nps) on the (TiO(2))(nps) surface and its dispersion in the silicate sol-gel film (EDAS/(TiO(2)-Au)(nps)) improved the photocatalytic reduction of Cr(VI) and oxidation of MB due to the effective interfacial electron transfer from the conduction band of the TiO(2) to Au(nps) by minimizing the charge recombination process when compared to the TiO(2) and (TiO(2)-Au)(nps) in the absence of EDAS. The EDAS/(TiO(2)-Au)(nps) nanocomposite materials provided beneficial role in the environmental remediation and purification process through synergistic photocatalytic activity by an advanced oxidation-reduction processes. Copyright © 2011 Elsevier B.V. All rights reserved.

A novel synthesis of magnetic and photoluminescent graphene quantum dots/MFe2O4 (M = Ni, Co) nanocomposites for catalytic application

NASA Astrophysics Data System (ADS)

Naghshbandi, Zhwan; Arsalani, Nasser; Zakerhamidi, Mohammad Sadegh; Geckeler, Kurt E.

2018-06-01

In recent year, the research is focused on the nanostructured catalyst with increase physiochemical properties. Herein, Different magnetic nanocomposites of graphene quantum dots (GQD) and MFe2O4 (M = Ni, Co) with intrinsic photoluminescent and ferromagnetic properties were synthesized by a convenient co-precipitation method. The structure, morphology, and properties of these nanocomposites as well as the catalytic activity of the nanocomposites for the reduction of p-nitrophenol were investigated. The catalytic activity was found to be in the order of NiFe2O4/GQD > CoFe2O4/GQD > NiFe2O4 > CoFe2O4. The sample NiFe2O4/GQD exhibited the best catalytic activity with an apparent rate constant of 3.56 min-1 and a reduction completion time to p-aminophenol of 60 s. The catalysts can be reused by a magnetic field and display good stability, which can be recycled for six successive experiment with a conversion percentage of more than 95%. These results demonstrate that the nanocomposite NiFe2O4/GQD is an efficient catalyst for the reduction of p-nitrophenol compound. Also, the new nanocomposites have shown a significant reduction in the direct and indirect energy bandgaps when compared to pure GQD and the corresponding magnetic metal oxides.

The direct reductive amination of electron-deficient amines with aldehydes: the unique reactivity of the Re2O7 catalyst.

PubMed

Das, Braja Gopal; Ghorai, Prasanta

2012-08-25

An unprecedented direct reductive amination of electron-deficient amines such as Cbz-, Boc-, EtOCO-, Fmoc-, Bz-, ArSO(2)-, Ar(2)PO-, etc. protected amines with aldehydes is achieved using the Re(2)O(7) catalyst and silanes as the hydride source. Excellent regioselective mono-alkylation and chemoselective reductive-amination were observed.

Reaction of ferrate (VI)/ferrate (V) with hydrogen peroxide and superoxide anion--a stopped-flow and premix pulse radiolysis study.

PubMed

Rush, J D; Zhao, Z; Bielski, B H

1996-03-01

The reduction of ferrate(VI) to ferrate(V) by superoxide ions was studied over the pH range 2.6-13.0 using the premix pulse radiolysis technique. The pH dependence indicates that only the unstable protonated forms of ferrate, H2FeO4 (pKa3.5) and HFeO4- (pKa7.3) are reactive, k(HFeO4(-) + O2) = (1.7 +/- 0.2) x 10(7) M-1 s-1. The stable ferrate ion, FeO4(2-), showed no significant reactivity towards either hydrogen peroxide or superoxide anion. The rate constants for the spontaneous dimerization and decomposition of the protonated ferrates, e.g. k(HFeO4(-) + HFe04) approximately 250 M-1s-1, are orders of magnitude slower than their corresponding reduction reduction by superoxide indicating an outer-sphere mode of electron transfer for the latter process. In contrast the ferrate(VI) species H3FeO4+ (pKa = 1.6 +/- 0.2), H2FeO4, and HFeO4- oxidize hydrogen peroxide, e.g. k(HFeO4(-) + H2O2) = 170 M-1 s-1), at rates which correspond closely to their dimerization rates suggesting an inner-sphere controlled mechanism.

Controls on Nitrous Oxide Emissions from the Hyporheic Zones of Streams.

PubMed

Quick, Annika M; Reeder, W Jeffery; Farrell, Tiffany B; Tonina, Daniele; Feris, Kevin P; Benner, Shawn G

2016-11-01

The magnitude and mechanisms of nitrous oxide (N 2 O) release from rivers and streams are actively debated. The complex interactions of hydrodynamic and biogeochemical controls on emissions of this important greenhouse gas preclude prediction of when and where N 2 O emissions will be significant. We present observations from column and large-scale flume experiments supporting an integrative model of N 2 O emissions from stream sediments. Our results show a distinct, replicable, pattern of nitrous oxide generation and consumption dictated by subsurface (hyporheic) residence times and biological nitrogen reduction rates. Within this model, N 2 O emission from stream sediments requires subsurface residence times (and microbially mediated reduction rates) be sufficiently long (and fast reacting) to produce N 2 O by nitrate reduction but also sufficiently short (or slow reacting) to limit N 2 O conversion to dinitrogen gas. Most subsurface exchange will not result in N 2 O emissions; only specific, intermediate, residence times (reaction rates) will both produce and release N 2 O to the stream. We also confirm previous observations that elevated nitrate and declining organic carbon reactivity increase N 2 O production, highlighting the importance of associated reaction rates in controlling N 2 O accumulation. Combined, these observations help constrain when N 2 O release will occur, providing a predictive link between stream geomorphology, hydrodynamics, and N 2 O emissions.

Using ultraviolet absorbance and color to assess pharmaceutical oxidation during ozonation of wastewater.

PubMed

Wert, Eric C; Rosario-Ortiz, Fernando L; Snyder, Shane A

2009-07-01

The reduction of ultraviolet (UV) absorbance at 254 nm (UV254) and true color were identified as appropriate surrogates to assess the oxidation of six pharmaceuticals (i.e., carbamazepine, meprobamate, dilantin, primidone, atenolol, and iopromide) during ozonation of wastewater. Three tertiary-treated wastewaters were evaluated during oxidation with ozone (O3) and O3 coupled with hydrogen peroxide (O3/H2O2). The correlation between pharmaceutical oxidation and removal of UV254 was dependent upon the reactivity of each specific compound toward ozone, as measured by the second-order rate constant (k'(O3)). Oxidation of compounds with k'(O3) > 10(3) M(-1) s(-1) correlated well (R2 > 0.73) with UV254 reduction between 0-50%. Oxidation of compounds with apparent k'(O3) < 10 M(-1) s(-1) resulted primarily from hydroxyl radicals and correlated well (R2 > 0.80) with the UV254 reduction of 15-85%. The removal of true color also correlated well (R2 > 0.85) with the oxidation of pharmaceuticals during the ozonation of two wastewaters. These correlations demonstrate that UV254 reduction and true color removal may be used as surrogates to evaluate pharmaceutical oxidation in the presence or absence of dissolved ozone residual during advanced wastewater treatment with O3 or O3/H2O2. The use of online UV254 measurements would allow wastewater utilities to optimize the ozone dose required to meet their specific treatment objectives.

Alternative electron transport mediated by flavodiiron proteins is operational in organisms from cyanobacteria up to gymnosperms.

PubMed

Ilík, Petr; Pavlovič, Andrej; Kouřil, Roman; Alboresi, Alessandro; Morosinotto, Tomas; Allahverdiyeva, Yagut; Aro, Eva-Mari; Yamamoto, Hiroshi; Shikanai, Toshiharu

2017-05-01

Photo-reduction of O 2 to water mediated by flavodiiron proteins (FDPs) represents a safety valve for the photosynthetic electron transport chain in fluctuating light. So far, the FDP-mediated O 2 photo-reduction has been evidenced only in cyanobacteria and the moss Physcomitrella; however, a recent phylogenetic analysis of transcriptomes of photosynthetic organisms has also revealed the presence of FDP genes in several nonflowering plant groups. What remains to be clarified is whether the FDP-dependent O 2 photo-reduction is actually operational in these organisms. We have established a simple method for the monitoring of FDP-mediated O 2 photo-reduction, based on the measurement of redox kinetics of P700 (the electron donor of photosystem I) upon dark-to-light transition. The O 2 photo-reduction is manifested as a fast re-oxidation of P700. The validity of the method was verified by experiments with transgenic organisms, namely FDP knock-out mutants of Synechocystis and Physcomitrella and transgenic Arabidopsis plants expressing FDPs from Physcomitrella. We observed the fast P700 re-oxidation in representatives of all green plant groups excluding angiosperms. Our results provide strong evidence that the FDP-mediated O 2 photo-reduction is functional in all nonflowering green plant groups. This finding suggests a major change in the strategy of photosynthetic regulation during the evolution of angiosperms. © 2017 The Authors. New Phytologist © 2017 New Phytologist Trust.

A Mechanistic Study of O2 Reduction on Water Soluble Phthalocyanines Adsorbed on Graphite Electrodes.

DTIC Science & Technology

1979-10-01

34 -2e- H20 Solution 4 2 dif.k 6 k3 , +2e" 22- k5 20 (ads) The disk-ring cuirrent ratio for the 02 reduction process is as follows: NI/R= 1 + (2k/k 2) + 0...k6/(ZH2f I/2 ) X (3) where X = (2k1/k2k5)(k2 + k3 + k4) + [(2k3 + k4) /k 5 ] (3a) and 0.62D 2/3 v 1 /6 (3b) � . H202 If we assume that...2k1/k2)(k’ 2 + k’ + k) (4) where k Kk-kk’ 1 4a) 2= K56 k 2; k = 󈧼 k3 ; A = K56k4 with K56 = k6 /k5. The diffusion limiting current for a 4

Dielectric properties and carbothermic reduction of zinc oxide and zinc ferrite by microwave heating

PubMed Central

Fabritius, Timo; Heikkinen, Eetu-Pekka; Chen, Guo

2017-01-01

This paper aims to study the dielectric properties and carbothermic reduction of zinc oxide (zincite, ZnO) and zinc ferrite (franklinite, ZnFe2O4) by microwave heating. To achieve this aim, the dielectric properties were measured with an open-ended coaxial method to understand the behaviour of the samples under microwave irradiation. The effects of microwave power, duration time and sample mass on the heating rate, and the effects of the stoichiometric amount of graphite on the reduction of ZnO and decomposition of ZnFe2O4 were investigated. The results show that ZnFe2O4 has significantly higher dielectric properties compared to ZnO. Generally, for both samples, the dielectric values at room temperature were quite low, indicating that both ZnO and ZnFe2O4 are poor microwave absorbers. It was found that the temperatures have a more significant effect on the imaginary permittivities than on the real permittivities. The heating rate showed that the sample temperature increased with increase in microwave power and sample mass. Using 700 W of microwave power and two times the stoichiometric amount of graphite, almost complete reduction of ZnO was achieved in 12 min, while ZnFe2O4 completely decomposed to zincite and wustite in 3 min. PMID:28989772

Formation of Fe nanoparticles on water-washed coal fly ash for enhanced reduction of p-nitrophenol.

PubMed

Park, Jaehyeong; Bae, Sungjun

2018-07-01

The catalytic reduction of p-nitrophenol (p-NP) by coal fly ash (FA) washed with water was investigated in this study. A significant increase in pH (from 7.0 to 10.1) was observed in the suspension of raw fly ash (RFA), while water-washed fly ash (WFA) showed a relatively lower increase in pH (7.2), which was caused by the dissolution of Ca species during the water-washing process. Almost 33.4% of p-NP reduction was observed in the RFA suspension with NaBH 4 in 1 h, while the enhanced reduction of p-NP (87.2%) was observed in the WFA suspension. The catalytic reduction of p-NP was inhibited by addition of CaO and Ca(OH) 2 , indicating that higher amount of CaO dissolved from RFA resulted in the inhibition effect. Similar experiments using different oxides (i.e., Al 2 O 3 , SiO 2 , CaO and MgO) revealed no significant reduction of p-NP, which was comparable with Fe 2 O 3 (75.8%). Results from various surface analyses revealed that iron oxides on the surface of WFA can be reduced to elemental Fe nanoparticles, which can effectively reduce p-NP with NaBH 4 . No significant leaching of heavy metals such as Cr, Pb, and As was observed during the catalytic reduction of p-NP and in the suspension of WFA after reaction at pH 3, 5, 7, and 9 for 24 h, which can solve the toxic effect when the FA is used for environmental applications. We also observed a good reusability of WFA during the recycling test, indicating the potential use of WFA for the treatment of wastewater containing reductively degradable pollutants. Copyright © 2018 Elsevier Ltd. All rights reserved.

Promotion effect of H2 on ethanol oxidation and NOx reduction with ethanol over Ag/Al2O3 catalyst.

PubMed

Yu, Yunbo; Li, Yi; Zhang, Xiuli; Deng, Hua; He, Hong; Li, Yuyang

2015-01-06

The catalytic partial oxidation of ethanol and selective catalytic reduction of NOx with ethanol (ethanol-SCR) over Ag/Al2O3 were studied using synchrotron vacuum ultraviolet (VUV) photoionization mass spectrometry (PIMS). The intermediates were identified by PIMS and their photoionization efficiency (PIE) spectra. The results indicate that H2 promotes the partial oxidation of ethanol to acetaldehyde over Ag/Al2O3, while the simultaneously occurring processes of dehydration and dehydrogenation were inhibited. H2 addition favors the formation of ammonia during ethanol-SCR over Ag/Al2O3, the occurrence of which creates an effective pathway for NOx reduction by direct reaction with NH3. Simultaneously, the enhancement of the formation of ammonia benefits its reaction with surface enolic species, resulting in producing -NCO species again, leading to enhancement of ethanol-SCR over Ag/Al2O3 by H2. Using VUV-PIMS, the reactive vinyloxy radical was observed in the gas phase during the NOx reduction by ethanol for the first time, particularly in the presence of H2. Identification of such a reaction occurring in the gas phase may be crucial for understanding the reaction pathway of HC-SCR over Ag/Al2O3.

Dielectric Properties of BST/(Y 2O 3) x(ZrO 2) 1-x/BST Trilayer Films

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

Sahoo, Santosh K.; Misra, D.

2011-01-31

Thin films of Ba1-xSrxTiO3 (BST) are being actively investigated for applications in dynamic random access memories (DRAM) because of their properties such as high dielectric constant, low leakage current, and high dielectric breakdown strength. Various approaches have been used to improve the dielectric properties of BST thin films such as doping, graded compositions, and multilayer structures. We have found that inserting a ZrO2 layer in between two BST layers results in a significant reduction in dielectric constant as well as dielectric loss. In this work the effect of Y2O3 doped ZrO2 on the dielectric properties of BST/ZrO2/BST trilayer structure ismore » studied. The structure Ba0.8Sr0.2TiO3/(Y2O3)x(ZrO2)1-x/Ba0.8Sr0.2TiO3 is deposited by a sol-gel process on platinized Si substrate. The composition (x) of the middle layer is varied while keeping the total thickness of the trilayer film constant. The dielectric constant of the multilayer film decreases with the increase of Y2O3 amount in the film whereas there is a slight variation in dielectric loss. In Y2O3 doped multilayer thin films, the dielectric loss is lower in comparison to other films and also there is good frequency stability in the loss in the measured frequency range and hence very suitable for microwave device applications.« less

Biochar and denitrification in soils: when, how much and why does biochar reduce N2O emissions?

PubMed Central

Cayuela, Maria Luz; Sánchez-Monedero, Miguel Angel; Roig, Asunción; Hanley, Kelly; Enders, Akio; Lehmann, Johannes

2013-01-01

Agricultural soils represent the main source of anthropogenic N2O emissions. Recently, interactions of black carbon with the nitrogen cycle have been recognized and the use of biochar is being investigated as a means to reduce N2O emissions. However, the mechanisms of reduction remain unclear. Here we demonstrate the significant impact of biochar on denitrification, with a consistent decrease in N2O emissions by 10–90% in 14 different agricultural soils. Using the 15N gas-flux method we observed a consistent reduction of the N2O/(N2 + N2O) ratio, which demonstrates that biochar facilitates the last step of denitrification. Biochar acid buffer capacity was identified as an important aspect for mitigation that was not primarily caused by a pH shift in soil. We propose the function of biochar as an “electron shuttle” that facilitates the transfer of electrons to soil denitrifying microorganisms, which together with its liming effect would promote the reduction of N2O to N2. PMID:23615819

Selective photocatalytic reduction of CO2 to methanol in CuO-loaded NaTaO3 nanocubes in isopropanol

PubMed Central

Xiang, Tianyu; Chen, Jingshuai; Wang, Yuwen; Yin, Xiaohong; Shao, Xiao

2016-01-01

Summary A series of NaTaO3 photocatalysts were prepared with Ta2O5 and NaOH via a hydrothermal method. CuO was loaded onto the surface of NaTaO3 as a cocatalyst by successive impregnation and calcination. The obtained photocatalysts were characterized by XRD, SEM, UV–vis, EDS and XPS and used to photocatalytically reduce CO2 in isopropanol. This worked to both absorb CO2 and as a sacrificial reagent to harvest CO2 and donate electrons. Methanol and acetone were generated as the reduction product of CO2 and the oxidation product of isopropanol, respectively. NaTaO3 nanocubes loaded with 2 wt % CuO and synthesized in 2 mol/L NaOH solution showed the best activity. The methanol and acetone yields were 137.48 μmol/(g·h) and 335.93 μmol/(g·h), respectively, after 6 h of irradiation. Such high activity could be attributed to the good crystallinity, morphology and proper amount of CuO loading, which functioned as reductive sites for selective formation of methanol. The reaction mechanism was also proposed and explained by band theory. PMID:27335766

V-doped TiO2 supported Pt as a promising oxygen reduction reaction catalyst: Synthesis, characterization and in-situ evaluation in proton exchange membrane fuel cell

NASA Astrophysics Data System (ADS)

Bharti, Abha; Cheruvally, Gouri

2017-09-01

This study deals with the synthesis and characterization of V-doped, TiO2 supported Pt catalyst (Pt/V-TiO2) for oxygen reduction reaction (ORR) and its in-situ performance investigation in proton exchange membrane (PEM) fuel cell. Pt/V-TiO2 nanocomposite catalyst is prepared via a facile sol-gel and microwave assisted, modified chemical reduction route and its performance is compared with the undoped TiO2 supported catalyst, Pt/TiO2 prepared in an identical way. The prepared Pt/V-TiO2 and Pt/TiO2 catalysts are employed as cathode catalyst in PEM fuel cell and compared with standard Pt/C catalyst. Their comparative studies are conducted with physical and electrochemical techniques. In-situ electrochemical characterization studies show improved ORR catalytic activity of Pt/V-TiO2 compared to Pt/TiO2. Furthermore, both Pt/TiO2 and Pt/V-TiO2 are more stable than Pt/C when subjected to 6000 voltammetric cycles in the range of 0.2-1.2 V vs. standard hydrogen electrode in operating fuel cell conditions, losing only <20% of its electrochemical surface area as compared to 50% loss exhibited by Pt/C. This study thus demonstrates Pt/V-TiO2 nanocomposite material as a potential cathode catalyst for PEM fuel cell with immense scope for further investigation.

Tunable Oxygen Functional Groups as Electrocatalysts on Graphite Felt Surfaces for All-Vanadium Flow Batteries.

PubMed

Estevez, Luis; Reed, David; Nie, Zimin; Schwarz, Ashleigh M; Nandasiri, Manjula I; Kizewski, James P; Wang, Wei; Thomsen, Edwin; Liu, Jun; Zhang, Ji-Guang; Sprenkle, Vincent; Li, Bin

2016-06-22

A dual oxidative approach using O2 plasma followed by treatment with H2 O2 to impart oxygen functional groups onto the surface of a graphite felt electrode. When used as electrodes for an all-vanadium redox flow battery (VRB) system, the energy efficiency of the cell is enhanced by 8.2 % at a current density of 150 mA cm(-2) compared with one oxidized by thermal treatment in air. More importantly, by varying the oxidative techniques, the amount and type of oxygen groups was tailored and their effects were elucidated. It was found that O-C=O groups improve the cells performance whereas the C-O and C=O groups degrade it. The reason for the increased performance was found to be a reduction in the cell overpotential after functionalization of the graphite felt electrode. This work reveals a route for functionalizing carbon electrodes to improve the performance of VRB cells. This approach can lower the cost of VRB cells and pave the way for more commercially viable stationary energy storage systems that can be used for intermittent renewable energy storage. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of Al2O3 encapsulation on multilayer MoSe2 thin-film transistors

NASA Astrophysics Data System (ADS)

Lee, Hyun Ah; Yeoul Kim, Seong; Kim, Jiyoung; Choi, Woong

2017-03-01

We report the effect of Al2O3 encapsulation on the device performance of multilayer MoSe2 thin-film transistors based on statistical investigation of 29 devices with a SiO2 bottom-gate dielectric. On average, Al2O3 encapsulation by atomic layer deposition increased the field-effect mobility from 10.1 cm2 V-1 s-1 to 14.8 cm2 V-1 s-1, decreased the on/off-current ratio from 8.5  ×  105 to 2.3  ×  105 and negatively shifted the threshold voltage from  -1.1 V to  -8.1 V. Calculation based on the Y-function method indicated that the enhancement of intrinsic carrier mobility occurred independently of the reduction of contact resistance after Al2O3 encapsulation. Furthermore, contrary to previous reports in the literature, we observe a negligible effect of thermal annealing on contact resistance and carrier mobility during the atomic layer deposition of Al2O3. These results demonstrate that Al2O3 encapsulation is a useful method for improving the carrier mobility of multilayer MoSe2 transistors, providing important implications on the application of MoSe2 and other 2D materials into high-performance transistors.

Visible light photoreactivity from hybridization states between carbon nitride bandgap states and valence states in Nb and Ti oxides

NASA Astrophysics Data System (ADS)

Lee, Hosik; Ohno, Takahisa

2013-03-01

For better efficiency as photocatalysts, N-doping for visible light reactivity has been intensively studied in Lamellar niobic and titanic solid acids (HNb3O8, H2Ti4O9), and its microscopic structures have been debated in this decade. We calculate the layered solid acids' structures and bandgaps. Bandgap reduction by carbon nitride adsorption in interlayer space is observed computationally. It originates from localized nitrogen states which form delocalized top-valence states by hybridizing with the host oxygen states and can contribute to photo-current.

Reduction of Selenite to Red Elemental Selenium by Rhodopseudomonas palustris Strain N

PubMed Central

Li, Baozhen; Liu, Na; Li, Yongquan; Jing, Weixin; Fan, Jinhua; Li, Dan; Zhang, Longyan; Zhang, Xiaofeng; Zhang, Zhaoming; Wang, Lan

2014-01-01

The trace metal selenium is in demand for health supplements to human and animal nutrition. We studied the reduction of selenite (SeO3 −2) to red elemental selenium by Rhodopseudomonas palustris strain N. This strain was cultured in a medium containing SeO3 −2 and the particles obtained from cultures were analyzed using transmission electron microscopy (TEM), energy dispersive microanalysis (EDX) and X ray diffraction analysis (XRD). Our results showed the strain N could reduce SeO3 −2 to red elemental selenium. The diameters of particles were 80–200 nm. The bacteria exhibited significant tolerance to SeO3 −2 up to 8.0 m mol/L concentration with an EC50 value of 2.4 m mol/L. After 9 d of cultivation, the presence of SeO3 2− up to 1.0 m mol/L resulted in 99.9% reduction of selenite, whereas 82.0% (p<0.05), 31.7% (p<0.05) and 2.4% (p<0.05) reduction of SeO3 −2 was observed at 2.0, 4.0 and 8.0 m mol/L SeO3 2− concentrations, respectively. This study indicated that red elemental selenium was synthesized by green technology using Rhodopseudomonas palustris strain N. This strain also indicated a high tolerance to SeO3 −2. The finding of this work will contribute to the application of selenium to human health. PMID:24759917

In-situ Measurements of Ozone Production Rates and Comparisons to Model-derived Production Rates During the Houston, TX and Denver, CO DISCOVER-AQ Campaigns

NASA Astrophysics Data System (ADS)

Baier, B. C.; Brune, W. H.; Miller, D. O.; Lefer, B. L.

2015-12-01

Tropospheric ozone (O3) is a secondary pollutant that has harmful effects on human and plant life. The climate and urban emissions in Houston, TX and Denver, CO can be conducive for significant ozone production and thus, high ozone events. Tighter government strategies for ozone mitigation have been proposed, which involve reducing the current EPA eight-hour ozone standard from 75 ppb to 65-70 ppb. These strategies rely on the reduction of ozone precursors in order to decrease the ozone production rate, P(O3). The changes in the ozone concentration at a certain location are dependent upon P(O3), so decreasing P(O3) can decrease ozone levels provided that it has not been transported from other areas. Air quality models test reduction strategies before they are implemented, locate ozone sources, and predict ozone episodes. Traditionally, P(O3) has been calculated by models. However, large uncertainties in model emissions inventories, chemical mechanisms, and meteorology can reduce confidence in this approach. A new instrument, the Measurement of Ozone Production Sensor (MOPS) directly measures P(O3) and can provide an alternate approach to determining P(O3). An updated version of the Penn State MOPS (MOPSv2.0) was deployed to Houston, TX and Denver, CO as a part of NASA's DISCOVER-AQ field campaign in the summers of 2013 and 2014, respectively. We present MOPS directly-measured P(O3) rates from these areas, as well as comparisons to zero-dimensional and three-dimensional modeled P(O3) using the RACM2 and MCMv2.2 mechanisms. These comparisons demonstrate the potential of the MOPS to test and evaluate model-derived P(O3), to advance the understanding of model chemical mechanisms, and to improve predictions of high ozone events.

Oxide surfaces in practical and model catalytic systems

NASA Astrophysics Data System (ADS)

Lanier, Courtney H.

Oxide surface structures play a key role in many technological processes, including catalysis, thin film growth, and layered structures, and a thorough understanding of surface structures and surface structure dynamics is required in order to better engineer materials systems for these processes. This research works towards understanding these fundamental principles through an investigation of practical and model catalytic systems. In this work, the surface structures and dynamics of Mg3(VO4)2, LaAlO3, SrTiO3, and alpha-Fe2O3/Fe3O 4 are investigated under a variety of conditions and by a range of experimental and computational techniques. The structure and morphology of LaAlO3 has been investigated over a range of annealing temperatures, and the ( 5x5 )R26.6° reconstruction of LaAlO3 (001) has been determined using transmission electron diffraction combined with direct methods. The structure is relatively simple, consisting of a lanthanum oxide termination with one lanthanum cation vacancy per surface unit cell. The electronic structure is unusual since a fractional number of holes or atomic occupancies per surface unit cell are required to achieve charge neutrality. The reconstruction can be understood in terms of expulsion of the more electropositive cation from the surface followed by an increased covalency between the remaining surface lanthanum atoms and adjacent oxygen atoms. The c(6x2) is a reconstruction of the SrTiO3 (001) surface that is formed between 1050-1100°C in oxidizing annealing conditions. This work proposes a model for the atomic structure for the c(6x2) obtained through a combination of results from transmission electron diffraction, surface x-ray diffraction, direct methods analysis, computational combinational screening, and density functional theory. As it is formed at high temperatures, the surface is complex and can be described as a short-range ordered phase featuring microscopic domains composed of four main structural motifs. Additionally, non-periodic TiO2 units are present on the surface. The surface and bulk of oriented single crystal Mg3(VO 4)2 have been characterized after treatment in a reducing environment. Annealing in a flow of 7% H2 in N2 causes the reduction of Mg3(VO4)2 to Mg3V 2O6, which is shown to be single-crystal to single-crystal and occurs in such a way that the oxygen framework of the crystal is preserved. Transmission electron microscopy images of crystals at the early stages of reduction show low angle grain boundaries and the formation of channels approximately 50nm in diameter. A model for reduction of Mg3(VO4) 2 to Mg3V2O6 based on the experimental observations and derived from classic nucleation theory is proposed. The so-called Biphase structure on alpha-Fe2O3 has been previously reported and described as islands of Fe1-xO and alpha-Fe2O3 arranged in a 40A periodic unit cell. Based on thermodynamic arguments and experimental evidence, including transmission electron diffraction, we find that the previous structure model was incorrect. Rather, it is found that the Biphase structure is, in fact, related to the reduction of alpha-Fe2O3 to Fe 3O4, is a layered structure, and does not contain islands of Fe1-xO. A model for the Biphase termination consisting of bulk alpha-Fe 2O3 with an Fe3O4 -derived overlayer is developed and is consistent with all current and previously reported experimental findings.

Carbon monoxide formation in UO2 kerneled HTR fuel particles containing oxygen getters

NASA Astrophysics Data System (ADS)

Proksch, E.; Strigl, A.; Nabielek, H.

1986-01-01

Mass spectrometric measurements of CO in irradiated UO2 fuel particles containing oxygen getters are summarized. Uranium carbide addition in the 3% to 15% range reduces the CO release by factors between 25 and 80, up to burn-up levels as high as 70% FIMA. Unintentional gettering by SiC in TRISO coated particles with failed inner pyrocarbon layers results in CO reduction factors between 15 and 110. For ZrC, ambiguous results are obtained; ZrC probably results in CO reduction by a factor of 40; Ce2O3 and La2O3 seem less effective than the carbides; for Ce2O3, reduction factors between 3 and 15 are found. However, the results are possibly incorrect due to premature oxidation of the getter already during fabrication. Addition of SiO2 + Al2O3 has no influence on CO release.

Potential effects of ultraviolet radiation reduction on tundra nitrous oxide and methane fluxes in maritime Antarctica.

PubMed

Bao, Tao; Zhu, Renbin; Wang, Pei; Ye, Wenjuan; Ma, Dawei; Xu, Hua

2018-02-27

Stratospheric ozone has begun to recover in Antarctica since the implementation of the Montreal Protocol. However, the effects of ultraviolet (UV) radiation on tundra greenhouse gas fluxes are rarely reported for Polar Regions. In the present study, tundra N 2 O and CH 4 fluxes were measured under the simulated reduction of UV radiation in maritime Antarctica over the last three-year summers. Significantly enhanced N 2 O and CH 4 emissions occurred at tundra sites under the simulated reduction of UV radiation. Compared with the ambient normal UV level, a 20% reduction in UV radiation increased tundra emissions by an average of 8 μg N 2 O m -2 h -1 and 93 μg CH 4 m -2 h -1 , whereas a 50% reduction in UV radiation increased their emissions by an average of 17 μg N 2 O m -2 h -1 and 128 μg CH 4 m -2 h -1 . No statistically significant correlation (P > 0.05) was found between N 2 O and CH 4 fluxes and soil temperature, soil moisture, total carbon, total nitrogen, NO 3 - -N and NH 4 + -N contents. Our results confirmed that UV radiation intensity is an important factor affecting tundra N 2 O and CH 4 fluxes in maritime Antarctica. Exclusion of the effects of reduced UV radiation might underestimate their budgets in Polar Regions with the recovery of stratospheric ozone.

O2 reduction and denitrification rates in shallow aquifers

NASA Astrophysics Data System (ADS)

Tesoriero, Anthony J.; Puckett, Larry J.

2011-12-01

O2 reduction and denitrification rates were determined in shallow aquifers of 12 study areas representing a wide range in sedimentary environments and climatic conditions. Zero- and first-order rates were determined by relating reactant or product concentrations to apparent groundwater age. O2 reduction rates varied widely within and between sites, with zero-order rates ranging from <3 μmol L-1 yr-1 to more than 140 μmol L-1 yr-1 and first-order rates ranging from 0.02 to 0.27 yr-1. Moderate denitrification rates (10-100 μmol N L-1 yr-1; 0.06-0.30 yr-1) were observed in most areas with O2 concentrations below 60 μmol L-1, while higher rates (>100 μmol N L-1 yr-1; >0.36 yr-1) occur when changes in lithology result in a sharp increase in the supply of electron donors. Denitrification lag times (i.e., groundwater travel times prior to the onset of denitrification) ranged from <20 yr to >80 yr. The availability of electron donors is indicated as the primary factor affecting O2 reduction rates. Concentrations of dissolved organic carbon (DOC) and/or sulfate (an indicator of sulfide oxidation) were positively correlated with groundwater age at sites with high O2 reduction rates and negatively correlated at sites with lower rates. Furthermore, electron donors from recharging DOC are not sufficient to account for appreciable O2 and nitrate reduction. These relations suggest that lithologic sources of DOC and sulfides are important sources of electrons at these sites but surface-derived sources of DOC are not. A review of published rates suggests that denitrification tends to occur more quickly when linked with sulfide oxidation than with carbon oxidation.

O 2 reduction and denitrification rates in shallow aquifers

USGS Publications Warehouse

Tesoriero, A.J.; Puckett, L.J.

2011-01-01

O 2 reduction and denitrification rates were determined in shallow aquifers of 12 study areas representing a wide range in sedimentary environments and climatic conditions. Zero-and first-order rates were determined by relating reactant or product concentrations to apparent groundwater age. O 2 reduction rates varied widely within and between sites, with zero-order rates ranging from <3 ??mol L -1 yr -1 to more than 140 ??mol L -1 yr -1 and first-order rates ranging from 0.02 to 0.27 yr -1. Moderate denitrification rates (10-100 ??mol N L -1 yr -1; 0.06-0.30 yr -1) were observed in most areas with O 2 concentrations below 60 mol L -1, while higher rates (>100 mol N L -1 yr -1; >0.36 yr -1) occur when changes in lithology result in a sharp increase in the supply of electron donors. Denitrification lag times (i.e., groundwater travel times prior to the onset of denitrification) ranged from <20 yr to >80 yr. The availability of electron donors is indicated as the primary factor affecting O 2 reduction rates. Concentrations of dissolved organic carbon (DOC) and/or sulfate (an indicator of sulfide oxidation) were positively correlated with groundwater age at sites with high O 2 reduction rates and negatively correlated at sites with lower rates. Furthermore, electron donors from recharging DOC are not sufficient to account for appreciable O 2 and nitrate reduction. These relations suggest that lithologic sources of DOC and sulfides are important sources of electrons at these sites but surface-derived sources of DOC are not. A review of published rates suggests that denitrification tends to occur more quickly when linked with sulfide oxidation than with carbon oxidation. copyright 2011 by the American Geophysical Union.

Generalized green synthesis and formation mechanism of sponge-like ferrite micro-polyhedra with tunable structure and composition

NASA Astrophysics Data System (ADS)

Tong, Guoxiu; Du, Fangfang; Xiang, Lingjing; Liu, Fangting; Mao, Lulu; Guan, Jianguo

2013-12-01

This paper describes a green versatile glucose-engineered precipitation-sintering process that allows for the selective and mass preparation of spongy porous ferrite (M = Fe, Zn, Co, Ni, Mn, etc.) micro-polyhedra with tunable morphology, texture, and composition. Some kinetic factors, such as the molar ratio of glucose to metal nitrates, reaction temperature, sintering temperature and time, and type of metal nitrates, can be expediently employed to modulate their aspect ratio, shape, size, composition, and textural properties. In this protocol, glucose functions as a reductant, protecting agent, structure-directing agent, and a sacrificial template to guide the assembly of sheet-like nuclei into polyhedral precursors and the formation of spongy porous structures. Owing to larger EM parameters, multiresonant behavior, and dissipative current, spongy porous Fe3O4 polyhedra exhibited enhanced microwave-absorbing properties. This endows them with important potential applications in magnetic devices, catalysis, sorption, photoluminescence, electromagnetic wave absorbing materials, anode materials, and so on. Meanwhile, this general approach can be extended to synthesize other porous sponges with regular geometric configuration because it is simple, inexpensive, environmentally benign, and suitable for extensive production.This paper describes a green versatile glucose-engineered precipitation-sintering process that allows for the selective and mass preparation of spongy porous ferrite (M = Fe, Zn, Co, Ni, Mn, etc.) micro-polyhedra with tunable morphology, texture, and composition. Some kinetic factors, such as the molar ratio of glucose to metal nitrates, reaction temperature, sintering temperature and time, and type of metal nitrates, can be expediently employed to modulate their aspect ratio, shape, size, composition, and textural properties. In this protocol, glucose functions as a reductant, protecting agent, structure-directing agent, and a sacrificial template to guide the assembly of sheet-like nuclei into polyhedral precursors and the formation of spongy porous structures. Owing to larger EM parameters, multiresonant behavior, and dissipative current, spongy porous Fe3O4 polyhedra exhibited enhanced microwave-absorbing properties. This endows them with important potential applications in magnetic devices, catalysis, sorption, photoluminescence, electromagnetic wave absorbing materials, anode materials, and so on. Meanwhile, this general approach can be extended to synthesize other porous sponges with regular geometric configuration because it is simple, inexpensive, environmentally benign, and suitable for extensive production. Electronic supplementary information (ESI) available: Nitrogen adsorption-desorption isotherms, the corresponding pore size distribution curves, TG-DSC curves, XRD pattern, and IR spectra for the precursors; XRD patterns of the samples obtained at various temperatures under N2; XRD pattern, reduction rate, and reactive oxygen species production of ZnO-ZnFe2O4 XRD patterns, SEM images, EDX patterns, nitrogen adsorption-desorption isotherms, and the corresponding pore size distribution curves of CoFe2O4-NiFe2O4-Co1.29Ni1.71O4 polyhedra and NiO-ZnFe2O4. See DOI: 10.1039/c3nr03745b

Hybrid CFx–Ag2V4O11 as a high-energy, power density cathode for application in an underwater acoustic microtransmitter

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

Meduri, Praveen; Chen, Honghao; Chen, Xilin

2011-12-01

This study demonstrates the excellent electrochemical performance of the hybrid carbon fluoride(CFx)/silver vanadium oxide(SVO)/graphene(G) cathode and its potential utilization in Acoustic Telemetry System Transmitter (ATST). The impedance increase issue caused by LiF formation from CFx is effectively addressed by the deposition of conductive silver metal from the reduction of SVO aided by the coexistence of graphene additive thus a prolonged operation voltage is observed with enhanced electronic conductivity throughout the whole discharge process. In particular, the hybrid shows capacity retention of {approx}462 mAhg-1 at 5C rate and 661 mAhg-1 at 1C rate. The peak current delivered from the as-designed hybridmore » cathode is improved compared with that of commercial Zn/Ag2O batteries suggesting the possibility of the further reduction on the size/weight of the micro batteries which is critical for the transmitters.« less

Significant advantages of sulfur-doped graphene in neutral media as electrocatalyst for oxygen reduction comparing with Pt/C

NASA Astrophysics Data System (ADS)

Shi, Xinxin; Zhang, Jiaona; Huang, Tinglin

2018-02-01

Sulfur-doped graphene (SDG) has been found to be an efficient electrocatalyst for oxygen reduction reaction. However, previous studies on the catalytic activity of SDG have been mainly confined to O2-saturated alkaline media which is a typical alkaline fuel cell environment. Air-cathode microbial fuel cells (ACMFCs), as a novel energy conversion and wastewater treatment technology, use the oxygen from air as cathodic reactant in neutral media with low concentration of O2. Thus, it is meaningful to explore the catalytic performance of SDG in such ACMFC environment. The result showed that in ACMFC environment, the peak current density of SDG in CV test was surprisingly 4.5 times higher than that of Pt/C, indicating a much stronger catalytic activity of SDG. Moreover, SDG exhibited a stronger tolerance against the crossover of glucose (a typical anodic fuel in ACMFC) and better stability than Pt/C in neutral media.

Intensified depolymerization of aqueous polyacrylamide solution using combined processes based on hydrodynamic cavitation, ozone, ultraviolet light and hydrogen peroxide.

PubMed

Prajapat, Amrutlal L; Gogate, Parag R

2016-07-01

The present work deals with intensification of depolymerization of polyacrylamide (PAM) solution using hydrodynamic cavitation (HC) reactors based on a combination with hydrogen peroxide (H2O2), ozone (O3) and ultraviolet (UV) irradiation. Effect of inlet pressure in hydrodynamic cavitation reactor and power dissipation in the case of UV irradiation on the extent of viscosity reduction has been investigated. The combined approaches such as HC+UV, HC+O3, HC+H2O2, UV+H2O2 and UV+O3 have been subsequently investigated and found to be more efficient as compared to individual approaches. For the approach based on HC+UV+H2O2, the extent of viscosity reduction under the optimized conditions of HC (3 bar inlet pressure)+UV (8 W power)+H2O2 (0.2% loading) was 97.27% in 180 min whereas individual operations of HC (3 bar inlet pressure) and UV (8 W power) resulted in about 35.38% and 40.83% intrinsic viscosity reduction in 180 min respectively. In the case of HC (3 bar inlet pressure)+UV (8 W power)+ozone (400 mg/h flow rate) approach, the extent of viscosity reduction was 89.06% whereas individual processes of only ozone (400 mg/h flow rate), ozone (400 mg/h flow rate)+HC (3 bar inlet pressure) and ozone (400 mg/h flow rate)+UV (8 W power) resulted in lower extent of viscosity reduction as 50.34%, 60.65% and 75.31% respectively. The chemical structure of the treated PAM by all approaches was also characterized using FTIR (Fourier transform infrared) spectra and it was established that no significant chemical structure changes were obtained during the treatment. Overall, it can be said that the combination of HC+UV+H2O2 is an efficient approach for the depolymerization of PAM solution. Copyright © 2016 Elsevier B.V. All rights reserved.

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

Selvamanickam, V; Chen, Y; Shi, T

The critical current and structural properties of (Gd,Y)BaCuO tapes made by metal organic chemical vapor deposition (MOCVD) with Zr addition levels up to 30 at.% have been investigated. The reduction in critical current beyond the previously optimized Zr addition level of 7.5 at.% was found to be due to structural deterioration of the (Gd,Y)Ba2Cu3Ox film. By a modified MOCVD process,enhanced critical current densities have been achieved with high levels of Zr addition,including 3.83 MA cm(-2) in 15 at.% Zr- added 1.1 mu m thick film at 77 K in zero magnetic field. Critical currents as high as 1072 A/ 12more » mm have been reached in (Gd,Y) BaCuO tapes with 15 at.% Zr addition at 30 K in a field of 3 T applied perpendicular to the tape,corresponding to a pinning force value of 268 GN m(-3). The enhanced critical currents achievable with a high density of nanoscale defects by employing high levels of second- phase additions enable the performance targets needed for the use of HTS tapes in coil applications involving high magnetic fields at temperatures below 50 K to be met.« less

On the mechanism of Candida tropicalis biofilm reduction by the combined action of naturally-occurring anthraquinones and blue light

PubMed Central

Agut, Montserrat; Comini, Laura R.; Cabrera, José L.; Paraje, María G.; Nonell, Santi

2017-01-01

The photoprocesses involved in the photo-induced Candida tropicalis biofilm reduction by two natural anthraquinones (AQs), rubiadin (1) and rubiadin-1-methyl ether (2), were examined. Production of singlet oxygen (1O2) and of superoxide radical anion (O2•−) was studied. Although it was not possible to detect the triplet state absorption of any AQs in biofilms, observation of 1O2 phosphorescence incubated with deuterated Phosphate Buffer Solution, indicated that this species is actually formed in biofilms. 2 was accumulated in the biofilm to a greater extent than 1 and produced measurable amounts of O2•− after 3h incubation in biofilms. The effect of reactive oxygen species scavengers on the photo-induced biofilm reduction showed that Tiron (a specific O2•− scavenger) is most effective than sodium azide (a specific 1O2 quencher). This suggests that O2•− formed by electron transfer quenching of the AQs excited states, is the main photosensitizing mechanism involved in the photo-induced antibiofilm activity, whereas 1O2 participation seems of lesser importance. PMID:28723923

The platinum microelectrode/Nafion interface - An electrochemical impedance spectroscopic analysis of oxygen reduction kinetics and Nafion characteristics

NASA Technical Reports Server (NTRS)

Parthasarathy, Arvind; Dave, Bhasker; Srinivasan, Supramaniam; Appleby, John A.; Martin, Charles R.

1992-01-01

The objectives of this study were to use electrochemical impedance spectroscopy (EIS) to study the oxygen-reduction reaction under lower humidification conditions than previously studied. The EIS technique permits the discrimination of electrode kinetics of oxygen reduction, mass transport of O2 in the membrane, and the electrical characteristics of the membrane. Electrode-kinetic parameters for the oxygen-reduction reaction, corrosion current densities for Pt, and double-layer capacitances were calculated. The production of water due to electrochemical reduction of oxygen greatly influenced the EIS response and the electrode kinetics at the Pt/Nafion interface. From the finite-length Warburg behavior, a measure of the diffusion coefficient of oxygen in Nafion and diffusion-layer thickness was obtained. An analysis of the EIS data in the high-frequency domain yielded membrane and interfacial characteristics such as ionic conductivity of the membrane, membrane grain-boundary capacitance and resistance, and uncompensated resistance.

Tuning the emission of ZnO nanorods based light emitting diodes using Ag doping

NASA Astrophysics Data System (ADS)

Echresh, Ahmad; Chey, Chan Oeurn; Shoushtari, Morteza Zargar; Nur, Omer; Willander, Magnus

2014-11-01

We have fabricated, characterized, and compared ZnO nanorods/p-GaN and n-Zn0.94Ag0.06O nanorods/p-GaN light emitting diodes (LEDs). Current-voltage measurement showed an obvious rectifying behaviour of both LEDs. A reduction of the optical band gap of the Zn0.94Ag0.06O nanorods compared to pure ZnO nanorods was observed. This reduction leads to decrease the valence band offset at n-Zn0.94Ag0.06O nanorods/p-GaN interface compared to n-ZnO nanorods/p-GaN heterojunction. Consequently, this reduction leads to increase the hole injection from the GaN to the ZnO. From electroluminescence measurement, white light was observed for the n-Zn0.94Ag0.06O nanorods/p-GaN heterojunction LEDs under forward bias, while for the reverse bias, blue light was observed. While for the n-ZnO nanorods/p-GaN blue light dominated the emission in both forward and reverse biases. Further, the LEDs exhibited a high sensitivity in responding to UV illumination. The results presented here indicate that doping ZnO nanorods might pave the way to tune the light emission from n-ZnO/p-GaN LEDs.

Consumer preferences, internal color and reduction of shigatoxigenic Escherichia coli in cooked hamburgers.

PubMed

Røssvoll, Elin; Sørheim, Oddvin; Heir, Even; Møretrø, Trond; Olsen, Nina Veflen; Langsrud, Solveig

2014-02-01

The aim of this study was to relate consumer preferences and preparation of hamburgers to color change, internal temperature and reduction of shigatoxigenic Escherichia coli (STEC) serogroups O157 and the "Big Six" (O26, O45, O103, O111, O121, O145) under two ground beef packaging scenarios: 75% O2 MAP and vacuum. 75% O2 MAP hamburgers cooked to 60 °C core temperature appeared done and showed less internal red color (lower a*) than corresponding vacuum hamburgers. Similar STEC reduction (<4 log10) was found for both hamburgers at core temperatures ≤ 66 °C. In a representative survey (N=1046) most consumers reported to judge hamburger doneness by the color and many preferred undercooked hamburgers. Premature browning of 75% O2 MAP hamburgers represents a risk of foodborne illness, when considering consumers' food handling practices. The risk is even greater if such ground beef is prepared by consumers who prefer undercooked hamburgers and judge doneness by color. © 2013.

The effect of X-ray exposure on Ba2SiO4:Eu3+

NASA Astrophysics Data System (ADS)

Volhard, Max-Fabian; Jüstel, Thomas

2018-03-01

The ortho-silicates Ba2SiO4:Eu3+ and Ba2SiO4:Eu2+ are well-established materials for fluorescent light sources, e.g., phosphor converted LEDs. Samples containing Eu2+or Eu3+were synthesised by the solid-state-method, and the phase purity was determined by X-ray powder diffractometry. The photoluminescence of both phosphors was examined as a function of the pre-treatment. Upon irradiation of Ba2SiO4:Eu3+ with X-rays (tungsten target source), the reduction of Eu3+ towards Eu2+ was observed. This reduction behaviour was thoroughly recorded, and the linearity of the process was determined. Furthermore, the relationship between the acceleration voltage and the reduction process is discussed.

Effect of an in situ Hydrogen Plasma Pre-treatment on the Reduction of GaSb Native oxides Prior to Atomic Layer Deposition

DTIC Science & Technology

2013-04-12

absence of Sb-oxides, a reduction in elemental Sb, and an increase in the Ga2O3 content at the interface. The use of an in situ hydrogen...elemental Sb, and an increase in the Ga2O3 content at the interface. The use of an in situ hydrogen plasma pre-treatment eliminates the need for wet...the +1 state (Ga2O) and the +3 state ( Ga2O3 ), with peak positions found at 530.5 eV (Sb2O4), 20.1 eV (Ga2O), and 20.7 eV ( Ga2O3 ) [11,18]. The AFM image

Independence of nutrient limitation and carbon dioxide impacts on the Southern Ocean coccolithophore Emiliania huxleyi.

PubMed

Müller, Marius N; Trull, Thomas W; Hallegraeff, Gustaaf M

2017-08-01

Future oceanic conditions induced by anthropogenic greenhouse gas emissions include warming, acidification and reduced nutrient supply due to increased stratification. Some parts of the Southern Ocean are expected to show rapid changes, especially for carbonate mineral saturation. Here we compare the physiological response of the model coccolithophore Emiliania huxleyi (strain EHSO 5.14, originating from 50 o S, 149 o E) with pH/CO 2 gradients (mimicking ocean acidification ranging from 1 to 4 × current pCO 2 levels) under nutrient-limited (nitrogen and phosphorus) and -replete conditions. Both nutrient limitations decreased per cell photosynthesis (particulate organic carbon (POC) production) and calcification (particulate inorganic carbon (PIC) production) rates for all pCO 2 levels, with more than 50% reductions under nitrogen limitation. These impacts, however, became indistinguishable from nutrient-replete conditions when normalized to cell volume. Calcification decreased three-fold and linearly with increasing pCO 2 under all nutrient conditions, and was accompanied by a smaller ~30% nonlinear reduction in POC production, manifested mainly above 3 × current pCO 2 . Our results suggest that normalization to cell volume allows the major impacts of nutrient limitation (changed cell sizes and reduced PIC and POC production rates) to be treated independently of the major impacts of increasing pCO 2 and, additionally, stresses the importance of including cell volume measurements to the toolbox of standard physiological analysis of coccolithophores in field and laboratory studies.

Independence of nutrient limitation and carbon dioxide impacts on the Southern Ocean coccolithophore Emiliania huxleyi

PubMed Central

Müller, Marius N; Trull, Thomas W; Hallegraeff, Gustaaf M

2017-01-01

Future oceanic conditions induced by anthropogenic greenhouse gas emissions include warming, acidification and reduced nutrient supply due to increased stratification. Some parts of the Southern Ocean are expected to show rapid changes, especially for carbonate mineral saturation. Here we compare the physiological response of the model coccolithophore Emiliania huxleyi (strain EHSO 5.14, originating from 50oS, 149oE) with pH/CO2 gradients (mimicking ocean acidification ranging from 1 to 4 × current pCO2 levels) under nutrient-limited (nitrogen and phosphorus) and -replete conditions. Both nutrient limitations decreased per cell photosynthesis (particulate organic carbon (POC) production) and calcification (particulate inorganic carbon (PIC) production) rates for all pCO2 levels, with more than 50% reductions under nitrogen limitation. These impacts, however, became indistinguishable from nutrient-replete conditions when normalized to cell volume. Calcification decreased three-fold and linearly with increasing pCO2 under all nutrient conditions, and was accompanied by a smaller ~30% nonlinear reduction in POC production, manifested mainly above 3 × current pCO2. Our results suggest that normalization to cell volume allows the major impacts of nutrient limitation (changed cell sizes and reduced PIC and POC production rates) to be treated independently of the major impacts of increasing pCO2 and, additionally, stresses the importance of including cell volume measurements to the toolbox of standard physiological analysis of coccolithophores in field and laboratory studies. PMID:28430186

Electrical conductivity and rate-capability of Li 4Ti 5O 12 as a function of heat-treatment atmosphere

NASA Astrophysics Data System (ADS)

Wolfenstine, J.; Lee, U.; Allen, J. L.

Recently there has considerable interest in Li 4Ti 5O 12 as a potential anode for use in Li-ion batteries [1-8]. It has many advantages compared to the currently used graphite. For example, it is a zero-strain lithium insertion host suggesting virtually unlimited cycle life. It features a flat, operating voltage of about 1.5 V versus lithium, above the reduction potential of common electrolyte solvents thus, it does not form a solid electrolyte interface based on solvent reduction which should be a favorable property for high rate and low temperature operation. This voltage also is sufficiently high such that the dangers of lithium plating that can occur at high rate and/or low temperature are removed. However, several disadvantages exist compared to graphite. These include low rate-capability as a result of its low electronic conductivity [6]. Consequently, there have been several studies which have focused on improving electronic conductivity with the intent of improving its rate-capability [4,6,8]. For example, recently Huang et al. [8] have shown that the formation of a Li 4Ti 5O 12/Cu xO composite anode that was formed by heat-treatment under a 3 vol.% H 2 in N 2 atmosphere at high rates (>2C) had a higher capacity over a similar powders heat-treated under air. For example, at 10C the capacity of the powders heated under the 3 vol.% H 2 in N 2 atmosphere was about 1.8 X that for the powders heated under air and was attributed to the higher electrical conductivity of the composite heated under the reducing atmosphere compared to under air. The electrical conductivity of the composite formed under the reducing atmosphere was about an order magnitude higher than that for the composite heated under air. Huang et al. [8] suggested that the improved electrical conductivity was a result of the reduction of some Ti 4+ to Ti 3+ in Li 4Ti 5O 12 and/or reduction of Cu 2+/Cu + in Cu xO to Cu metal under the reducing atmosphere. However, they did not separate these effects. For example, they did not compare the results of the Li 4Ti 5O 12 matrix material heated under the reducing atmosphere to that for heat-treatment under air. It is the purpose of this letter to investigate and compare the electronic conductivity and rate-capability of Li 4Ti 5O 12 heated under a reducing atmosphere to that for heat-treatment under air and to determine the contribution of the Li 4Ti 5O 12 matrix to the excellent rate-capability of the Li 4Ti 5O 12/Cu xO composite heated under a reducing atmosphere.

Negative voltage modulated multi-level resistive switching by using a Cr/BaTiOx/TiN structure and quantum conductance through evidence of H2O2 sensing mechanism.

PubMed

Chakrabarti, Somsubhra; Ginnaram, Sreekanth; Jana, Surajit; Wu, Zong-Yi; Singh, Kanishk; Roy, Anisha; Kumar, Pankaj; Maikap, Siddheswar; Qiu, Jian-Tai; Cheng, Hsin-Ming; Tsai, Ling-Na; Chang, Ya-Ling; Mahapatra, Rajat; Yang, Jer-Ren

2017-07-05

Negative voltage modulated multi-level resistive switching with quantum conductance during staircase-type RESET and its transport characteristics in Cr/BaTiO x /TiN structure have been investigated for the first time. The as-deposited amorphous BaTiO x film has been confirmed by high-resolution transmission electron microscopy. X-ray photo-electron spectroscopy shows different oxidation states of Ba in the switching material, which is responsible for tunable more than 10 resistance states by varying negative stop voltage owing to slow decay value of RESET slope (217.39 mV/decade). Quantum conductance phenomenon has been observed in staircase RESET cycle of the memory devices. By inspecting the oxidation states of Ba + and Ba 2+ through measuring H 2 O 2 with a low concentration of 1 nM in electrolyte/BaTiO x /SiO 2 /p-Si structure, the switching mechanism of each HRS level as well as the multi-level phenomenon has been explained by gradual dissolution of oxygen vacancy filament. Along with negative stop voltage modulated multi-level, current compliance dependent multi-level has also been demonstrated and resistance ratio up to 2000 has been achieved even for a thin (<5 nm) switching material. By considering oxidation-reduction of the conducting filaments, the current-voltage switching curve has been simulated as well. Hence, multi-level resistive switching of Cr/BaTiO x /TiN structure implies the promising applications in high dense, multistate non-volatile memories in near future.

Facile one-pot synthesis of platinum nanoparticles decorated nitrogen-graphene with high electrocatalytic performance for oxygen reduction and anodic fuels oxidation

NASA Astrophysics Data System (ADS)

Navaee, Aso; Salimi, Abdollah; Soltanian, Saeid; Servati, Peyman

2015-03-01

Due to exceptional electronic properties of graphene (Gr) and nitrogen doped graphene (N-Gr), they are considered as superior supporting platforms for novel metal nanoparticle decorations. Here, we report, a novel one-step electrochemical method for synthesis of Nitrogen-doped graphene sheets uniformly decorated with platinum nanoparticles (Pt/N-Gr). A graphite rod and platinum wire are respectively used for graphene and platinum nanoparticles production. The potential is cycled from -3V to +3V in acetonitrile solution as a nitrogen dopant source. By increasing the number of cycles the nitrogen-doped graphene/platinum nanoparticles composite is generated. After heat-treating the composite is characterized with various techniques such as FTIR, Raman, XPS, SEM and TEM. The electrocatalytic activity of the prepared composite toward the reduction of O2 and the oxidation of usual anodic fuels such as methanol, ethanol, hydrazine and formic acid is investigated using cyclic voltammetry technique. In comparison to commercial platinum/carbon, the onset potentials and the current densities for both O2 reduction and fuels oxidation are remarkably improved. Furthermore, the modified electrode by this composite shows good long-term stability and poisoning tolerance.

TiN/Al2O3/ZnO gate stack engineering for top-gate thin film transistors by combination of post oxidation and annealing

NASA Astrophysics Data System (ADS)

Kato, Kimihiko; Matsui, Hiroaki; Tabata, Hitoshi; Takenaka, Mitsuru; Takagi, Shinichi

2018-04-01

Control of fabrication processes for a gate stack structure with a ZnO thin channel layer and an Al2O3 gate insulator has been examined for enhancing the performance of a top-gate ZnO thin film transistor (TFT). The Al2O3/ZnO interface and the ZnO layer are defective just after the Al2O3 layer formation by atomic layer deposition. Post treatments such as plasma oxidation, annealing after the Al2O3 deposition, and gate metal formation (PMA) are promising to improve the interfacial and channel layer qualities drastically. Post-plasma oxidation effectively reduces the interfacial defect density and eliminates Fermi level pinning at the Al2O3/ZnO interface, which is essential for improving the cut-off of the drain current of TFTs. A thermal effect of post-Al2O3 deposition annealing at 350 °C can improve the crystalline quality of the ZnO layer, enhancing the mobility. On the other hand, impacts of post-Al2O3 deposition annealing and PMA need to be optimized because the annealing can also accompany the increase in the shallow-level defect density and the resulting electron concentration, in addition to the reduction in the deep-level defect density. The development of the interfacial control technique has realized the excellent TFT performance with a large ON/OFF ratio, steep subthreshold characteristics, and high field-effect mobility.

Reduction in Susceptibility of MOS Devices to Radiation- and Electrically-Induced Defects

DTIC Science & Technology

2012-05-01

current density of 150 nA/cm2 for a time varying between 5 and 60 sec. Following implantation , the PMMA was etched off, and circular Al dots (2.67 x 10...calculations showing location of He ions implanted at 5.2 keV through 70 nm of PMMA on 35.6 nm SiO2. We have done TRIM calculations for energies...Instability (NBTI) and to radiation damage could be reduced. To that end, two techniques were attempted. In the first attempt, helium ions were implanted

Intensification of depolymerization of polyacrylic acid solution using different approaches based on ultrasound and solar irradiation with intensification studies.

PubMed

Prajapat, Amrutlal L; Gogate, Parag R

2016-09-01

Depolymerization of polyacrylic acid (PAA) as sodium salt has been investigated using ultrasonic and solar irradiations with process intensification studies based on combination with hydrogen peroxide (H2O2) and ozone (O3). Effect of solar intensity, ozone flow and ultrasonic power dissipation on the extent of viscosity reduction has been investigated for individual treatment approaches. The combined approaches such as US+solar, solar+O3, solar+H2O2, US+H2O2 and US+O3 have been subsequently investigated under optimum conditions and established to be more efficient as compared to individual approaches. Approach based on US (60W)+solar+H2O2 (0.01%) resulted in the maximum extent of viscosity reduction as 98.97% in 35min whereas operation of solar+H2O2 (0.01%), US (60W), H2O2 (0.3%) and solar irradiation resulted in about 98.08%, 90.13%, 8.91% and 90.77% intrinsic viscosity reduction in 60min respectively. Approach of US (60W)+solar+ozone (400mg/h flow rate) resulted in extent of viscosity reduction as 99.47% in 35min whereas only ozone (400mg/h flow rate), ozone (400mg/h flow rate)+US (60W) and ozone (400mg/h flow rate)+solar resulted in 69.04%, 98.97% and 98.51% reduction in 60min, 55min and 55min respectively. The chemical identity of the treated polymer using combined approaches was also characterized using FTIR (Fourier transform infrared) spectra and it was established that no significant structural changes were obtained during the treatment. Overall, it can be said that the combination technique based on US and solar irradiations in the presence of hydrogen peroxide is the best approach for the depolymerization of PAA solution. Copyright © 2016 Elsevier B.V. All rights reserved.

Role of acetate and nitrates in the selective catalytic reduction of NO by propene over alumina catalyst as investigated by FTIR

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

Shimizu, Kenichi; Kawabata, Hisaya; Satsuma, Atsushi

1999-06-24

It is widely accepted that selective catalytic reduction (SCR) of NO by hydrocarbons is a potential method to remove NO{sub x} practically in excess O{sub 2}. Although many studies on SCR are related to zeolitic catalysts, metal oxides are also of importance as promising SCR catalysts due to their high durability. Among oxide catalysts, {gamma}-Al{sub 2}O{sub 3} is one of the most active single oxides for SCR. The mechanism of the selective catalytic reduction (SCR) of NO by C{sub 3}H{sub 6} on Al{sub 2}O{sub 3} was investigated using in situ IR spectroscopy. Attention was focused on the reactivity of themore » adsorbed acetate and nitrates on the Al{sub 2}O{sub 3} surface. IR spectra showed that the reaction starts with the nitrates formation from NO + O{sub 2} followed by its reaction with C{sub 3}H{sub 6} to form acetate, which becomes the predominant surface species in the steady-state condition. The acetate band, which was stable in He or NO, significantly decreased when the flowing gas was switched to NO + O{sub 2}. A complementary set of experiments monitoring gas composition showed that N{sub 2} and CO{sub x} were produced by the reaction of acetate with NO + O{sub 2}. The rate of acetate consumption in NO + O{sub 2} exhibited the same order of magnitude as the NO reduction rate, indicating that the acetate is active as a reductant and takes part in the N{sub 2} formation. Nitrates can oxidize both C{sub 3}H{sub 6} and acetate, and are mostly reduced to N{sub 2}. A proposed reaction scheme explains the role of O{sub 2} in facilitating SCR of NO.« less

Emissions reduction policies and recent trends in Southern California's ambient air quality.

PubMed

Lurmann, Fred; Avol, Ed; Gilliland, Frank

2015-03-01

To assess accountability and effectiveness of air regulatory policies, we reviewed more than 20 years of monitoring data, emissions estimates, and regulatory policies across several southern California communities participating in a long-term study of children's health. Between 1994 and 2011, air quality improved for NO2 and PM2.5 in virtually all the monitored communities. Average NO2 declined 28% to 53%, and PM2.5 decreased 13% to 54%. Year-to-year PM2.5 variability at lower pollution sites was large compared to changes in long-term trends. PM10 and O3 decreases were largest in communities that were initially among the most polluted. Trends in annual average NO2, PM2.5, and PM10 concentrations in higher pollution communities were generally consistent with NOx, ROG, SOx, PM2.5, and PM10 emissions decreases. Reductions observed at one of the higher PM2.5 sites, Mira Loma, were generally within the range expected from reductions observed in ROG, NOx, SOx, and PM2.5 emissions. Despite a 38% increase in regional motor vehicle activity, vigorous economic growth, and a 30% population increase, total estimated emissions of NOx, ROG, SOx, PM2.5, and PM10 decreased by 54%, 65%, 40%, 21%, and 15%, respectively, during the 20-year time period. Emission control strategies in California have achieved dramatic reductions in ambient NO2, O3, PM2.5, and PM10. However, additional reductions will still be needed to achieve current health-based clean air standards. For many cities facing the challenge of reducing air pollution to meet health-based standards, the emission control policies and pollution reduction programs adopted in southern California should serve as an example of the potential success of aggressive, comprehensive, and integrated approaches. Policies targeting on-road mobile emissions were the single most important element for observed improvements in the Los Angeles region. However, overall program success was the result of a much broader approach designed to achieve emission reductions across all major pollutants and emissions categories.

Dark current suppression of MgZnO metal-semiconductor-metal solar-blind ultraviolet photodetector by asymmetric electrode structures.

PubMed

Wang, Ping; Zheng, Qinghong; Tang, Qing; Yang, Yintang; Guo, Lixin; Huang, Feng; Song, Zhenjie; Zhang, Zhiyong

2014-01-15

The application of asymmetric Schottky barrier and electrode area in an MgZnO metal-semiconductor-metal (MSM) solar-blind ultraviolet photodetector has been investigated by a physical-based numerical model in which the electron mobility is obtained by an ensemble Monte Carlo simulation combined with first principle calculations using the density functional theory. Compared with the experimental data of symmetric and asymmetric MSM structures based on ZnO substrate, the validity of this model is verified. The asymmetric Schottky barrier and electrode area devices exhibit reductions of 20 times and 1.3 times on dark current, respectively, without apparent photocurrent scarification. The plots of photo-to-dark current ratio (PDR) indicate that the asymmetric MgZnO MSM structure has better dark current characteristic than that of the symmetric one.

Synthesis of ZnO nanoparticles for oil-water interfacial tension reduction in enhanced oil recovery

NASA Astrophysics Data System (ADS)

Soleimani, Hassan; Baig, Mirza Khurram; Yahya, Noorhana; Khodapanah, Leila; Sabet, Maziyar; Demiral, Birol M. R.; Burda, Marek

2018-02-01

Nanoparticles show potential use in applications associated with upstream oil and gas engineering to increase the performance of numerous methods such as wettability alteration, interfacial tension reduction, thermal conductivity and enhanced oil recovery operations. Surface tension optimization is an important parameter in enhanced oil recovery. Current work focuses on the new economical method of surface tension optimization of ZnO nanofluids for oil-water interfacial tension reduction in enhanced oil recovery. In this paper, zinc oxide (ZnO) nanocrystallites were prepared using the chemical route and explored for enhanced oil recovery (EOR). Adsorption of ZnO nanoparticles (NPs) on calcite (111) surface was investigated using the adsorption locator module of Materials Studio software. It was found that ZnO nanoparticles show maximum adsorption energy of - 253 kcal/mol. The adsorption of ZnO on the rock surface changes the wettability which results in capillary force reduction and consequently increasing EOR. The nanofluids have been prepared by varying the concentration of ZnO nanoparticles to find the optimum value for surface tension. The surface tension (ST) was calculated with different concentration of ZnO nanoparticles using the pendant drop method. The results show a maximum value of ST 35.57 mN/m at 0.3 wt% of ZnO NPs. It was found that the nanofluid with highest surface tension (0.3 wt%) resulted in higher recovery efficiency. The highest recovery factor of 11.82% at 0.3 wt% is due to the oil/water interfacial tension reduction and wettability alteration.

Comparative analysis of the effects of tantalum doping and annealing on atomic layer deposited (Ta{sub 2}O{sub 5}){sub x}(Al{sub 2}O{sub 3}){sub 1−x} as potential gate dielectrics for GaN/Al{sub x}Ga{sub 1−x}N/GaN high electron mobility transistors

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

Partida-Manzanera, T., E-mail: sgtparti@liv.ac.uk; Institute of Materials Research and Engineering, A*STAR; Roberts, J. W.

2016-01-14

This paper describes a method to optimally combine wide band gap Al{sub 2}O{sub 3} with high dielectric constant (high-κ) Ta{sub 2}O{sub 5} for gate dielectric applications. (Ta{sub 2}O{sub 5}){sub x}(Al{sub 2}O{sub 3}){sub 1−x} thin films deposited by thermal atomic layer deposition (ALD) on GaN-capped Al{sub x}Ga{sub 1−x}N/GaN high electron mobility transistor (HEMT) structures have been studied as a function of the Ta{sub 2}O{sub 5} molar fraction. X-ray photoelectron spectroscopy shows that the bandgap of the oxide films linearly decreases from 6.5 eV for pure Al{sub 2}O{sub 3} to 4.6 eV for pure Ta{sub 2}O{sub 5}. The dielectric constant calculated from capacitance-voltage measurementsmore » also increases linearly from 7.8 for Al{sub 2}O{sub 3} up to 25.6 for Ta{sub 2}O{sub 5}. The effect of post-deposition annealing in N{sub 2} at 600 °C on the interfacial properties of undoped Al{sub 2}O{sub 3} and Ta-doped (Ta{sub 2}O{sub 5}){sub 0.12}(Al{sub 2}O{sub 3}){sub 0.88} films grown on GaN-HEMTs has been investigated. These conditions are analogous to the conditions used for source/drain contact formation in gate-first HEMT technology. A reduction of the Ga-O to Ga-N bond ratios at the oxide/HEMT interfaces is observed after annealing, which is attributed to a reduction of interstitial oxygen-related defects. As a result, the conduction band offsets (CBOs) of the Al{sub 2}O{sub 3}/GaN-HEMT and (Ta{sub 2}O{sub 5}){sub 0.16}(Al{sub 2}O{sub 3}){sub 0.84}/GaN-HEMT samples increased by ∼1.1 eV to 2.8 eV and 2.6 eV, respectively, which is advantageous for n-type HEMTs. The results demonstrate that ALD of Ta-doped Al{sub 2}O{sub 3} can be used to control the properties of the gate dielectric, allowing the κ-value to be increased, while still maintaining a sufficient CBO to the GaN-HEMT structure for low leakage currents.« less

Global Warming in the Twenty-First Century: An Alternative Scenario

NASA Technical Reports Server (NTRS)

Hansen, James; Sato, Makiko; Ruedy, Reto; Lacis, Andrew; Oinas, Valdar; Travis, Larry (Technical Monitor)

2000-01-01

A common view is that the current global warming rate will continue or accelerate. But we argue that rapid warming in recent decades has been driven mainly by non-CO2 greenhouse gases (GHGs), such as chlorofluorocarbons, CH4, and N2O, not by the products of fossil fuel burning, CO2 and aerosols, the positive and negative climate forcings of which are partially offsetting. The growth rate of non-CO2 GHGs has declined in the past decade. If sources of CH4 and O3 precursors were reduced in the future, the change in climate forcing by non-CO2 GHGs in the next 50 years could be near zero. Combined with a reduction of black carbon emissions and plausible success in slowing CO2 emissions, this reduction of non-CO2 GHGs could lead to a decline in the rate of global warming, reducing the danger of dramatic climate change. Such a focus on air pollution has practical benefits that unite the interests of developed and developing countries. However, assessment of ongoing and future climate change requires composition specific long-term global monitoring of aerosol properties.

Global warming in the twenty-first century: an alternative scenario.

PubMed

Hansen, J; Sato, M; Ruedy, R; Lacis, A; Oinas, V

2000-08-29

A common view is that the current global warming rate will continue or accelerate. But we argue that rapid warming in recent decades has been driven mainly by non-CO(2) greenhouse gases (GHGs), such as chlorofluorocarbons, CH(4), and N(2)O, not by the products of fossil fuel burning, CO(2) and aerosols, the positive and negative climate forcings of which are partially offsetting. The growth rate of non-CO(2) GHGs has declined in the past decade. If sources of CH(4) and O(3) precursors were reduced in the future, the change in climate forcing by non-CO(2) GHGs in the next 50 years could be near zero. Combined with a reduction of black carbon emissions and plausible success in slowing CO(2) emissions, this reduction of non-CO(2) GHGs could lead to a decline in the rate of global warming, reducing the danger of dramatic climate change. Such a focus on air pollution has practical benefits that unite the interests of developed and developing countries. However, assessment of ongoing and future climate change requires composition-specific long-term global monitoring of aerosol properties.

Global warming in the twenty-first century: An alternative scenario

PubMed Central

Hansen, James; Sato, Makiko; Ruedy, Reto; Lacis, Andrew; Oinas, Valdar

2000-01-01

A common view is that the current global warming rate will continue or accelerate. But we argue that rapid warming in recent decades has been driven mainly by non-CO2 greenhouse gases (GHGs), such as chlorofluorocarbons, CH4, and N2O, not by the products of fossil fuel burning, CO2 and aerosols, the positive and negative climate forcings of which are partially offsetting. The growth rate of non-CO2 GHGs has declined in the past decade. If sources of CH4 and O3 precursors were reduced in the future, the change in climate forcing by non-CO2 GHGs in the next 50 years could be near zero. Combined with a reduction of black carbon emissions and plausible success in slowing CO2 emissions, this reduction of non-CO2 GHGs could lead to a decline in the rate of global warming, reducing the danger of dramatic climate change. Such a focus on air pollution has practical benefits that unite the interests of developed and developing countries. However, assessment of ongoing and future climate change requires composition-specific long-term global monitoring of aerosol properties. PMID:10944197

Pre-converted nitric oxide gas in catalytic reduction system

DOEpatents

Hsiao, Mark C.; Merritt, Bernard T.; Penetrante, Bernardino M.; Vogtlin, George E.

1999-01-01

A two-stage catalyst comprises an oxidative first stage and a reductive second stage. The first stage is intended to convert NO to NO.sub.2 in the presence of O.sub.2. The second stage serves to convert NO.sub.2 to environmentally benign gases that include N2, CO2, and H.sub.2 O. By preconverting NO to NO.sub.2 in the first stage, the efficiency of the second stage for NO.sub.x reduction is enhanced. For example, an internal combustion engine exhaust is connected by a pipe to a first chamber. An oxidizing first catalyst converts NO to NO.sub.2 in the presence of O.sub.2 and includes platinum/alumina, e.g., Pt/Al.sub.2 O.sub.3 catalyst. A flow of hydrocarbons (C.sub.x H.sub.y) is input from a pipe into a second chamber. For example, propene can be used as a source of hydrocarbons. The NO.sub.2 from the first catalyst mixes with the hydrocarbons in the second chamber. The mixture proceeds to a second reduction catalyst that converts NO.sub.2 to N2, CO2, and H.sub.2 O, and includes a gamma-alumina .gamma.-Al.sub.2 O.sub.3. The hydrocarbons and NO.sub.x are simultaneously reduced while passing through the second catalyst.

Pre-converted nitric oxide gas in catalytic reduction system

DOEpatents

Hsiao, M.C.; Merritt, B.T.; Penetrante, B.M.; Vogtlin, G.E.

1999-04-06

A two-stage catalyst comprises an oxidative first stage and a reductive second stage. The first stage is intended to convert NO to NO{sub 2} in the presence of O{sub 2}. The second stage serves to convert NO{sub 2} to environmentally benign gases that include N{sub 2}, CO{sub 2}, and H{sub 2}O. By preconverting NO to NO{sub 2} in the first stage, the efficiency of the second stage for NO{sub x} reduction is enhanced. For example, an internal combustion engine exhaust is connected by a pipe to a first chamber. An oxidizing first catalyst converts NO to NO{sub 2} in the presence of O{sub 2} and includes platinum/alumina, e.g., Pt/Al{sub 2}O{sub 3} catalyst. A flow of hydrocarbons (C{sub x}H{sub y}) is input from a pipe into a second chamber. For example, propene can be used as a source of hydrocarbons. The NO{sub 2} from the first catalyst mixes with the hydrocarbons in the second chamber. The mixture proceeds to a second reduction catalyst that converts NO{sub 2} to N{sub 2}, CO{sub 2}, and H{sub 2}O, and includes a {gamma}-Al{sub 2}O{sub 3}. The hydrocarbons and NO{sub x} are simultaneously reduced while passing through the second catalyst. 9 figs.

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

Sadeghi, Omid; Falaise, Clément; Molina, Pedro I.

The iron Keggin ion is identified as a structural building block in both magnetite and ferrihydrite, two important iron oxide phases in nature and in technology. Discrete molecular forms of the iron Keggin ion that can be both manipulated in water and chemically converted to the related metal oxides are important for understanding growth mechanisms, in particular non-classical nucleation in which cluster building units are preserved in the aggregation and condensation processes. Here we describe two iron Keggin ion structures, formulated [Bi6FeO4Fe12O12(OH)12(CF3COO)10(H2O)2]3+ and [Bi6FeO4Fe12O12(OH)12(CF3COO)12]1+. Experimental and simulated X-ray scattering studies show indefinite stability of these clusters in water from pHmore » 1-3. The tridecameric iron Keggin-ion core is protected from hydrolysis by a synergistic effect of the capping Bi3+-cations and the trifluoroacetate ligands that respectively bond to the iron and bridge to the bismuth. By introducing electrons to the aqueous solution of clusters, we achieve complete separation of bismuth from the cluster, and the iron Keggin ion rapidly converts to magnetite and/or ferrihydrite, depending on the mechanism of reduction. In this strategy, we take advantage of the easily accessible reduction potential and crystallization energy of bismuth. Reduction was executed in bulk by chemical means, by voltammetry, and by secondary effects of transmission electron microscopy imaging of solutions. Prior, we showed a less stable analogue of the iron Keggin cluster converted to ferrihydrite simply upon dissolution. The prior and currently studied clusters with a range of reactivity provide a chemical system to study molecular cluster metal oxide conversion processes in detail.« less

Pharmacological properties of excitatory amino acid induced changes in extracellular calcium concentration in rat hippocampal slices.

PubMed

Arens, J; Stabel, J; Heinemann, U

1992-01-01

We have studied extracellular ionic changes induced by iontophoretic application of excitatory amino acids in rat hippocampal slices. In contrast to kinetics of changes in [Ca2+]o, kinetics of changes in [K+]o, [Na+]o, [Cl-]o as well as in extracellular space size were comparable for different glutamate receptor agonists. Thus, alpha-amino-3-hydroxy-5-methylisoxazolepropionic acid (AMPA), quisqualate (quis), and kainate caused reductions in [Ca2+]o followed by an increase of [Ca2+]o above baseline, whereas glutamate, aspartate, N-methyl-D-aspartate (NMDA), and DL-homocysteic acid caused only reductions in [Ca2+]o. After blocking the NMDA receptors with ketamine and 2-amino-5- phosphonovaleric acid (2-APV), glutamate-induced decreases in [Ca2+]o were followed by an overshoot. Reduction of the transmembrane Na+ gradient by lowering [Na+]o, blocking of the Na(+)-K+ ATPase by lowering [K+]o, and application of ouabain blocked the overshoots after quis application, whereas vanadate, a blocker of the Ca(2+)-Mg2+ ATPase, had no effects. Lithium enhanced the reductions in [Ca2+]o and blocked the overshoots. Amiloride also reduced the overshoots. All organic Ca2+ entry blockers diminished reductions of [Ca2+]o but increased the overshoots. Inorganic Ca2+ antagonists had variable effects. Ni2+ had similar effects as the organic Ca2+ entry blockers while Cd2+ reduced both the [Ca2+]o decreases as well as the subsequent overshoots. Co2+ had initially a similar action as Ni2+. With prolonged application, [Ca2+]o decreases became augmented and, during wash, overshoots could no longer be elicited. We suggest that the overshoots in [Ca2+]o are due to a combined effect of extracellular space shrinkage and activation of the Na+/Ca2+ exchangers. This would imply that NMDA receptor activation blocks extrusion of Ca2+ from the cells. We tested the hypothesis that quis-induced intracellular Ca2+ release and extrusion of Ca2+ from the cells contributed to the overshoots. Dantrolene was without effect on the quis-induced signals, while ryanodine reduced the overshoots. Caffeine on the other hand diminished the [Ca2+]o decreases with no effects on the overshoots. To test for possible second messenger routes by which NMDA receptor activation might slow Ca2+ extrusion from cells, we investigated the effects of arachidonic acid and N-monomethyl-D- arginine on the quis-induced signals. While these agents reduced decreases in [Ca2+]o, they had no clear effects on the overshoots. Thus a possible route by which NMDA receptor activation may affect Ca2+ extrusion from cells has still to be elucidated.

Low temperature RF plasma nitriding of self-organized TiO2 nanotubes for effective bandgap reduction

NASA Astrophysics Data System (ADS)

Bonelli, Thiago Scremin; Pereyra, Inés

2018-06-01

Titanium dioxide is a widely studied semiconductor material found in many nanostructured forms, presenting very interesting properties for several applications, particularly photocatalysis. TiO2 nanotubes have a high surface-to-volume ratio and functional electronic properties for light harvesting. Despite these manifold advantages, TiO2 photocatalytic activity is limited to UV radiation due to its large band gap. In this work, TiO2 nanotubes produced by electrochemical anodization were submitted to plasma nitriding processes in a PECVD reactor. The plasma parameters were evaluated to find the best conditions for gap reduction, in order to increase their photocatalytic activity. The pressure and RF power density were varied from 0.66 to 2.66 mbar and 0.22 to 3.51 W/cm2 respectively. The best gap reduction, to 2.80 eV, was achieved using a pressure of 1.33 mbar and 1.75 W/cm2 RF power at 320 °C, during a 2-h process. This leads to a 14% reduction in the band gap value and an increase of 25.3% in methylene blue reduction, doubling the range of solar photons absorption from 5 to 10% of the solar spectrum.

Luminescent Sensors for Tracking Spatial Particle Distribution in an Explosion

NASA Astrophysics Data System (ADS)

Eilers, Hergen; Gunawidjaja, Ray; Diez-Y-Riega, Helena; Svingala, Forrest; Daniels, Amber; Lightstone, James; Washington State University Collaboration; Nswc Iheodtd Collaboration

2015-06-01

We previously developed and tested thermally sensitive particles that, when seeded into an explosive event, flow with the expanding post-detonation fireball and provide ex-situ measurements of this thermal environment. This current work presents the development and testing of tracking particles that are used in concert with the thermally sensitive particles to encode the initial positions of materials recovered for ex-situ analysis. These tracking sensors consist of fully-crystallized (c) rare-earth-doped yttria particles such as c-Dy:Y2O3, c-Sm:Y2O3, and c-Er,Yb:Y2O3. The temperature sensors consist of mixtures of precursor (p) and fully crystallized materials such as p-Eu:Y2O3/c-Tb:Y2O3 orp-Eu:ZrO2/c-Tb:Y2O3. Three mixtures containing one of the tracking sensors and one of the temperature sensing mixtures are placed at different locations within the chamber. Post-detonation, the tracking particles in the debris are excited by 365 nm light, resulting in different color luminescence, and allowing for potential visual inspection of the particle distribution originating from the different locations. Meanwhile, the temperature is determined from spectral changes of the precursor sensor materials or by comparison of the precursor sensor materials with the Tb:Y2O3 intensity reference. Defense Threat Reduction Agency, HDTRA1-10-1-0005.

Experimental study of NO2 reduction in N2/Ar and O2/Ar mixtures by pulsed corona discharge.

PubMed

Zhu, Xinbo; Zheng, Chenghang; Gao, Xiang; Shen, Xu; Wang, Zhihua; Luo, Zhongyang; Cen, Kefa

2014-11-01

Non-thermal plasma technology has been regarded as a promising alternative technology for NOx removal. The understanding of NO2 reduction characteristics is extremely important since NO2 reduction could lower the total NO oxidation rate in the plasma atmosphere. In this study, NO2 reduction was experimentally investigated using a non-thermal plasma reactor driven by a pulsed power supply for different simulated gas compositions and operating parameters. The NO2 reduction was promoted by increasing the specific energy density (SED), and the highest conversion rates were 33.7%, 42.1% and 25.7% for Ar, N2/Ar and O2/Ar, respectively. For a given SED, the NO2 conversion rate had the order N2/Ar>Ar>O2/Ar. The highest energy yield of 3.31g/kWh was obtained in N2/Ar plasma and decreased with increasing SED; the same trends were also found in the other two gas compositions. The conversion rate decreased with increasing initial NO2 concentration. Furthermore, the presence of N2 or O2 led to different reaction pathways for NO2 conversion due to the formation of different dominating reactive radicals. Copyright © 2014. Published by Elsevier B.V.

Robust electrodes based on coaxial TiC/C-MnO2 core/shell nanofiber arrays with excellent cycling stability for high-performance supercapacitors.

PubMed

Zhang, Xuming; Peng, Xiang; Li, Wan; Li, Limin; Gao, Biao; Wu, Guosong; Huo, Kaifu; Chu, Paul K

2015-04-17

A coaxial electrode structure composed of manganese oxide-decorated TiC/C core/shell nanofiber arrays is produced hydrothermally in a KMnO4 solution. The pristine TiC/C core/shell structure prepared on the Ti alloy substrate provides the self-sacrificing carbon shell and highly conductive TiC core, thus greatly simplifying the fabrication process without requiring an additional reduction source and conductive additive. The as-prepared electrode exhibits a high specific capacitance of 645 F g(-1) at a discharging current density of 1 A g(-1) attributable to the highly conductive TiC/C and amorphous MnO2 shell with fast ion diffusion. In the charging/discharging cycling test, the as-prepared electrode shows high stability and 99% capacity retention after 5000 cycles. Although the thermal treatment conducted on the as-prepared electrode decreases the initial capacitance, the electrode undergoes capacitance recovery through structural transformation from the crystalline cluster to layered birnessite type MnO2 nanosheets as a result of dissolution and further electrodeposition in the cycling. 96.5% of the initial capacitance is retained after 1000 cycles at high charging/discharging current density of 25 A g(-1). This study demonstrates a novel scaffold to construct MnO2 based SCs with high specific capacitance as well as excellent mechanical and cycling stability boding well for future design of high-performance MnO2-based SCs. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Enhancing the stability of copper chromite catalysts for the selective hydrogenation of furfural using ALD overcoating

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

Zhang, Hongbo; Lei, Yu; Kropf, A. Jeremy

2014-08-01

The stability of a gas-phase furfural hydrogenation catalyst (CuCr2O4 center dot CuO) was enhanced by depositing a thin Al2O3 layer using atomic layer deposition (ALD). Based on temperature-programed reduction (TPR) measurements, the reduction temperature of Cu was raised significantly, and the activation energy for furfural reduction was decreased following the ALD treatment. Thinner ALD layers yielded higher furfural hydrogenation activities. X-ray absorption fine structure (XAFS) spectroscopy studies indicated that Cu1+/Cu-0 are the active species for furfural reduction.

An Inner-Sphere Mechanism for Molecular Oxygen Reduction Catalyzed by Copper Amine Oxidases

PubMed Central

Mukherjee, Arnab; Smirnov, Valeriy V.; Lanci, Michael P.; Brown, Doreen E.; Shepard, Eric M.; Dooley, David M.; Roth, Justine P.

2008-01-01

Copper and topaquinone (TPQ) containing amine oxidases utilize O2 for the metabolism of biogenic amines while concomitantly generating H2O2 for use by the cell. The mechanism of O2 reduction has been the subject of long-standing debate due to the obscuring influence of a proton-coupled electron transfer between the tyrosine-derived TPQ and copper, a rapidly established equilibrium precluding assignment of the enzyme in its reactive form. Here we show that substrate-reduced pea seedling amine oxidase (PSAO) exists predominantly in the CuI, TPQ semiquinone state. A new mechanistic proposal for O2 reduction is advanced on the basis of thermodynamic considerations together with kinetic studies (at varying pH, temperature and viscosity), the identification of steady-state intermediates and the analysis of competitive oxygen kinetic isotope effects: 18O KIEs, [kcat/KM(16,16O2)]/[kcat/KM(16,18O2)]. The 18O KIE = 1.0136 ± 0.0013 at pH 7.2 is independent of temperature from 5 to 47°C and insignificantly changed to 1.0122 ± 0.0020 upon raising the pH to 9, thus indicating the absence of kinetic complexity. Using density functional methods, the effect is found to be precisely in the range expected for reversible O2 binding to CuI to afford a superoxide, [CuII(η1-O2)−I]+, intermediate. Electron transfer from the TPQ semiquinone follows in the first irreversible step to form a peroxide, CuII(η1-O2)−II, intermediate driving the reduction of O2. The similar 18O KIEs reported for copper amine oxidases from other sources raise the possibility that all enzymes react by related inner-sphere mechanisms although additional experiments are needed to test this proposal. PMID:18582059

Photoelectrochemical cell for simultaneous electricity generation and heavy metals recovery from wastewater.

PubMed

Wang, Dawei; Li, Yi; Li Puma, Gianluca; Lianos, Panagiotis; Wang, Chao; Wang, Peifang

2017-02-05

The feasibility of simultaneous recovery of heavy metals from wastewater (e.g., acid mining and electroplating) and production of electricity is demonstrated in a novel photoelectrochemical cell (PEC). The photoanode of the cell bears a nanoparticulate titania (TiO 2 ) film capped with the block copolymer [poly(ethylene glycol)-b-poly(propylene glycol)-b-poly(ethylene glycol)] hole scavenger, which consumed photogenerated holes, while the photogenerated electrons transferred to a copper cathode reducing dissolved metal ions and produced electricity. Dissolved silver Ag + , copper Cu 2+ , hexavalent chromium as dichromate Cr 2 O 7 2- and lead Pb 2+ ions in a mixture (0.2mM each) were removed at different rates, according to their reduction potentials. Reduced Ag + , Cu 2+ and Pb 2+ ions produced metal deposits on the cathode electrode which were mechanically recovered, while Cr 2 O 7 2- reduced to the less toxic Cr 3+ in solution. The cell produced a current density J sc of 0.23mA/cm 2 , an open circuit voltage V oc of 0.63V and a maximum power density of 0.084mW/cm 2 . A satisfactory performance of this PEC for the treatment of lead-acid battery wastewater was observed. The cathodic reduction of heavy metals was limited by the rate of electron-hole generation at the photoanode. The PEC performance decreased by 30% after 9 consecutive runs, caused by the photoanode progressive degradation. Copyright © 2016 Elsevier B.V. All rights reserved.

Determining the N and O isotope effects of microbial nitrite reduction: the global N cycle implications of an enzyme-dependent isotope effect

NASA Astrophysics Data System (ADS)

Martin, T. S.; Casciotti, K. L.

2014-12-01

The marine nitrogen (N) cycle is a dynamic system of critical importance, since nitrogen is the limiting nutrient in over half of the world's oceans. Denitrification and anammox, the main N loss processes from the ocean, have different effects on carbon cycling and greenhouse gas emission. Understanding the balance between the two processes is vital to understanding the role of the N cycle in global climate change. One approach for investigating these processes is by using stable isotope analysis to estimate the relative magnitudes of N fluxes, particularly for biologically mediated processes. In order to make the most of the currently available isotope analysis techniques, it is necessary to know the isotope effects for each processes occurring in the environment. Nitrite reduction is an important step in denitrification. Previous work had begun to explore the N isotope effects for nitrite reduction, but no oxygen (O) isotope effect has been measured. Additionally, no consideration has been given to the type of nitrite reductase carrying out the reaction. There are two main types of respiratory nitrite reductase, one that is Cu-based and another that is Fe-based. We performed batch culture experiments with denitrifier strains possessing either a Cu-type or Fe-type nitrite reductase. Both N and O isotope effects for nitrite reduction were determined for each of these experiments by measuring the NO2- concentration, as well as the N and O isotopes of nitrite and applying a Rayleigh fractionation model. Both the N and O isotope effects were found to be significantly different between the two types of enzymes. This enzyme-linked difference in isotope effects emphasizes the importance of microbial community composition within the global N cycle.

Organic radicals for the enhancement of oxygen reduction reaction in Li-O2 batteries.

PubMed

Tesio, A Y; Blasi, D; Olivares-Marín, M; Ratera, I; Tonti, D; Veciana, J

2015-12-25

We examine for the first time the ability of inert carbon free-radicals as soluble redox mediators to catalyze and enhance the oxygen reduction reaction in a (TEGDME)-based electrolyte. We demonstrate that the tris(2,4,6-trichlorophenyl)methyl (TTM) radical is capable of chemically favoring the oxygen reduction reaction improving significantly the Li-O2 battery performance.

Quantification of the enhanced effectiveness of NOx control from simultaneous reductions of VOC and NH3 for reducing air pollution in the Beijing-Tianjin-Hebei region, China

NASA Astrophysics Data System (ADS)

Xing, Jia; Ding, Dian; Wang, Shuxiao; Zhao, Bin; Jang, Carey; Wu, Wenjing; Zhang, Fenfen; Zhu, Yun; Hao, Jiming

2018-06-01

As one common precursor for both PM2.5 and O3 pollution, NOx gains great attention because its controls can be beneficial for reducing both PM2.5 and O3. However, the effectiveness of NOx controls for reducing PM2.5 and O3 are largely influenced by the ambient levels of NH3 and VOC, exhibiting strong nonlinearities characterized as NH3-limited/NH3-poor and NOx-/VOC-limited conditions, respectively. Quantification of such nonlinearities is a prerequisite for making suitable policy decisions but limitations of existing methods were recognized. In this study, a new method was developed by fitting multiple simulations of a chemical transport model (i.e., Community Multiscale Air Quality Modeling System, CMAQ) with a set of polynomial functions (denoted as pf-RSM) to quantify responses of ambient PM2.5 and O3 concentrations to changes in precursor emissions. The accuracy of the pf-RSM is carefully examined to meet the criteria of a mean normalized error within 2 % and a maximal normalized error within 10 % by using 40 training samples with marginal processing. An advantage of the pf-RSM method is that the nonlinearity in PM2.5 and O3 responses to precursor emission changes can be characterized by quantitative indicators, including (1) a peak ratio (denoted as PR) representing VOC-limited or NOx-limited conditions, (2) a suggested ratio of VOC reduction to NOx reduction to avoid increasing O3 under VOC-limited conditions, (3) a flex ratio (denoted as FR) representing NH3-poor or NH3-rich conditions, and (4) enhanced benefits in PM2.5 reductions from simultaneous reduction of NH3 with the same reduction rate of NOx. A case study in the Beijing-Tianjin-Hebei region suggested that most urban areas present strong VOC-limited conditions with a PR from 0.4 to 0.8 in July, implying that the NOx emission reduction rate needs to be greater than 20-60 % to pass the transition from VOC-limited to NOx-limited conditions. A simultaneous VOC control (the ratio of VOC reduction to NOx reduction is about 0.5-1.2) can avoid increasing O3 during the transition. For PM2.5, most urban areas present strong NH3-rich conditions with a PR from 0.75 to 0.95, implying that NH3 is sufficiently abundant to neutralize extra nitric acid produced by an additional 5-35 % of NOx emissions. Enhanced benefits in PM2.5 reductions from simultaneous reduction of NH3 were estimated to be 0.04-0.15 µg m-3 PM2.5 per 1 % reduction of NH3 along with NOx, with greater benefits in July when the NH3-rich conditions are not as strong as in January. Thus, the newly developed pf-RSM model has successfully quantified the enhanced effectiveness of NOx control, and simultaneous reduction of VOC and NH3 with NOx can assure the control effectiveness of PM2.5 and O3.

Carbothermic reduction of uranium oxides into solvent metallic baths

NASA Astrophysics Data System (ADS)

Guisard Restivo, Thomaz A.; Capocchi, José D. T.

2004-09-01

The carbothermic reduction of UO 2 and U 3O 8 is studied employing tin and silicon solvent metallic baths in thermal analysis equipment, under Ar inert and N 2 reactive atmospheres. The metallic solvents are expected to lower the U activity by several orders of magnitude owing to strong interactions among the metals. The reduction products are composed of the solvent metal matrix and intermetallic U compounds. Silicon is more effective in driving the reduction since there is no residual UO 2 after the reaction. The gaseous product detected by mass spectrometer (MS) during the reduction is CO. A kinetic study for the Si case was accomplished by the stepwise isothermal analysis (SAI) method, leading to the identification of the controlling mechanisms as chemical reaction at the surface and nucleation, for UO 2 and U 3O 8 charges, respectively. One example for another system containing Al 2O 3 is also shown.

rGO-ZnO nanocomposites for high electrocatalytic effect on water oxidation obtained by microwave-hydrothermal method

NASA Astrophysics Data System (ADS)

Romeiro, Fernanda C.; Rodrigues, Mônica A.; Silva, Luiz A. J.; Catto, Ariadne C.; da Silva, Luis F.; Longo, Elson; Nossol, Edson; Lima, Renata C.

2017-11-01

Reduced graphene oxide-zinc oxide (rGO-ZnO) nanocomposites were successfully synthesized using a facile microwave-hydrothermal method under mild conditions, and their electrocatalytic properties towards O2 evolution were investigated. The microwave radiation played an important role in obtainment of well dispersed ZnO nanoparticles directly on reduced graphene oxide sheets without any additional reducing reagents or passivation agent. X-ray diffraction (XRD), Raman and infrared spectroscopies indicated the reduction of GO as well as the successful synthesis of rGO-ZnO nanocomposites. The chemical states of the samples were shown by XPS analyses. Due to the synergic effect, the resulting nanocomposites exhibited high electronic interaction between ZnO and rGO sheets, which improved the electrocatalytic oxidation of water with low onset potential of 0.48 V (vs. Ag/AgCl) in neutral pH and long-term stability, with high current density during electrolysis. The overpotential for water oxidation decreased in alkaline pH, suggesting useful insight on the catalytic mechanism for O2 evolution.

Oxygen Reduction Reaction for Generating H2 O2 through a Piezo-Catalytic Process over Bismuth Oxychloride.

PubMed

Shao, Dengkui; Zhang, Ling; Sun, Songmei; Wang, Wenzhong

2018-02-09

Oxygen reduction reaction (ORR) for generating H 2 O 2 through green pathways have gained much attention in recent years. Herein, we introduce a piezo-catalytic approach to obtain H 2 O 2 over bismuth oxychloride (BiOCl) through an ORR pathway. The piezoelectric response of BiOCl was directly characterized by piezoresponse force microscopy (PFM). The BiOCl exhibits efficient catalytic performance for generating H 2 O 2 (28 μmol h -1 ) only from O 2 and H 2 O, which is above the average level of H 2 O 2 produced by solar-to-chemical processes. A piezo-catalytic mechanism was proposed: with ultrasonic waves, an alternating electric field will be generated over BiOCl, which can drive charge carriers (electrons) to interact with O 2 and H 2 O, then to form H 2 O 2 . © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Corrosion testing of candidates for the alkaline fuel cell cathode

NASA Technical Reports Server (NTRS)

Singer, Joseph; Fielder, William L.

1989-01-01

Current/voltage data was obtained for specially made corrosion electrodes of some oxides and of gold materials for the purpose of developing a screening test of catalysts and supports for use at the cathode of the alkaline fuel cell. The data consists of measurements of current at fixed potentials and cyclic voltammograms. These data will have to be correlated with longtime performance data in order to fully evaluate this approach to corrosion screening. Corrosion test screening of candidates for the oxygen reduction electrode of the alkaline fuel cell was applied to two substances, the pyrochlore Pb2Ru2O6.5 and the spinel NiCo2O4. The substrate gold screen and a sample of the IFC Orbiter Pt-Au performance electrode were included as blanks. The pyrochlore data indicate relative stability, although nothing yet can be said about long term stability. The spinel was plainly unstable. For this type of testing to be validated, comparisons will have to be made with long term performance tests.

Electrical Field Dependence of Protein Conformation and Channel Function in Lipid Membranes of Different Compositions

DTIC Science & Technology

1989-07-01

surface because of the previous potential sweeps ). c- Cyclic voltamograms after different exposure times of the Hg drop electrode to a solution of lpg/ml...Cd + and 10-M NaCl. b - Cyclic voltamograms under similar conditions. Exposure time indicated, sweep rate O.2V/sec. specific capacitance < 4pf/cm 2...alamethicin. Cyclic voltametry shows (Fig. 3b) that it is the reduction current depending on the transport of TI+ ions across the monolayer to the electrode