Determination of rate constants for the oxygen reduction reaction

Energy Technology Data Exchange (ETDEWEB)

Racz, A.; Walter, T.; Stimming, U. [Munich Technical Univ., Garching (Germany). Dept. of Physics

2008-07-01

The oxygen reduction reaction (ORR) in fuel cells is a complex and fundamental electrochemical reaction. However, greater insight is needed into this multi-electron reaction in order to develop efficient and innovative catalysts. The rotating ring disc electrode (RRDE) is a useful tool for studying reaction intermediates of the ORR and to better understand the reaction pathway. Carbon materials such as carbon nanofilaments-platelets (CNF-PL) have high electrical conductivity and may be considered for fuel cells. In particular Pt and RuSe{sub x}, deposited on CNF-PL materials could act as efficient catalysts in fuel cells. This study used the RRDE to evaluate the oxygen reduction kinetics of these catalysts in oxygen-saturated, diluted sulphuric acid at room temperature. Kinetic data and hydrogen peroxide formation were determined by depositing a thin-film of the catalyst on the Au disc. The values for the constants k1, k2 and k3 were obtained using diagnostic criteria and expressions to calculate the rate constants of the cathodic oxygen reduction reaction for RuSe on new carbon supports. A potential dependency of the constants k1 and k2 for RuSe{sub x}/CNF-PL was observed. The transition of the Tafel slopes for this catalyst was obtained. 4 refs., 1 fig.

Fabrication of high surface area graphene electrodes with high performance towards enzymatic oxygen reduction

International Nuclear Information System (INIS)

Di Bari, Chiara; Goñi-Urtiaga, Asier; Pita, Marcos; Shleev, Sergey; Toscano, Miguel D.; Sainz, Raquel; De Lacey, Antonio L.

2016-01-01

High surface area graphene electrodes were prepared by simultaneous electrodeposition and electroreduction of graphene oxide. The electrodeposition process was optimized in terms of pH and conductivity of the solution and the obtained graphene electrodes were characterized by X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, scanning electron microscopy and electrochemical methods (cyclic voltammetry and impedance spectroscopy). Electrodeposited electrodes were further functionalized to carry out covalent immobilization of two oxygen-reducing multicopper oxidases: laccase and bilirubin oxidase. The enzymatic electrodes were tested as direct electron transfer based biocathodes and catalytic currents as high as 1 mA/cm 2 were obtained. Finally, the mechanism of the enzymatic oxygen reduction reaction was studied for both enzymes calculating the Tafel slopes and transfer coefficients.

Electrocatalytic reduction of oxygen at glassy carbon electrode modified by polypyrrole/anthraquinones composite film in various pH media

International Nuclear Information System (INIS)

Valarselvan, S.; Manisankar, P.

2011-01-01

Graphical abstract: The electrocatalytic reduction of dioxygen by one mono and four dihydroxy derivatives of 9,10-anthraquinone (AQ) incorporated in polypyrrole (PPy) matrix on glassy carbon electrode has been investigated. AQ and PPy composite film showed excellent electrocatalytic performance for the reduction of O 2 to H 2 O 2 . Highlights: → Hydroxyl derivatives of anthraquinones as electrocatalysts for dioxygen reduction. → AQ/PPy composite film on GC electrode exhibits potent electrocatalytic activity. → Substituent groups influence electrocatalytic dioxygen reduction. → Surface coverage varies the rate of electrocatalytic dioxygen reduction. - Abstract: The electrocatalytic reduction of dioxygen by one mono and four dihydroxy derivatives of 9,10-anthraquinone (AQ) incorporated in polypyrrole (PPy) matrix on glassy carbon electrode has been investigated. The electrochemical behaviour of the modified electrodes was examined in various pH media and both the formal potential of anthraquinones and reduction potential of dioxygen exhibited pH dependence. AQ and PPy composite film showed excellent electrocatalytic performance for the reduction of O 2 to H 2 O 2 . pH 6.0 was chosen as the most suitable medium to study the electrocatalysis by comparing the peak potential of oxygen reduction and enhancement in peak current for oxygen reduction. The diffusion coefficient values of AQ at the modified electrodes and the number of electrons involved in AQ reduction were evaluated by chronoamperometric and chronocoulometric techniques, respectively. In addition, hydrodynamic voltammetric studies showed the involvement of two electrons in O 2 reduction. The mass specific activity of AQ used, the diffusion coefficient of oxygen and the heterogeneous rate constants for the oxygen reduction at the surface of modified electrodes were also determined by rotating disk voltammetry.

Photochemical oxygen reduction by zinc phthalocyanine and silver/gold nanoparticle incorporated silica thin films

Energy Technology Data Exchange (ETDEWEB)

Pal, Manas; Ganesan, Vellaichamy, E-mail: velganesh@yahoo.com; Azad, Uday Pratap

2012-12-15

Silver or gold nanoparticles are synthesized using a borohydride reduction method and are anchored simultaneously into/onto the mercaptopropyl functionalized silica. Later, zinc phthalocyanine is adsorbed onto the above materials. Thin films of these materials are prepared by coating an aqueous colloidal suspension of the respective material onto glass plates. Visible light irradiation of these films in oxygen saturated, stirred aqueous solutions effectively reduces oxygen to hydrogen peroxide. The photocatalytic reduction of oxygen is explained on the basis of the semiconducting properties of the silica films. The back electron transfer reaction is largely prevented by means of a sacrificial electron donor, triethanolamine. - Highlights: Black-Right-Pointing-Pointer Zinc phthalocyanine adsorbed silica materials were prepared. Black-Right-Pointing-Pointer Thin films of these materials photocatalytically reduce oxygen. Black-Right-Pointing-Pointer The photocatalysis is explained based on semiconductor properties of the materials. Black-Right-Pointing-Pointer Metal nanoparticles increase the photocatalytic efficiency of the materials.

Oxygen reduction of several gold alloys in 1-molar potassium hydroxide

Science.gov (United States)

Miller, R. O.

1975-01-01

With rotated disk-and-ring equipment, polarograms and other electrochemical measurements were made of oxygen reduction in 1-molar potassium hydroxide on an equiatomic gold-copper (Au-Cu) alloy and a Au-Cu alloy doped with either indium (In) or cobalt (Co) and on Au doped with either nickel (Ni) or platinum (Pt). The results were compared with those for pure Au and pure Pt. The two-electron reaction dominated on all Au alloys as it did on Au. The polarographic results at lower polarization potentials were compared, assuming exclusively a two-step reduction. A qualified ranking of cathodic electrocatalytic activity on the freshly polished reduced disks was indicated: anodized Au Au-Cu-In Au-Cu Au-Cu-Co is equivalent or equal to Au-Pt Au-Ni. Aging in distilled water improved the electrocatalytic efficiency of Au-Cu-Co, Au-Cu, and (to a lesser extent) Au-Cu-In.

A potentiodynamic study of the reduction of oxygen on copper

International Nuclear Information System (INIS)

King, F.; Litke, C.D.

1994-07-01

The reduction of oxygen on copper has been studied in 0.1 mol·dm -3 NaCl solutions using potentiodynamic techniques. Experiments were carried out in unbuffered and phosphate-buffered solutions at pH 7. Additional experiments in NaCl solution were performed at pH 10, with the bulk pH adjusted by adding NaOH. Some voltammetric studies in deaerated electrolytes were carried out to examine the nature of the surface films formed on the electrode. The reduction of oxygen on copper is dominated by the 4-electron reduction to OH - . Limited quantities of peroxide were detected by the ring electrode at disc potentials in the joint- and kinetic-control regions. No peroxide was detected in the transport-limiting region. The rate of reduction of oxygen is influenced by the nature of the surface film on the electrode. At interfacial pH values of ∼10, a catalytic surface film forms, thought to be submonolayer Cu(OH) ads or submonolayer Cu 2 O. simultaneously, a peak is observed on the current-potential curve. This peak is observed in neutral solutions with atmospheres of 50% O 2 /N 2 and 100% O 2 and in pH 10 solution with atmospheres >∼10% O 2 /N 2 . The peak is not observed in phosphate-buffered solution because of the buffering action on the interfacial pH. At potentials positive of the peak potential, a thin Cu 2 O layer forms in unbuffered solutions on which the rate of oxygen reduction is partially inhibited. (author). 44 refs., 17 figs

An Oxygen Reduction Study of Graphene-Based Nanomaterials of Different Origin

Directory of Open Access Journals (Sweden)

Jaana Lilloja

2016-07-01

Full Text Available The aim of this study is to compare the electrochemical behaviour of graphene-based materials of different origin, e.g., commercially available graphene nanosheets from two producers and reduced graphene oxide (rGO towards the oxygen reduction reaction (ORR using linear sweep voltammetry, rotating disc electrode and rotating ring-disc electrode methods. We also investigate the effect of catalyst ink preparation using two different solvents (2-propanol containing OH− ionomer or N,N-dimethylformamide on the ORR. The graphene-based materials are characterised by scanning electron microscopy, transmission electron microscopy, Raman spectroscopy and X-ray photoelectron spectroscopy. Clearly, the catalytic effect depends on the origin of graphene material and, interestingly, the electrocatalytic activity of the catalyst material for ORR is lower when using the OH− ionomer in electrode modification. The graphene electrodes fabricated with commercial graphene show better ORR performance than rGO in alkaline solution.

Charge transfer induced activity of graphene for oxygen reduction

International Nuclear Information System (INIS)

Shen, Anli; Xia, Weijun; Dou, Shuo; Wang, Shuangyin; Zhang, Lipeng; Xia, Zhenhai

2016-01-01

Tetracyanoethylene (TCNE), with its strong electron-accepting ability, was used to dope graphene as a metal-free electrocatalyst for the oxygen reduction reaction (ORR). The charge transfer process was observed from graphene to TCNE by x-ray photoelectron spectroscopy and Raman characterizations. Our density functional theory calculations found that the charge transfer behavior led to an enhancement of the electrocatalytic activity for the ORR. (paper)

Critical appraisal on the role of catalysts for the oxygen reduction reaction in lithium-oxygen batteries

International Nuclear Information System (INIS)

Lodge, Andrew W.; Lacey, Matthew J.; Fitt, Matthew; Garcia-Araez, Nuria; Owen, John R.

2014-01-01

This work reports a detailed characterization of the reduction of oxygen in pyrrolidinium-based ionic liquids for application to lithium-oxygen batteries. It is found that, in the absence of Li + , all electron transfer kinetics are fast, and therefore, the reactions are limited by the mass transport rate. Reversible reduction of O 2 to O 2 • − and O 2 • − to O 2 2− take place at E 0 = 2.1 V and 0.8 V vs. Li + /Li, respectively. In the presence of Li + , O 2 is reduced to LiO 2 first and then to Li 2 O 2 . The solubility product constant of Li 2 O 2 is found to be around 10 −51 , corroborating the hypothesis that electrode passivation by Li 2 O 2 deposition is an important issue that limits the capacity delivered by lithium-oxygen batteries. Enhancing the rate of Li 2 O 2 formation by using different electrode materials would probably lead to faster electrode passivation and hence smaller charge due to oxygen reduction (smaller capacity of the battery). On the contrary, soluble redox catalysts can not only increase the reaction rate of Li 2 O 2 formation but also avoid electrode passivation since the fast diffusion of the soluble redox catalyst would displace the formation of Li 2 O 2 at a sufficient distance from the electrode surface

Electrochemical reduction of oxygen catalyzed by a wide range of bacteria including Gram-positive

Energy Technology Data Exchange (ETDEWEB)

Cournet, Amandine [Universite de Toulouse, UPS, LU49, Adhesion Bacterienne et Formation de Biofilms, 35 chemin des Maraichers, 31 062 Toulouse cedex 09 (France); Laboratoire de Genie Chimique CNRS, Universite de Toulouse, 4 allee Emile Monso, BP 84234, 31432 Toulouse cedex 04 (France); Delia, Marie-Line; Bergel, Alain [Laboratoire de Genie Chimique CNRS, Universite de Toulouse, 4 allee Emile Monso, BP 84234, 31432 Toulouse cedex 04 (France); Roques, Christine; Berge, Mathieu [Universite de Toulouse, UPS, LU49, Adhesion Bacterienne et Formation de Biofilms, 35 chemin des Maraichers, 31 062 Toulouse cedex 09 (France)

2010-04-15

Most bacteria known to be electrochemically active have been harvested in the anodic compartments of microbial fuel cells (MFCs) and are able to use electrodes as electron acceptors. The reverse phenomenon, i.e. using solid electrodes as electron donors, is not so widely studied. To our knowledge, most of the electrochemically active bacteria are Gram-negative. The present study implements a transitory electrochemical technique (cyclic voltammetry) to study the microbial catalysis of the electrochemical reduction of oxygen. It is demonstrated that a wide range of aerobic and facultative anaerobic bacteria are able to catalyze oxygen reduction. Among these electroactive bacteria, several were Gram-positive. The transfer of electrons was direct since no activity was obtained with the filtrate. These findings, showing a widespread property among bacteria including Gram-positive ones, open new and interesting routes in the field of electroactive bacteria research. (author)

Synthesis and electrocatalytic activity towards oxygen reduction reaction of gold-nanostars

OpenAIRE

Oyunbileg G; Batnyagt G; Enkhsaruul B; T Takeguchi

2018-01-01

The oxygen reduction reaction (ORR) is a characteristic reaction which determines the performance of fuel cells which convert a chemical energy into an electrical energy. Aims of this study are to synthesize Au-based nanostars (AuNSs) and determine their preliminary electro-catalytic activities towards ORR by a rotating-disk electrode method in alkaline electrolyte. The images obtained from a scanning electron microscope (SEM) and a transmission electron microscope (TEM) analyses confirm the ...

A Nanopore-Structured Nitrogen-Doped Biocarbon Electrocatalyst for Oxygen Reduction from Two-Step Carbonization of Lemna minor Biomass

Science.gov (United States)

Guo, Chaozhong; Li, Zhongbin; Niu, Lidan; Liao, Wenli; Sun, Lingtao; Wen, Bixia; Nie, Yunqing; Cheng, Jing; Chen, Changguo

2016-05-01

So far, the development of highly active and stable carbon-based electrocatalysts for oxygen reduction reaction (ORR) to replace commercial Pt/C catalyst is a hot topic. In this study, a new nanoporous nitrogen-doped carbon material was facilely designed by two-step pyrolysis of the renewable Lemna minor enriched in crude protein under a nitrogen atmosphere. Electrochemical measurements show that the onset potential for ORR on this carbon material is around 0.93 V (versus reversible hydrogen electrode), slightly lower than that on the Pt/C catalyst, but its cycling stability is higher compared to the Pt/C catalyst in an alkaline medium. Besides, the ORR at this catalyst approaches to a four-electron transfer pathway. The obtained ORR performance can be basically attributed to the formation of high contents of pyridinic and graphitic nitrogen atoms inside this catalyst. Thus, this work opens up the path in the ORR catalysis for the design of nitrogen-doped carbon materials utilizing aquatic plants as starting precursors.

Electron scattering by molecular oxygen

International Nuclear Information System (INIS)

Duddy, P.E.

1999-03-01

Collisions of electrons with molecules is one of the fundamental processes which occur both in atomic and molecular physics and also in chemistry. These collisions are vital in determining the energy balance and transport properties of electrons in gases and plasmas at low temperatures. There are many important applications for the basic understanding of these collision processes. For example, the study of planetary atmospheres and the interstellar medium involves electron collisions with both molecules and molecular ions. In particular, two of the major cooling mechanisms of electrons in the Earth's ionosphere are (i) the fine structure changing transitions of oxygen atoms by electron impact and (ii) the resonant electron-impact vibrational excitation of N 2 . Other applications include magnetohydrodynamic power generation and laser physics. A molecule, by definition, will contain more than one nucleus and consequently the effect of nuclear motion in the molecule leads to many extra processes in electron scattering by molecules which cannot occur in electron-atom scattering. As for atoms, both elastic and inelastic scattering occur, but in the case of inelastic electron scattering by molecules, the target molecule is excited to a different state by the process. The excitation may be one, or some combination, of rotational, vibrational and electronic transitions. Other reactions which may occur include dissociation of the molecule into its constituent atoms or ionisation. Another difficulty arises when considering the interactions between the electron and the molecule, This interaction, which considerably complicates the calculation, is non-spherical and various methods have been developed over the years to represent this interaction. This thesis considers electron scattering by molecular oxygen in the low energy range i.e. 0-15eV. These collisions are of considerable interest in atmospheric physics and chemistry where the electron impact excitation of O 2 has

Synthesis and electrocatalytic activity towards oxygen reduction reaction of gold-nanostars

Directory of Open Access Journals (Sweden)

Oyunbileg G

2018-02-01

Full Text Available The oxygen reduction reaction (ORR is a characteristic reaction which determines the performance of fuel cells which convert a chemical energy into an electrical energy. Aims of this study are to synthesize Au-based nanostars (AuNSs and determine their preliminary electro-catalytic activities towards ORR by a rotating-disk electrode method in alkaline electrolyte. The images obtained from a scanning electron microscope (SEM and a transmission electron microscope (TEM analyses confirm the formation of the star-shaped nanoparticles. Among the investigated nanostar catalysts, an AuNS5 with smaller size and a few branches showed the higher electrocatalytic activity towards ORR than other catalysts with a bigger size. In addition, the electron numbers transferred for all the catalysts are approximately two. The present study results infer that the size of the Au-based nanostars may influence greatly on their catalytic activity. The present study results show that the further improvement is needed for Au-based nanostar catalysts towards the ORR reaction.

KOH-activated multi-walled carbon nanotubes as platinum supports for oxygen reduction reaction

Science.gov (United States)

He, Chaoxiong; Song, Shuqin; Liu, Jinchao; Maragou, Vasiliki; Tsiakaras, Panagiotis

In the present investigation, multi-walled carbon nanotubes (MWCNTs) thermally treated by KOH were adopted as the platinum supporting material for the oxygen reduction reaction electrocatalysts. FTIR and Raman spectra were used to investigate the surface state of MWCNTs treated by KOH at different temperatures (700, 800, and 900 °C) and showed MWCNTs can be successfully functionalized. The structural properties of KOH-activated MWCNTs supported Pt were determined by X-ray diffraction (XRD) and transmission electron microscopy (TEM), and their electrochemical performance was evaluated by the aid of cyclic voltammetry (CV) and rotating disk electrode (RDE) voltammetry. According to the experimental findings of the present work, the surrface of MWCNTs can be successfully functionalized with oxygen-containing groups after activation by KOH, favoring the good dispersion of Pt nanoparticles with narrow size distribution. The as-prepared Pt catalysts supported on KOH treated MWCNTs at higher temperature, possess higher electrochemical surface area and exhibit desirable activity towards oxygen reduction reaction (ORR). More precisely, it has been found that the electrochemical active area of Pt/MWCNTs-900 is approximately two times higher than that of Pt/MWCNTs. It can be concluded that KOH activation is an effective way to decorate MWCNTs' surface with oxygen-containing groups and bigger surface area, which makes them more suitable as electrocatalyst support materials.

Titanium Nitride Nanoparticle Electrocatalysts for Oxygen Reduction Reaction in Alkaline Solution

KAUST Repository

Ohnishi, R.

2013-03-12

Monodispersed TiN nanoparticles with a narrow size distribution (7–23 nm) were synthesized using mesoporous graphitic (mpg)-C3N4 templates with different pore sizes. The nano-materials were examined as electrocatalysts for oxygen reduction reaction (ORR) in alkaline media. The TiN nanoparticles were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), N2 sorption, transmission electron microscopy (TEM), and C-H-N elemental analysis. The ORR current increased as the TiN particle size decreased, and hence the surface area of TiN nanoparticles reactive to ORR increased. Rotating ring disk electrode (RRDE) measurements revealed that the ORR on TiN surfaces proceeded mainly via a two-electron pathway, producing H2O2 as the main product. Mechanistic aspects of ORR on TiN surfaces are discussed.

Titanium Nitride Nanoparticle Electrocatalysts for Oxygen Reduction Reaction in Alkaline Solution

KAUST Repository

Ohnishi, R.; Katayama, M.; Cha, Dong Kyu; Takanabe, Kazuhiro; Kubota, J.; Domen, K.

2013-01-01

Monodispersed TiN nanoparticles with a narrow size distribution (7–23 nm) were synthesized using mesoporous graphitic (mpg)-C3N4 templates with different pore sizes. The nano-materials were examined as electrocatalysts for oxygen reduction reaction (ORR) in alkaline media. The TiN nanoparticles were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), N2 sorption, transmission electron microscopy (TEM), and C-H-N elemental analysis. The ORR current increased as the TiN particle size decreased, and hence the surface area of TiN nanoparticles reactive to ORR increased. Rotating ring disk electrode (RRDE) measurements revealed that the ORR on TiN surfaces proceeded mainly via a two-electron pathway, producing H2O2 as the main product. Mechanistic aspects of ORR on TiN surfaces are discussed.

Catalytic activity of dual catalysts system based on nano-manganese oxide and cobalt octacyanophthalocyanine toward four-electron reduction of oxygen in alkaline media

International Nuclear Information System (INIS)

Zhang, Dun; Chi, Dahe; Okajima, Takeyoshi; Ohsaka, Takeo

2007-01-01

The electrocatalysis of the dual functional catalysts system composed of electrolytic nano-manganese oxide (nano-MnOx) and cobalt octacyanophthalocyanine (CoPcCN) toward 4-electron reduction of oxygen (O 2 ) in alkaline media was studied. Nano-MnOx electrodeposited on the CoPcCN monolayer-modified glassy carbon (GC) electrode was clarified as the nano-rods with ca. 10-20 nm diameter by scanning electron microscopy. The peak current for O 2 reduction at the dual catalysts-modified GC electrode increases largely and the peak potential shifts by ca. 160 mV to the positive direction in cyclic voltammograms compared with those obtained at the bare GC electrode. The Koutecky-Levich plots indicate that the O 2 reduction at the dual catalysts-modified GC electrode is an apparent 4-electron process. Collection efficiencies obtained at the dual catalysts-modified GC electrode are much lower than those at the GC electrode and are almost similar to those at the Pt nano-particles modified GC electrode. The obtained results demonstrate that the dual catalysts system possesses a bifuctional catalytic activity for redox-mediating 2-electron reduction of O 2 to HO 2 - by CoPcCN as well as catalyzing the disproportionation of HO 2 - to OH - and O 2 by nano-MnOx, and enables an apparent 4-electron reduction of O 2 at a relatively low overpotential in alkaline media. In addition, it has been found that the cleaning of the dual catalysts-modified electrode by soaking in 0.1 M sulfuric acid solution enhances its catalytic activity toward the reduction of O 2

Metal porphyrin intercalated reduced graphene oxide nanocomposite utilized for electrocatalytic oxygen reduction

Directory of Open Access Journals (Sweden)

Mingyan Wang

2017-07-01

Full Text Available In this paper, we report a simple and facile self-assembly method to successfully fabricate cationic metal porphyrin –MtTMPyP (Mt= Cobalt (II, Manganese (III, or Iron (III; TMPyP = 5, 10, 15, 20-tetrakis (N-methylpyridinium-4-yl porphyrin intercalated into the layer of graphene oxide (GO by the cooperative effects of electrostatic and π–π stacking interaction between positively charged metal porphyrin and negatively charged GO sheets. Followed by reduction with hydrazine vapor, a series of novel 2D MtTMPyP/rGOn were fabricated. The as-prepared 2D hybrids were fully characterized and tested as non-noble metal catalysts for oxygen reduction reaction (ORR in an alkaline medium. The MtTMPyP/rGOn hybrids, especially CoTMPyP/rGO5, demonstrated an improved electrocatalytic activity for ORR and a number of exchanged electrons close to 4-electron reaction, increased stability and excellent tolerance to methanol, showing a potential alternative catalyst for ORR in fuel cells and air batteries. Keywords: Metal porphyrin, Reduced graphene oxide, Intercalation, Oxygen reduction reaction, Catalyst

Nano-Structured Bio-Inorganic Hybrid Material for High Performing Oxygen Reduction Catalyst.

Science.gov (United States)

Jiang, Rongzhong; Tran, Dat T; McClure, Joshua P; Chu, Deryn

2015-08-26

In this study, we demonstrate a non-Pt nanostructured bioinorganic hybrid (BIH) catalyst for catalytic oxygen reduction in alkaline media. This catalyst was synthesized through biomaterial hemin, nanostructured Ag-Co alloy, and graphene nano platelets (GNP) by heat-treatment and ultrasonically processing. This hybrid catalyst has the advantages of the combined features of these bio and inorganic materials. A 10-fold improvement in catalytic activity (at 0.8 V vs RHE) is achieved in comparison of pure Ag nanoparticles (20-40 nm). The hybrid catalyst reaches 80% activity (at 0.8 V vs RHE) of the state-of-the-art catalyst (containing 40% Pt and 60% active carbon). Comparable catalytic stability for the hybrid catalyst with the Pt catalyst is observed by chronoamperometric experiment. The hybrid catalyst catalyzes 4-electron oxygen reduction to produce water with fast kinetic rate. The rate constant obtained from the hybrid catalyst (at 0.6 V vs RHE) is 4 times higher than that of pure Ag/GNP catalyst. A catalytic model is proposed to explain the oxygen reduction reaction at the BIH catalyst.

Performance Limits of Photoelectrochemical CO2 Reduction Based on Known Electrocatalysts and the Case for Two-Electron Reduction Products

DEFF Research Database (Denmark)

Vesborg, Peter Christian Kjærgaard; Seger, Brian

2016-01-01

Solar-drivenreduction of CO2 to solar fuels as an alternative to H2 via water splitting is an intriguing proposition. We modelthe solar-to-fuel (STF) efficiencies using realistic parameters basedon recently reported CO2 reduction catalysts with a highperformance tandem photoabsorber structure. CO...... due to excessiveoverpotentials and poor selectivity. This work considers breakingup the multielectron reduction pathway into individually optimized,separate two-electron steps as a way forward....

Nanostructured Mn{sub x}O{sub y} for oxygen reduction reaction (ORR) catalysts

Energy Technology Data Exchange (ETDEWEB)

Delmondo, Luisa, E-mail: luisa.delmondo@polito.it [Department of Applied Science and Technology—DISAT, Politecnico di Torino, C.so Duca degli Abruzzi 24, 10129 Torino (Italy); Salvador, Gian Paolo; Muñoz-Tabares, José Alejandro; Sacco, Adriano; Garino, Nadia; Castellino, Micaela [Center for Space Human Robotics @PoliTo, Istituto Italiano di Tecnologia, C.so Trento 21, 10129 Torino (Italy); Gerosa, Matteo; Massaglia, Giulia [Department of Applied Science and Technology—DISAT, Politecnico di Torino, C.so Duca degli Abruzzi 24, 10129 Torino (Italy); Center for Space Human Robotics @PoliTo, Istituto Italiano di Tecnologia, C.so Trento 21, 10129 Torino (Italy); Chiodoni, Angelica; Quaglio, Marzia [Center for Space Human Robotics @PoliTo, Istituto Italiano di Tecnologia, C.so Trento 21, 10129 Torino (Italy)

2016-12-01

Highlights: • Good performance catalysts for oxygen reduction reaction. • Nanostructured low-cost catalysts respect to platinum ones. • Synthesis using environmental benign chemical reagents. - Abstract: In the field of fuel cells, oxygen plays a key role as the final electron acceptor. To facilitate its reduction (Oxygen Reduction Reaction—ORR), a proper catalyst is needed and platinum is considered the best one due to its low overpotential for this reaction. By considering the high price of platinum, alternative catalysts are needed and manganese oxides (Mn{sub x}O{sub y}) can be considered promising substitutes. They are inexpensive, environmental friendly and can be obtained into several forms; most of them show significant electro-catalytic performance, even if strategies are needed to increase their efficiency. In particular, by developing light and high-surface area materials and by optimizing the presence of catalytic sites, we can obtain a cathode with improved electro-catalytic performance. In this case, nanofibers and xerogels are two of the most promising nanostructures that can be used in the field of catalysis. In this work, a study of the morphological and catalytic behavior of Mn{sub x}O{sub y} nanofibers and xerogels is proposed. Nanofibers were obtained by electrospinning, while xerogels were prepared by sol-gel and freeze drying techniques. Despite of the different preparation approaches, the obtained nanostructured manganese oxides exhibited similar catalytic performance for the ORR, comparable to those obtained from Pt catalysts.

Solid-phase reduction of silico-12-molybdic acid H4SiMo12O40 by some organic oxygen containing compounds

International Nuclear Information System (INIS)

Chuvaev, V.F.; Pinchuk, I.N.; Spitsyn, V.I.

1982-01-01

A study is made on reduction reactions of anhydrous silico-12-molybdic acid by vapors of organic oxygen-containing compounds at 170 deg C: alcohols, simple carbonyl compounds. Methods of thermal analysis, electron paramagnetic resonance, paramagnetic resonance were used to established that depending on the nature of organic reagent and temperature, H 6 SiMo 2 5 Mo 10 6 O 40 two-electron or H 8 SiMo 4 5 Mo 8 6 O 40 four-electron flues form. It is shown that the increase of heterogeneous reduction temperature can lead to formation of anhydrous phases of SiMo 12 O 38 -(n/2), able to attach water reversibly with formation of corresponding blue. Characteristics of blues, prepared during solid-phase reduction of silico-12-molybdic acid and mixed valent forms with corresponding reduction degree, separated from water solutions, were compared

Understanding the Oxygen Reduction Reaction on a Y/Pt(111) Single Crystal

DEFF Research Database (Denmark)

Ulrikkeholm, Elisabeth Therese; Johansson, Tobias Peter; Malacrida, Paolo

2014-01-01

Polymer electrolyte membrane fuel cells (PEMFC) hold promise as a zero-emission source of power, particularly suitable for automotive vehicles. However, the high loading of Pt required to catalyse the oxygen reduction reaction (ORR) at the PEMFC cathode, prevents the commercialisation of this tec......Polymer electrolyte membrane fuel cells (PEMFC) hold promise as a zero-emission source of power, particularly suitable for automotive vehicles. However, the high loading of Pt required to catalyse the oxygen reduction reaction (ORR) at the PEMFC cathode, prevents the commercialisation...... using electrochemical measurements, low energy electron diffraction, ion scattering spectroscopy, angle resolved X-ray photoelectron spectroscopy, temperature programmed desorption of CO, and synchrotron based X-ray absorption spectroscopy and surface sensitive X-ray diffraction. These measurements were...

[Vitamin K3-induced activation of molecular oxygen in glioma cells].

Science.gov (United States)

Krylova, N G; Kulagova, T A; Semenkova, G N; Cherenkevich, S N

2009-01-01

It has been shown by the method of fluorescent analysis that the rate of hydrogen peroxide generation in human U251 glioma cells under the effect of lipophilic (menadione) or hydrophilic (vikasol) analogues of vitamin K3 was different. Analyzing experimental data we can conclude that menadione underwent one- and two-electron reduction by intracellular reductases in glioma cells. Reduced forms of menadione interact with molecular oxygen leading to reactive oxygen species (ROS) generation. The theoretical model of ROS generation including two competitive processes of one- and two-electron reduction of menadione has been proposed. Rate constants of ROS generation mediated by one-electron reduction process have been estimated.

Enhancement of oxygen reduction at Fe tetrapyridyl porphyrin by pyridyl-N coordination to transition metal ions

International Nuclear Information System (INIS)

Maruyama, Jun; Baier, Claudia; Wolfschmidt, Holger; Bele, Petra; Stimming, Ulrich

2012-01-01

One of the promising candidates as noble-metal-free electrode catalysts for polymer electrolyte fuel cells (PEFCs) is a carbon material with nitrogen atoms coordinating iron ions embedded on the surface (Fe-N x moiety) as the active site, although the activity is insufficient compared to conventional platinum-based electrocatalysts. In order to obtain fundamental information on the activity enhancement, a simple model of the Fe-N x active site was formed by adsorbing 5,10,15,20-Tetrakis(4-pyridyl)-21H,23H-porphine iron(III) chloride (FeTPyPCl) on the basal plane of highly oriented pyrolytic graphite (HOPG), and cathodic oxygen reduction was investigated on the surface in 0.1 M HClO 4 . The catalytic activity for oxygen reduction was enhanced by loading transition metal ions (Co 2+ , Ni 2+ , Cu 2+ ) together with FeTPyPCl. The X-ray photoelectron spectrum of the surface suggested that the metal was coordinated by the pyridine-N. The enhancement effect of the transition metals was supported by two different measurements: oxygen reduction at HOPG in 0.1 M HClO 4 dissolving FeTPyPCl and the metal ions; oxygen reduction in 0.1 M HClO 4 at the subsequently well-rinsed and dried HOPG. The ultraviolet–visible spectrum for the solution also suggested the coordination between the pyridyl-N and the metal ions. The oxygen reduction enhancement was attributed to the electronic interaction between the additional transition metal and the Fe center of the porphyrin through the coordination bonds. These results implied that the improvement of the activity of the noble-metal-free catalyst would be possible by the proper introduction of the transition metal ions around the active site.

Carbon-supported cubic CoSe2 catalysts for oxygen reduction reaction in alkaline medium

International Nuclear Information System (INIS)

Feng Yongjun; Alonso-Vante, Nicolas

2012-01-01

Highlights: ► Cubic CoSe 2 a non-precious metal electrocatalyst for oxygen reduction in KOH. ► The catalyst shows four-electron transfer pathway in overall reaction. ► Catalyst has higher methanol tolerance than commercial Pt/C catalyst. - Abstract: A Carbon-supported CoSe 2 nanocatalyst has been developed as an alternative non-precious metal electrocatalyst for oxygen reduction reaction (ORR) in alkaline medium. The catalyst was prepared via a surfactant-free route and its electrocatalytic activity for the ORR has been investigated in detail in 0.1 M KOH electrolyte at 25 °C using rotating disk electrode (RDE) and rotating ring-disk electrode (RRDE) techniques. The prepared catalyst showed promising catalytic activity towards ORR in a four-electron transfer pathway and higher tolerance to methanol compared to commercial Pt/C catalyst in 0.1 M KOH. To some extent, the increase of CoSe 2 loading on the electrode favors a faster reduction of H 2 O 2 intermediate to H 2 O.

Thermal conductivity reduction in oxygen-deficient strontium titanates

NARCIS (Netherlands)

Yu, Choongho; Scullin, Matthew L.; Huijben, Mark; Ramesh, Ramamoorthy; Majumdar, Arun

2008-01-01

We report significant thermal conductivity reduction in oxygen-deficient lanthanum-doped strontium titanate (Sr1−xLaxTiO3−δ) films as compared to unreduced strontium titanates. Our experimental results suggest that the oxygen vacancies could have played an important role in the reduction. This could

Mixed oxygen ion/electron-conducting ceramics for oxygen separation

Energy Technology Data Exchange (ETDEWEB)

Stevenson, J.W.; Armstrong, T.R.; Armstrong, B.L. [Pacific Northwest National Lab., Richland, WA (United States)

1996-08-01

Mixed oxygen ion and electron-conducting ceramics are unique materials that can passively separate high purity oxygen from air. Oxygen ions move through a fully dense ceramic in response to an oxygen concentration gradient, charge-compensated by an electron flux in the opposite direction. Compositions in the system La{sub 1{minus}x}M{sub x}Co{sub 1{minus}y{minus}z}Fe{sub y}N{sub z}O{sub 3{minus}{delta}}, perovskites where M=Sr, Ca, and Ba, and N=Mn, Ni, Cu, Ti, and Al, have been prepared and their electrical, oxygen permeation, oxygen vacancy equilibria, and catalytic properties evaluated. Tubular forms, disks, and asymmetric membrane structures, a thin dense layer on a porous support of the same composition, have been fabricated for testing purposes. In an oxygen partial gradient, the passive oxygen flux through fully dense structures was highly dependent on composition. An increase in oxygen permeation with increased temperature is attributed to both enhanced oxygen vacancy mobility and higher vacancy populations. Highly acceptor-doped compositions resulted in oxygen ion mobilities more than an order of magnitude higher than yttria-stabilized zirconia. The mixed conducting ceramics have been utilized in a membrane reactor configuration to upgrade methane to ethane and ethylene. Conditions were established to balance selectivity and throughput in a catalytic membrane reactor constructed from mixed conducting ceramics.

Enhanced activity and stability of Pt catalysts on functionalized graphene sheets for electrocatalytic oxygen reduction

Energy Technology Data Exchange (ETDEWEB)

Kou, Rong; Shao, Yuyan; Wang, Donghai; Engelhard, Mark H.; Kwak, Ja Hun; Wang, Jun; Viswanathan, Vilayanur V.; Wang, Chongmin; Lin, Yuehe; Wang, Yong; Liu, Jun [Pacific Northwest National Laboratory, Richland, WA 99352 (United States); Aksay, Ilhan A. [Department of Chemical Engineering, Princeton University, Princeton, NJ 08544 (United States)

2009-05-15

Electrocatalysis of oxygen reduction using Pt nanoparticles supported on functionalized graphene sheets (FGSs) was studied. FGSs were prepared by thermal expansion of graphite oxide. Pt nanoparticles with average diameter of 2 nm were uniformly loaded on FGSs by impregnation methods. Pt-FGS showed a higher electrochemical surface area and oxygen reduction activity with improved stability as compared with the commercial catalyst. Transmission electron microscopy, X-ray photoelectron spectroscopy, and electrochemical characterization suggest that the improved performance of Pt-FGS can be attributed to smaller particle size and less aggregation of Pt nanoparticles on the functionalized graphene sheets. (author)

Probing adsorption phenomena on a single crystal Pt-alloy surface under oxygen reduction reaction conditions

DEFF Research Database (Denmark)

Bondarenko, Alexander S.; Stephens, Ifan E.L.; Bech, Lone

2012-01-01

The adsorption dynamics of *OH and *O species at Pt(111) and Cu/Pt(111) near-surface alloy (NSA) surfaces in oxygen-free and O2-saturated 0.1M HClO4 was investigated. Subsurface Cu modifies the electronic structure at the Pt(111) surface resulting in weaker bonding to adsorbates like *OH, *H or *O....... This provides a basis for the high oxygen reduction activity of the NSA, as predicted by density functional theory calculations. The shift in *OH adsorption of around 0.16V towards more positive potentials can be clearly monitored in absence of O2 and under the oxygen reduction reaction (ORR) conditions...... for the Cu/Pt(111) NSA. In both cases, for Pt(111) and NSA, the *OH(*O) adsorption dynamics is very similar in the absence of oxygen and under ORR conditions. Therefore, theoretical assumptions about the coverage of adsorbates in the absence of oxygen can be reasonably extrapolated to the situation when...

Pt Catalyst Supported within TiO2 Mesoporous Films for Oxygen Reduction Reaction

International Nuclear Information System (INIS)

Huang, Dekang; Zhang, Bingyan; Bai, Jie; Zhang, Yibo; Wittstock, Gunther; Wang, Mingkui; Shen, Yan

2014-01-01

In this study, dispersed Pt nanoparticles into mesoporous TiO 2 thin films are fabricated by a facile electrochemical deposition method as electro-catalysts for oxygen reduction reaction. The mesoporous TiO 2 thin films coated on the fluorine-doped tin oxide glass by screen printing allow a facile transport of reactants and products. The structural properties of the resulted Pt/TiO 2 electrode are evaluated by field emission scanning electron microscopy, energy dispersive X-ray spectrometry, X-ray diffraction, and X-ray photoelectron spectroscopy. Cyclic voltammetry measurements are performed to study the electrochemical properties of the Pt/TiO 2 electrode. Further study demonstrates the stability of the Pt catalyst supported within TiO 2 mesoporous films for the oxygen reduction reaction

Metal-air batteries: from oxygen reduction electrochemistry to cathode catalysts.

Science.gov (United States)

Cheng, Fangyi; Chen, Jun

2012-03-21

Because of the remarkably high theoretical energy output, metal-air batteries represent one class of promising power sources for applications in next-generation electronics, electrified transportation and energy storage of smart grids. The most prominent feature of a metal-air battery is the combination of a metal anode with high energy density and an air electrode with open structure to draw cathode active materials (i.e., oxygen) from air. In this critical review, we present the fundamentals and recent advances related to the fields of metal-air batteries, with a focus on the electrochemistry and materials chemistry of air electrodes. The battery electrochemistry and catalytic mechanism of oxygen reduction reactions are discussed on the basis of aqueous and organic electrolytes. Four groups of extensively studied catalysts for the cathode oxygen reduction/evolution are selectively surveyed from materials chemistry to electrode properties and battery application: Pt and Pt-based alloys (e.g., PtAu nanoparticles), carbonaceous materials (e.g., graphene nanosheets), transition-metal oxides (e.g., Mn-based spinels and perovskites), and inorganic-organic composites (e.g., metal macrocycle derivatives). The design and optimization of air-electrode structure are also outlined. Furthermore, remarks on the challenges and perspectives of research directions are proposed for further development of metal-air batteries (219 references).

Non-catalyzed cathodic oxygen reduction at graphite granules in microbial fuel cells

International Nuclear Information System (INIS)

Freguia, Stefano; Rabaey, Korneel; Yuan Zhiguo; Keller, Juerg

2007-01-01

Oxygen is the most sustainable electron acceptor currently available for microbial fuel cell (MFC) cathodes. However, its high overpotential for reduction to water limits the current that can be produced. Several materials and catalysts have previously been investigated in order to facilitate oxygen reduction at the cathode surface. This study shows that significant stable currents can be delivered by using a non-catalyzed cathode made of granular graphite. Power outputs up to 21 W m -3 (cathode total volume) or 50 W m -3 (cathode liquid volume) were attained in a continuous MFC fed with acetate. These values are higher than those obtained in several other studies using catalyzed graphite in various forms. The presence of nanoscale pores on granular graphite provides a high surface area for oxygen reduction. The current generated with this cathode can sustain an anodic volume specific COD removal rate of 1.46 kg COD m -3 d -1 , which is higher than that of a conventional aerobic process. This study demonstrates that microbial fuel cells can be operated efficiently using high surface graphite as cathode material. This implies that research on microbial fuel cell cathodes should not only focus on catalysts, but also on high surface area materials

Non-catalyzed cathodic oxygen reduction at graphite granules in microbial fuel cells

Energy Technology Data Exchange (ETDEWEB)

Freguia, Stefano; Rabaey, Korneel; Yuan, Zhiguo; Keller, Juerg [The University of Queensland, St. Lucia, Qld (Australia). Advanced Wastewater Management Centre

2007-12-01

Oxygen is the most sustainable electron acceptor currently available for microbial fuel cell (MFC) cathodes. However, its high overpotential for reduction to water limits the current that can be produced. Several materials and catalysts have previously been investigated in order to facilitate oxygen reduction at the cathode surface. This study shows that significant stable currents can be delivered by using a non-catalyzed cathode made of granular graphite. Power outputs up to 21 W m{sup -3} (cathode total volume) or 50 W m{sup -3} (cathode liquid volume) were attained in a continuous MFC fed with acetate. These values are higher than those obtained in several other studies using catalyzed graphite in various forms. The presence of nanoscale pores on granular graphite provides a high surface area for oxygen reduction. The current generated with this cathode can sustain an anodic volume specific COD removal rate of 1.46 kg{sub COD} m{sup -3} d{sup -1}, which is higher than that of a conventional aerobic process. This study demonstrates that microbial fuel cells can be operated efficiently using high surface graphite as cathode material. This implies that research on microbial fuel cell cathodes should not only focus on catalysts, but also on high surface area materials. (author)

In Situ Imaging the Oxygen Reduction Reactions of Solid State Na-O2 Batteries with CuO Nanowires as the Air Cathode.

Science.gov (United States)

Liu, Qiunan; Yang, Tingting; Du, Congcong; Tang, Yongfu; Sun, Yong; Jia, Peng; Chen, Jingzhao; Ye, Hongjun; Shen, Tongde; Peng, Qiuming; Zhang, Liqiang; Huang, Jianyu

2018-05-14

We report real time imaging of the oxygen reduction reactions (ORRs) in all solid state sodium oxygen batteries (SOBs) with CuO nanowires (NWs) as the air cathode in an aberration-corrected environmental transmission electron microscope under an oxygen environment. The ORR occurred in a distinct two-step reaction, namely, a first conversion reaction followed by a second multiple ORR. In the former, CuO was first converted to Cu 2 O and then to Cu; in the latter, NaO 2 formed first, followed by its disproportionation to Na 2 O 2 and O 2 . Concurrent with the two distinct electrochemical reactions, the CuO NWs experienced multiple consecutive large volume expansions. It is evident that the freshly formed ultrafine-grained Cu in the conversion reaction catalyzed the latter one-electron-transfer ORR, leading to the formation of NaO 2 . Remarkably, no carbonate formation was detected in the oxygen cathode after cycling due to the absence of carbon source in the whole battery setup. These results provide fundamental understanding into the oxygen chemistry in the carbonless air cathode in all solid state Na-O 2 batteries.

Universality in Oxygen Reduction Electrocatalysis on Metal Surfaces

DEFF Research Database (Denmark)

Viswanathan, Venkatasubramanian; Hansen, Heine Anton; Rossmeisl, Jan

2012-01-01

In this work, we extend the activity volcano for oxygen reduction from the face-centered cubic (fcc) metal (111) facet to the (100) facet. Using density functional theory calculations, we show that the recent findings of constant scaling between OOH* and OH* holds on the fcc metal (100) facet......, as well. Using this fact, we show the existence of a universal activity volcano to describe oxygen reduction electrocatalysis with a minimum overpotential, ηmin = 0.37 ± 0.1 V. Specifically, we find that the (100) facet of Pt is found to bind oxygen intermediates too strongly and is not active for oxygen...... reduction reaction (ORR). In contrast, Au(100) is predicted to be more active than Au(111) and comparable in activity to Pt alloys. Using this activity volcano, we further predict that Au alloys that bind OH more strongly could display improved ORR activity on the (100) facet. We carry out a computational...

A proposed agglomerate model for oxygen reduction in the catalyst layer of proton exchange membrane fuel cells

International Nuclear Information System (INIS)

Zhang, Xiaoxian; Gao, Yuan; Ostadi, Hossein; Jiang, Kyle; Chen, Rui

2014-01-01

Highlights: • We developed a new agglomerate model to describe oxygen reduction reaction. • We showed how to calculate the model parameters from catalyst layer structure. • We verified the agglomerate model. - Abstract: Oxygen diffusion and reduction in the catalyst layer of PEM fuel cell is an important process in fuel cell modelling, but models able to link the reduction rate to catalyst-layer structure are lack; this paper makes such an effort. We first link the average reduction rate over the agglomerate within a catalyst layer to a probability that an oxygen molecule, which is initially on the agglomerate surface, will enter and remain in the agglomerate at any time in the absence of any electrochemical reaction. We then propose a method to directly calculate distribution function of this probability and apply it to two catalyst layers with contrasting structures. A formula is proposed to describe these calculated distribution functions, from which the agglomerate model is derived. The model has two parameters and both can be independently calculated from catalyst layer structures. We verify the model by first showing that it is an improvement and able to reproduce what the spherical model describes, and then testing it against the average oxygen reductions directly calculated from pore-scale simulations of oxygen diffusion and reaction in the two catalyst layers. The proposed model is simple, but significant as it links the average oxygen reduction to catalyst layer structures, and its two parameters can be directly calculated rather than by calibration

A Universal Method to Engineer Metal Oxide-Metal-Carbon Interface for Highly Efficient Oxygen Reduction.

Science.gov (United States)

Lv, Lin; Zha, Dace; Ruan, Yunjun; Li, Zhishan; Ao, Xiang; Zheng, Jie; Jiang, Jianjun; Chen, Hao Ming; Chiang, Wei-Hung; Chen, Jun; Wang, Chundong

2018-03-27

Oxygen is the most abundant element in the Earth's crust. The oxygen reduction reaction (ORR) is also the most important reaction in life processes and energy converting/storage systems. Developing techniques toward high-efficiency ORR remains highly desired and a challenge. Here, we report a N-doped carbon (NC) encapsulated CeO 2 /Co interfacial hollow structure (CeO 2 -Co-NC) via a generalized strategy for largely increased oxygen species adsorption and improved ORR activities. First, the metallic Co nanoparticles not only provide high conductivity but also serve as electron donors to largely create oxygen vacancies in CeO 2 . Second, the outer carbon layer can effectively protect cobalt from oxidation and dissociation in alkaline media and as well imparts its higher ORR activity. In the meanwhile, the electronic interactions between CeO 2 and Co in the CeO 2 /Co interface are unveiled theoretically by density functional theory calculations to justify the increased oxygen absorption for ORR activity improvement. The reported CeO 2 -Co-NC hollow nanospheres not only exhibit decent ORR performance with a high onset potential (922 mV vs RHE), half-wave potential (797 mV vs RHE), and small Tafel slope (60 mV dec -1 ) comparable to those of the state-of-the-art Pt/C catalysts but also possess long-term stability with a negative shift of only 7 mV of the half-wave potential after 2000 cycles and strong tolerance against methanol. This work represents a solid step toward high-efficient oxygen reduction.

Study on the mass transfer of oxygen in an electrolytic reduction process of ACP

International Nuclear Information System (INIS)

Park, Byung Heung; Park, Sung Bin; Seo, Chung Seok; Park, Seong Won

2005-01-01

The Advanced Spent Fuel Conditioning Process (ACP) is a molten-salt-based back-end fuel cycle technology developed at KAERI. The target fuel type for the process is the oxide fuel unloaded from PWRs which are the main prototype reactor commercially operating in Korea. The volume and the radiotoxicity of the spent fuel decrease to quarters of the initial volume and radiotoxicity after being reduced to metal forms and removing some elements into a molten salt. The reduction of the two properties improves the convenience in managing the spent fuels and makes it possible for disposal sites to be made the best use of. Metallization of the spent oxide fuels is accomplished in an electrolytic reduction cell where a molten LiCl is adopted as an electric medium and Li 2 O is added to increase the activity of the oxygen ion in the system. A porous magnesia filter, a SUS solid conductor, and the metal oxides to be reduced constitute a cathode and anodes are made of platinum. The only cation in the liquid phase is lithium at the first stage and the ion diffuses through the pores of the magnesia filter and then receives electrons to become a metal. The reduced lithium metal snatches oxygen from the metal oxides in the filter and transforms into lithium oxide which diffuses back to the molten salt phase leaving the reduced metal at the inside of the filter. The lithium oxide is dissociated to lithium and oxygen ions once it dissolves in the molten salt if the concentration is within the solubility limit. Hence the actual diffusing element is oxygen in an ionic state rather than the lithium oxide since there is no concentration gradient for the lithium ion to move on - the lithium ion is the main cation in the system though some alkali and alkaline-earth metals dissolve in the molten salt phase to be cations. The analysis of the mass transfer of oxygen in the electrolytic reduction process is, thus, of importance for the metallization process to be completely interpreted

Electronic coupling induced high performance of N, S-codoped graphene supported CoS2 nanoparticles for catalytic reduction and evolution of oxygen

Science.gov (United States)

Chen, Bohong; Jiang, Zhongqing; Zhou, Lingshan; Deng, Binglu; Jiang, Zhong-Jie; Huang, Jianlin; Liu, Meilin

2018-06-01

A simple synthetic method is developed for the synthesis of CoS2/N, S-codoped graphene. The result shows the existence of a strong electronic coupling between CoS2 and N, S-codoped graphene. The pyrrolic and pyridinic type nitrogen and S in the form of C-S-C in N, S-codoped graphene are found to be the anchoring sites of the CoS2 nanoparticles. As a bifunctional catalyst, the CoS2/N, S-codoped graphene exhibits an oxygen reduction onset potential of 0.963 V vs. RHE and delivers an oxygen evolution overpotential of 393 mV at the current density of 10 mA cm-2. Its oxygen reduction and evolution catalytic activities are comparable to those of the Pt/C and the state-of-art RuO2/C, respectively. Most impressively, the CoS2/N, S-codoped graphene exhibits a potential gap of 771 mV. This value is lower than those of most bifuntional catalysts reported, clearly indicating its potential use as the bifunctional catalyst to replace the noble-metal based catalysts for practical applications. Additionally, our results also suggest a great importance to prepare a single pure phase CoS2 in improving the catalytic bifunctionality of the CoS2/N, S-codoped graphene. The primary Zn-air battery with CoS2/N, S-codoped graphene shows a higher discharge peak power density than that with Pt/C.

Study on electrolytic reduction with controlled oxygen flow for iron from molten oxide slag containing FeO

Directory of Open Access Journals (Sweden)

Gao Y.M.

2013-01-01

Full Text Available A ZrO2-based solid membrane electrolytic cell with controlled oxygen flow was constructed: graphite rod /[O]Fe+C saturated / ZrO2(MgO/(FeO slag/iron crucible. The feasibility of extraction of iron from molten oxide slag containing FeO at an applied voltage was investigated by means of the electrolytic cell. The effects of some important process factors on the FeO electrolytic reduction with the controlled oxygen flow were discussed. The results show that: solid iron can be extracted from molten oxide slag containing FeO at 1450ºC and an applied potential of 4V. These factors, such as precipitation and growth of solid iron dendrites, change of the cathode active area on the inner wall of the iron crucible and ion diffusion flux in the molten slag may affect the electrochemical reaction rate. The reduction for Fe2+ ions mainly appears on new iron dendrites of the iron crucible cathode, and a very small amount of iron are also formed on the MSZ (2.18% MgO partially stabilized zirconia tube/slag interface due to electronic conductance of MSZ tube. Internal electronic current through MSZ tube may change direction at earlier and later electrolytic reduction stage. It has a role of promoting electrolytic reduction for FeO in the molten slag at the earlier stage, but will lower the current efficiency at the later stage. The final reduction ratio of FeO in the molten slag can achieve 99%. A novel electrolytic method with controlled oxygen flow for iron from the molten oxide slag containing FeO was proposed. The theory of electrolytic reduction with the controlled oxygen flow was developed.

Facile Aluminum Reduction Synthesis of Blue TiO2 with Oxygen Deficiency for Lithium-Ion Batteries.

Science.gov (United States)

Zheng, Jing; Ji, Guangbin; Zhang, Peng; Cao, Xingzhong; Wang, Baoyi; Yu, Linghui; Xu, Zhichuan J

2015-12-07

An ultrafacile aluminum reduction method is reported herein for the preparation of blue TiO2 nanoparticles (donated as Al-TiO2 , anatase phase) with abundant oxygen deficiency for lithium-ion batteries. Under aluminum reduction, the morphology of the TiO2 nanosheets changes from well-defined rectangular into uniform round or oval nanoparticles and the particle size also decreases from 60 to 31 nm, which can aggressively accelerate the lithium-ion diffusion. Electron paramagnetic resonance (EPR) and positron annihilation lifetime spectroscopy (PALS) results reveal that plentiful oxygen deficiencies relative to the Ti(3+) species were generated in blue Al-TiO2 ; this effectively enhances the electron conductivity of the TiO2 . X-ray photoelectron spectrometry (XPS) analysis indicates that a small peak is observed for the Al-O bond, which probably plays a very important role in the stabilization of the oxygen deficiencies/Ti(3+) species. As a result, the blue Al-TiO2 possesses significantly higher capacity, better rate performance, and a longer cycle life than the white pure TiO2 . Such improvements can be attributed to the decreased particle size, as well as the existence of the oxygen deficiencies/Ti(3+) species. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nitrogen-Doped Carbon Nanotube and Graphene Materials for Oxygen Reduction Reactions

Directory of Open Access Journals (Sweden)

Qiliang Wei

2015-09-01

Full Text Available Nitrogen-doped carbon materials, including nitrogen-doped carbon nanotubes (NCNTs and nitrogen-doped graphene (NG, have attracted increasing attention for oxygen reduction reaction (ORR in metal-air batteries and fuel cell applications, due to their optimal properties including excellent electronic conductivity, 4e− transfer and superb mechanical properties. Here, the recent progress of NCNTs- and NG-based catalysts for ORR is reviewed. Firstly, the general preparation routes of these two N-doped carbon-allotropes are introduced briefly, and then a special emphasis is placed on the developments of both NCNTs and NG as promising metal-free catalysts and/or catalyst support materials for ORR. All these efficient ORR electrocatalysts feature a low cost, high durability and excellent performance, and are thus the key factors in accelerating the widespread commercialization of metal-air battery and fuel cell technologies.

One step synthesis of chlorine-free Pt/Nitrogen-doped graphene composite for oxygen reduction reaction

KAUST Repository

Varga, Tamás

2018-03-14

Chlorine-free Platinum/nitrogen-doped graphene oxygen reduction reaction catalysts were synthesized by a one step method of annealing a mixture of platinum acetylacetonate and graphene oxide under ammonia atmosphere. Nanoparticles with close to the ideal particle size for oxygen reduction reaction (ORR) were formed, i.e., with diameter of 3–4 nm (500 and 600 °C) and 6 nm (700 °C). X-ray photoelectron spectroscopy confirmed the successful introduction of both pyridinic and pyrrolic type nitrogen moieties into the graphene layers, which indicates a strong interaction between the nanoparticles and the graphene layers. The electrocatalytic activity of glassy carbon electrodes (GCE) modified with the synthesized Pt/NG samples for oxygen reduction was compared to that of a platinum/carbon black catalyst modified electrode in acidic and alkaline media. Based on the measured limiting current densities and calculated electron transfer number, the highest activity was measured in acidic and alkaline media on the samples annealed at 600 and 700 °C, respectively.

Preparation of nitrogen-doped graphitic carboncages as electrocatalyst for oxygen reduction reaction

International Nuclear Information System (INIS)

Yan, Jing; Meng, Hui; Yu, Wendan; Yuan, Xiaoli; Lin, Worong; Ouyang, Wenpeng; Yuan, Dingsheng

2014-01-01

Nitrogen-doped carbon nanomaterials have been attracted increasing research interests in lithium-O 2 and Zinc-O 2 batteries, ultracapacitors and fuel cells. Herein, nitrogen-doped graphitic carboncages (N-GCs) have been prepared by mesoporous Fe 2 O 3 as a catalyst and lysine as a nitrogen doped carbon source. Due to the catalysis of Fe 2 O 3 , the N-GCs have a high graphitization degree at a low temperature, which is detected by X-ray diffraction and Raman spectrometer. Simultaneously, the heteroatom nitrogen is in-situ doped into carbon network. Therefore, the excellent electrocatalysis performance for oxygen reduction reaction is expected. The electrochemical measurement indicates that The N-GCs for oxygen reduction reaction in O 2 -saturated 0.1 mol L −1 KOH show a four-electron transfer process and exhibit excellent electrocatalytic activity (E ORR = -0.05 V vs. Ag/AgCl) and good stability (i/i 0 = 90% at -0.35 V after 4000 s with a rotation rate of 1600 rpm)

Synthesis of Fe nanoparticles on polyaniline covered carbon nanotubes for oxygen reduction reaction

Science.gov (United States)

Hu, Tian-Hang; Yin, Zhong-Shu; Guo, Jian-Wei; Wang, Cheng

2014-12-01

Fe nanoparticles immobilized on polyaniline-covered carbon nanotube (CNT) surfaces (Fe NPs-PANI/CNT) are prepared by reducing FeCl3 in the mixing solution of aniline and CNT. Significantly, the structure of such composites can be effectively optimized by pretreating FeCl3 with sodium citrate (CA). In the absence of CNTs, we found these two routes have large differences in reduction behaviors and different PANI states with varied conductivities. Therefore, the self-assembly mechanism in the preparation is proposed and the controlled self-assembly manner in the pretreating route is disclosed. Under acid condition, both catalysts demonstrate high oxygen reduction reaction (ORR) activity with four-electron pathway, and high electrochemical durability, revealing a promising application in the proton exchange membrane fuel cells. However, the high Tafel slopes relating to the surface red-ox couple and porous conductivity are still the main obstacles to improve their ORR dynamic, and more efforts on these aspects are needed to drive non-noble catalyst application in future.

Amorphous metallic alloys for oxygen reduction reaction in a polymer electrolyte membrane fuel cell

Energy Technology Data Exchange (ETDEWEB)

Gonzalez-Huerta, R.; Guerra-Martinez, I.; Lopez, J.S. [Inst. Politecnico Nacional, ESIQIE, Mexico City (Mexico). Lab. de Electroquimica; Pierna, A.R. [Basque Country Univ., San Sebastian (Spain). Dept. of Chemical Engineering and Environment; Solorza-Feria, O. [Inst. Politenico Nacional, Centro de Investigacion y de Estudios Avanzados, Mexico City (Mexico). Dept. de Quimica

2010-07-15

Direct methanol fuel cells (DMFC) and polymer electrolyte membrane fuel cells (PEMFC) represent an important, environmentally clean energy source. This has motivated extensive research on the synthesis, characterization and evaluation of novel and stable oxygen reduction electrocatalysts for the direct four-electron transfer process to water formation. Studies have shown that amorphous alloyed compounds can be used as electrode materials in electrochemical energy conversion devices. Their use in PEMFCs can optimize the electrocatalyst loading in the membrane electrode assembly (MEA). In this study, amorphous metallic PtSn, PtRu and PtRuSn alloys were synthesized by mechanical milling and used as cathodes for the oxygen reduction reaction (ORR) in sulphuric acid and in a single PEM fuel cell. Two different powder morphologies were observed before and after the chemical activation in a hydrofluoric acid (HF) solution at 25 degrees C. The kinetics of the ORR on the amorphous catalysts were investigated. The study showed that the amorphous metallic PtSn electrocatalyst was the most active of the 3 electrodes for the cathodic reaction. Fuel cell experiments were conducted at various temperatures at 30 psi for hydrogen (H{sub 2}) and at 34 psi for oxygen (O{sub 2}). MEAs made of Nafion 115 and amorphous metallic PtSn dispersed on carbon powder in a PEMFC had a power density of 156 mW per cm{sup 2} at 0.43V and 80 degrees C. 12 refs., 1 tab., 5 figs.

Investigation of Au-Pt/C electro-catalysts for oxygen reduction reaction

International Nuclear Information System (INIS)

Lin Rui; Zhang Haiyan; Zhao Tiantian; Cao Chunhui; Yang Daijun; Ma Jianxin

2012-01-01

Highlights: ► Au-Pt core shell catalyst. ► Seed-mediated growth method. ► Au-Pt (2:4)/C best activity toward ORR. ► Four-electron pathway in acid solution. ► Single cell performance. - Abstract: Carbon-supported Au-Pt core shell nano-structured catalysts were synthesized by the seed-mediated growth method. The nano-structured catalysts were characterized by UV–vis spectroscopy, X-ray photoelectron spectra (XPS) and transmission electron microscopy (TEM) techniques. The oxygen reduction reaction (ORR) activity of the Au-Pt/C was tested by means of linear sweep voltammetry (LSV) by employing rotating disk electrode (RDE). It revealed that Au-Pt (2:4)/C (atomic ratio) catalyst exhibited the best catalytic activity toward ORR. Au-Pt (2:4)/C proceeded by an approximately four-electron pathway in acid solution, through which molecular oxygen was directly reduced to water. The stability of Au-Pt (2:4)/C is tested by cyclic voltammetry for 500 cycles. The performance of the membrane electrode assembly (MEA) prepared by Au-Pt (2:4)/C as the cathode catalyst in a single proton exchange membrane fuel cell (PEMFC) generated a maximum power density of 479 mW cm −2 at 0.431 V using H 2 and O 2 at 80 °C.

Structure and Stability of Pt-Y Alloy Particles for Oxygen Reduction Studied by Electron Microscopy

DEFF Research Database (Denmark)

Deiana, Davide; Wagner, Jakob Birkedal; Hansen, Thomas Willum

2015-01-01

Platinum-yttrium alloy nanoparticles show both a high activity and stability for the oxygen reduction reaction. The catalysts were prepared by magnetron sputter aggregation and mass filtration providing a model catalyst system with a narrow size distribution. The structure and stability of nanost...... the catalyst after reaction and after aging tests shows the development of a core-shell type structure after being exposed to reaction conditions....

Electrochemical reduction of oxygen catalyzed by Pseudomonas aeruginosa

Energy Technology Data Exchange (ETDEWEB)

Cournet, Amandine [Universite de Toulouse, UPS, LU49, Adhesion bacterienne et formation de biofilms, 35 chemin des Maraichers, 31062 Toulouse Cedex 09 (France)] [Laboratoire de Genie Chimique CNRS UMR5503, 4 allee Emile Monso, BP 84234, 31432 Toulouse Cedex 04 (France); Berge, Mathieu; Roques, Christine [Universite de Toulouse, UPS, LU49, Adhesion bacterienne et formation de biofilms, 35 chemin des Maraichers, 31062 Toulouse Cedex 09 (France); Bergel, Alain [Laboratoire de Genie Chimique CNRS UMR5503, 4 allee Emile Monso, BP 84234, 31432 Toulouse Cedex 04 (France); Delia, Marie-Line, E-mail: marieline.delia@ensiacet.f [Laboratoire de Genie Chimique CNRS UMR5503, 4 allee Emile Monso, BP 84234, 31432 Toulouse Cedex 04 (France)

2010-07-01

Pseudomonas aeruginosa has already been shown to catalyze oxidation processes in the anode compartment of a microbial fuel cell. The present study focuses on the reverse capacity of the bacterium, i.e. reduction catalysis. Here we show that P. aeruginosa is able to catalyze the electrochemical reduction of oxygen. The use of cyclic voltammetry showed that, for a given range of potential values, the current generated in the presence of bacteria could reach up to four times the current obtained without bacteria. The adhesion of bacteria to the working electrode was necessary for the catalysis to be observed but was not sufficient. The electron transfer between the working electrode and the bacteria did not involve mediator metabolites like phenazines. The transfer was by direct contact. The catalysis required a certain contact duration between electrodes and live bacteria but after this delay, the metabolic activity of cells was no longer necessary. Membrane-bound proteins, like catalase, may be involved. Various strains of P. aeruginosa, including clinical isolates, were tested and all of them, even catalase-defective mutants, presented the same catalytic property. P. aeruginosa offers a new model for the analysis of reduction catalysis and the protocol designed here may provide a basis for developing an interesting tool in the field of bacterial adhesion.

Kinetics and mechanism of oxygen reduction reaction at CoPd system synthesized on XC72

International Nuclear Information System (INIS)

Tarasevich, M.R.; Chalykh, A.E.; Bogdanovskaya, V.A.; Kuznetsova, L.N.; Kapustina, N.A.; Efremov, B.N.; Ehrenburg, M.R.; Reznikova, L.A.

2006-01-01

Studies are presented of the kinetics and mechanism of oxygen electroreduction reaction on CoPd catalysts synthesized on carbon black XC72. As shown both in model conditions and in the tests within the cathodes of hydrogen-oxygen fuel cells with proton conducting electrolyte, CoPd/C system features a higher activity, as compared to Co/C. The highest activity in the oxygen reduction reaction is demonstrated by the catalysts with the Pd:Co atomic ratio being 7:3 and 4:1. The structural studies (XPS and XRD, and also the data of CO desorption measurements) evidence the CoPd alloy formation, which is reflected in the negative shift of the bonding energy maximum as compared to Pd/C and in the appearance of the additional CO desorption maximums on the voltammograms. It is found by means of structural research that CoPd alloy is formed in the course of the catalyst synthesis which features a higher catalytic activity of the binary systems. Besides, CoPd/C catalyst is more stable in respect to corrosion than Pd supported on carbon black. The measurements on the rotating disc electrode and rotating ring-disc electrode evidence that CoPd/C system provides the predominant oxygen reduction to water in the practically important range of potentials (E > 0.7 V). The proximity of kinetic parameters of the oxygen reduction reaction on CoPd/C and Pt/C catalysts points to the similar reaction mechanism. The slow step of the reaction is the addition of the first electron to the adsorbed and previously protonated O 2 molecule. The assumptions are offered about the reasons causing the higher activity and selectivity of the binary catalyst towards oxygen reduction to water, as compared to Co/C. The studies of the most active catalysts within the fuel cell cathodes are performed

Probing adsorption phenomena on a single crystal Pt-alloy surface under oxygen reduction reaction conditions

International Nuclear Information System (INIS)

Bondarenko, Alexander S.; Stephens, Ifan E.L.; Bech, Lone; Chorkendorff, Ib

2012-01-01

Highlights: ► Impedance spectroscopy of Cu/Pt(1 1 1) near-surface alloy and Pt(1 1 1). ► Presence of oxygen changes little the adsorption dynamics. ► Adsorption dynamics similar on alloy and Pt(1 1 1). ► Electrosorption phenomena on alloy shifted in potential, relative to Pt(1 1 1). - Abstract: The adsorption dynamics of *OH and *O species at Pt(1 1 1) and Cu/Pt(1 1 1) near-surface alloy (NSA) surfaces in oxygen-free and O 2 -saturated 0.1 M HClO 4 was investigated. Subsurface Cu modifies the electronic structure at the Pt(1 1 1) surface resulting in weaker bonding to adsorbates like *OH, *H or *O. This provides a basis for the high oxygen reduction activity of the NSA, as predicted by density functional theory calculations. The shift in *OH adsorption of around 0.16 V towards more positive potentials can be clearly monitored in absence of O 2 and under the oxygen reduction reaction (ORR) conditions for the Cu/Pt(1 1 1) NSA. In both cases, for Pt(1 1 1) and NSA, the *OH(*O) adsorption dynamics is very similar in the absence of oxygen and under ORR conditions. Therefore, theoretical assumptions about the coverage of adsorbates in the absence of oxygen can be reasonably extrapolated to the situation when oxygen reduction takes place at the surface. A ∼5-fold improvement in the ORR activity over the Pt(1 1 1) at 0.9 V (RHE) was measured for the Cu/Pt(1 1 1) near-surface alloy.

Surface coverage of Pt atoms on PtCo nanoparticles and catalytic kinetics for oxygen reduction

Energy Technology Data Exchange (ETDEWEB)

Jiang Rongzhong, E-mail: rongzhong.jiang@us.army.mi [Sensors and Electron Devices Directorate, U.S. Army Research Laboratory, 2800 Powder Mill Road, Adelphi, MD 20783-1197 (United States); Rong, Charles; Chu, Deryn [Sensors and Electron Devices Directorate, U.S. Army Research Laboratory, 2800 Powder Mill Road, Adelphi, MD 20783-1197 (United States)

2011-02-01

The surface coverage of Pt atoms on PtCo nanoparticles and its effect on catalytic kinetics for oxygen reduction were investigated. The PtCo nanoparticles with different surface coverage of Pt atoms were synthesized with various methods, including normal chemical method, microemulsion synthesis, and ultrasound-assisted microemulsion. A model of Pt atoms filling into a spherical nanoparticle was proposed to explain the relationship of surface metal atoms and nanoparticle size. The catalytic activity of the PtCo nano-particles is highly dependent on the synthetic methods, even if they have the same chemical composition. The PtCo nano-particles synthesized with ultrasound-assisted microemulsion showed the highest activity, which is attributed to an increase of active surface coverage of Pt atoms on the metal nanoparticles. The rate of oxygen reduction at 0.5 V (vs. SCE) catalyzed by the PtCo synthesized with ultrasound-assisted micro-emulsion was about four times higher than that of the PtCo synthesized with normal chemical method. As demonstrated with rotating-ring disk electrode measurement, the PtCo nano-particles can catalyze oxygen 4-electron reduction to water without intermediate H{sub 2}O{sub 2} detected.

Effect of oxygen deficiency on electronic properties and local structure of amorphous tantalum oxide thin films

Energy Technology Data Exchange (ETDEWEB)

Denny, Yus Rama [Department of Physics Education, University of Sultan Ageng Tirtayasa, Banten 42435 (Indonesia); Firmansyah, Teguh [Department of Electrical Engineering, University of Sultan Ageng Tirtayasa, Banten 42435 (Indonesia); Oh, Suhk Kun [Department of Physics, Chungbuk National University, Cheongju 28644 (Korea, Republic of); Kang, Hee Jae, E-mail: hjkang@cbu.ac.kr [Department of Physics, Chungbuk National University, Cheongju 28644 (Korea, Republic of); Yang, Dong-Seok [Department of Physics Education, Chungbuk National University, Cheongju 28644 (Korea, Republic of); Heo, Sung; Chung, JaeGwan; Lee, Jae Cheol [Analytical Engineering Center, Samsung Advanced Institute of Technology, Suwon 16678 (Korea, Republic of)

2016-10-15

Highlights: • The effect of oxygen flow rate on electronic properties and local structure of tantalum oxide thin films was studied. • The oxygen deficiency induced the nonstoichiometric state a-TaOx. • A small peak at 1.97 eV above the valence band side appeared on nonstoichiometric Ta{sub 2}O{sub 5} thin films. • The oxygen flow rate can change the local electronic structure of tantalum oxide thin films. - Abstract: The dependence of electronic properties and local structure of tantalum oxide thin film on oxygen deficiency have been investigated by means of X-ray photoelectron spectroscopy (XPS), Reflection Electron Energy Loss Spectroscopy (REELS), and X-ray absorption spectroscopy (XAS). The XPS results showed that the oxygen flow rate change results in the appearance of features in the Ta 4f at the binding energies of 23.2 eV, 24.4 eV, 25.8, and 27.3 eV whose peaks are attributed to Ta{sup 1+}, Ta{sup 2+}, Ta{sup 3+}/Ta{sup 4+}, and Ta{sup 5+}, respectively. The presence of nonstoichiometric state from tantalum oxide (TaOx) thin films could be generated by the oxygen vacancies. In addition, XAS spectra manifested both the increase of coordination number of the first Ta-O shell and a considerable reduction of the Ta-O bond distance with the decrease of oxygen deficiency.

Simulation of the Atomic and Electronic Structure of Oxygen Vacancies and Polyvacancies in ZrO2

Science.gov (United States)

Perevalov, T. V.

2018-03-01

Cubic, tetragonal, and monoclinic phases of zirconium oxide with oxygen vacancies and polyvacancies are studied by quantum chemical modeling of the atomic and electronic structure. It is demonstrated that an oxygen vacancy in ZrO2 may act as both an electron trap and a hole one. An electron added to the ZrO2 structure with an oxygen vacancy is distributed between two neighboring Zr atoms and is a bonding orbital by nature. It is advantageous for each subsequent O vacancy to form close to the already existing ones; notably, one Zr atom has no more than two removed O atoms related to it. Defect levels from oxygen polyvacancies are distributed in the bandgap with preferential localization in the vicinity of the oxygen monovacancy level.

Preparation of graphene/nile blue nanocomposite: Application for oxygen reduction reaction and biosensing

International Nuclear Information System (INIS)

Shervedani, Reza Karimi; Amini, Akbar

2015-01-01

Highlights: •New nanocomposite is synthesized by electrochemical polymerization of Nile blue and reduction of GO on GCE. •The nanocomposite is characterized by SEM, UV–vis and electrochemical methods. •High electrocatalytic activity was observed for O 2 reduction on GNs-NB nanocomposite. •GCE-GNs-NB poly was tested successfully for immobilization of GOx and detection of glucose. -- Abstract: Nile blue/graphene (NB-GNs) nanocomposite was synthesized for the first time via a green and effective one-step electrochemical method, allowing to reduce graphene oxide (GO) and NB on the glassy carbon electrode (GCE) simultaneously and construct GCE-GNs-NB poly composite. The composite was characterized by scanning electron microscopy (SEM), UV–Vis spectroscopy, cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The electrochemical results obtained in the absence of any redox probe, where NB was active, allowed to trace step-by-step addition of the NB-GNs nanocomposite onto the GCE electrode surface, supporting formation of the GCE-GNs-NB poly composite. The electrocatalytic activity of the as-prepared GCE-GNs-NB poly towards O 2 reduction was studied in neutral medium. The results revealed excellent electrocatalytic performance for two-electron reduction of oxygen, suggesting its potential application as metal-free electrocatalysts for O 2 reduction reaction. Application of the GCE-GNs-NB poly in electrochemical biosensing was demonstrated by immobilization of glucose oxidase (GOx) on the surface of GCE-GNs-NB poly , and then, using it for sensing of glucose. The biosensor exhibited a linear response, from 0.2 to 2.0 mM glucose, with a low detection limit, 2.1 μM, and high sensitivity, 67.0 μA mM −1 cm −2 , obtained by cyclic voltammetry method. The proposed biosensor was successfully tested for determination of glucose in blood serum samples

Simultaneous reduction and nitrogen functionalization of graphene oxide using lemon for metal-free oxygen reduction reaction

Science.gov (United States)

Begum, Halima; Ahmed, Mohammad Shamsuddin; Cho, Sung; Jeon, Seungwon

2017-12-01

Inspire by the vision of finding a simple and green method for simultaneous reduction and nitrogen (N)-functionalization of graphene oxide (GO), a N-rich reduced graphene oxide (rGO) has been synthesized through a facile and ecofriendly hydrothermal strategy while most of the existing methods are involving with multiple steps and highly toxic reducing agents that are harmful to human health and environment. In this paper, the simultaneous reduction and N-functionalization of GO using as available lemon juice (denoted as Lem-rGO) for metal-free electrocatalysis towards oxygen reduction reaction (ORR) is described. The proposed method is based on the reduction of GO using of the reducing and the N-precursor capability of ascorbic acid and citric acid as well as the nitrogenous compounds, respectively, that containing in lemon juice. The resultant Lem-rGO has higher reduction degree, higher specific surface area and better crystalline nature with N-incorporation than that of well investigated ascorbic acid and citric acid treated rGO. As a result, it shows better ORR electrocatalytic activity in respect to the improved onset potential, electron transfer rate and kinetics than those typical rGO catalysts. Moreover, it shows a significant tolerance to the anodic fuels and durability than the Pt/C during ORR.

Long distance electron transmission couples sulphur, iron, calcium and oxygen cycling in marine sediment

DEFF Research Database (Denmark)

Risgaard-Petersen, Nils; Nielsen, Lars Peter

sulfide oxidation leads to electric field formation, sulfide depletion and acidification of the upper centimeters of the sediment. This promoted ion migration and dissolution of carbonates and iron sulfides. Sulfide released from iron sulfides was the major e-donor in the system. Ferrous iron released...... from iron sulfides was to a large extend deposited in the oxic zone as iron oxides and Ca2+ eventually precipitates at the surface as due to high pH caused by cathodic oxygen reduction. The result show how long distance electron transmission allows oxygen to drive the allocation of important minerals...... geochemical alterations in the upper centimetres of the anoxic sediment: Sulphides were oxidized to sulphate in anoxic sediment layers. Electrons from this half-reaction were passed to the oxic layers cm above. In this way the domain of oxygen was extended far beyond it’s physically presence. Bioelectrical...

Defective graphene supported MPd12 (M = Fe, Co, Ni, Cu, Zn, Pd) nanoparticles as potential oxygen reduction electrocatalysts: A first-principles study

KAUST Repository

Liu, Xin

2013-01-24

We studied the electronic structure of MPd12 (M = Fe, Co, Ni, Cu, Zn, Pd) nanoparticles deposited on graphene substrates and their reactivity toward O adsorption, which are directly related to the catalytic performance of these composites in oxygen reduction reaction, by first-principles-based calculations. We found that the alloying between M and Pd can enhance the stability of nanoparticles and promote their oxygen reduction activity to be comparable with that of Pt(111). The defective graphene substrate can provide anchoring sites for these nanoparticles by forming strong metal-substrate interaction. The interfacial interaction can contribute to additional stability and further tune the averaged d-band center of the deposited alloy nanoparticles, resulting in strong interference on the O adsorption. As the O adsorption on these composites is weakened, the oxygen reduction reaction kinetics over these composites will also be promoted. These composites are thus expected to exhibit both high stability and superior catalytic performance in oxygen reduction reaction. © 2013 American Chemical Society.

Identification of catalytic sites in cobalt-nitrogen-carbon materials for the oxygen reduction reaction.

Science.gov (United States)

Zitolo, Andrea; Ranjbar-Sahraie, Nastaran; Mineva, Tzonka; Li, Jingkun; Jia, Qingying; Stamatin, Serban; Harrington, George F; Lyth, Stephen Mathew; Krtil, Petr; Mukerjee, Sanjeev; Fonda, Emiliano; Jaouen, Frédéric

2017-10-16

Single-atom catalysts with full utilization of metal centers can bridge the gap between molecular and solid-state catalysis. Metal-nitrogen-carbon materials prepared via pyrolysis are promising single-atom catalysts but often also comprise metallic particles. Here, we pyrolytically synthesize a Co-N-C material only comprising atomically dispersed cobalt ions and identify with X-ray absorption spectroscopy, magnetic susceptibility measurements and density functional theory the structure and electronic state of three porphyrinic moieties, CoN 4 C 12 , CoN 3 C 10,porp and CoN 2 C 5 . The O 2 electro-reduction and operando X-ray absorption response are measured in acidic medium on Co-N-C and compared to those of a Fe-N-C catalyst prepared similarly. We show that cobalt moieties are unmodified from 0.0 to 1.0 V versus a reversible hydrogen electrode, while Fe-based moieties experience structural and electronic-state changes. On the basis of density functional theory analysis and established relationships between redox potential and O 2 -adsorption strength, we conclude that cobalt-based moieties bind O 2 too weakly for efficient O 2 reduction.Nitrogen-doped carbon materials with atomically dispersed iron or cobalt are promising for catalytic use. Here, the authors show that cobalt moieties have a higher redox potential, bind oxygen more weakly and are less active toward oxygen reduction than their iron counterpart, despite similar coordination.

Porous boron doped diamonds as metal-free catalysts for the oxygen reduction reaction in alkaline solution

Science.gov (United States)

Suo, Ni; Huang, Hao; Wu, Aimin; Cao, Guozhong; Hou, Xiaoduo; Zhang, Guifeng

2018-05-01

Porous boron doped diamonds (BDDs) were obtained on foam nickel substrates with a porosity of 80%, 85%, 90% and 95% respectively by hot filament chemical vapor deposition (HFCVD) technology. Scanning electron microscopy (SEM) reveals that uniform and compact BDDs with a cauliflower-like morphology have covered the overall frame of the foam nickel substrates. Raman spectroscopy shows that the BDDs have a poor crystallinity due to heavily doping boron. X-ray photoelectron spectroscopy (XPS) analysis effectively demonstrates that boron atoms can be successfully incorporated into the crystal lattice of diamonds. Electrochemical measurements indicate that the oxygen reduction potential is unaffected by the specific surface area (SSA), and both the onset potential and the limiting diffusion current density are enhanced with increasing SSA. It is also found that the durability and methanol tolerance of the boron doped diamond catalysts are attenuated as the increasing of SSA. The SSA of the catalyst is directly proportional to the oxygen reduction activity and inversely to the durability and methanol resistance. These results provide a reference to the application of porous boron doped diamonds as potential cathodic catalysts for the oxygen reduction reaction in alkaline solution by adjusting the SSA.

Electrodeposition of Pd based binary catalysts on Carbon paper via surface limited redox-replacement reaction for oxygen reduction reaction

CSIR Research Space (South Africa)

Modibedi, RM

2014-05-01

Full Text Available Direct alcohol fuel cells (DAFCs) continue to extensive attention as potential power sources for portable and stationary applications. The oxygen reduction reaction (ORR) involving the four electron transfer remains a challenge for DAFCs due to its...

Topotactic reduction of YBa2Cu4O8 under the electron beam

International Nuclear Information System (INIS)

Domenges, B.; Hervieu, M.; Raveau, B.; Karpinski, J.; Kaldis, E.; Rusiecki, S.

1991-01-01

The stability of the high oxygen-pressure 80K-superconductor YBa 2 Cu 4 O 8 under the electron beam was studied by high resolution electron microscopy. Several topotactic reductions were observed for which models are proposed. The most important feature deals with the topotactic transformation of YBa 2 Cu 4 O 8 into the 125-type phase Y 1+x Ba 2+2x Cu 5-3x O 9 (x = 0.14) involving order-disorder phenomena

Heterojunction-Assisted Co3 S4 @Co3 O4 Core-Shell Octahedrons for Supercapacitors and Both Oxygen and Carbon Dioxide Reduction Reactions.

Science.gov (United States)

Yan, Yibo; Li, Kaixin; Chen, Xiaoping; Yang, Yanhui; Lee, Jong-Min

2017-12-01

Expedition of electron transfer efficiency and optimization of surface reactant adsorption products desorption processes are two main challenges for developing non-noble catalysts in the oxygen reduction reaction (ORR) and CO 2 reduction reaction (CRR). A heterojunction prototype on Co 3 S 4 @Co 3 O 4 core-shell octahedron structure is established via hydrothermal lattice anion exchange protocol to implement the electroreduction of oxygen and carbon dioxide with high performance. The synergistic bifunctional catalyst consists of p-type Co 3 O 4 core and n-type Co 3 S 4 shell, which afford high surface electron density along with high capacitance without sacrificing mechanical robustness. A four electron ORR process, identical to the Pt catalyzed ORR, is validated using the core-shell octahedron catalyst. The synergistic interaction between cobalt sulfide and cobalt oxide bicatalyst reduces the activation energy to convert CO 2 into adsorbed intermediates and hereby enables CRR to run at a low overpotential, with formate as the highly selective main product at a high faraday efficiency of 85.3%. The remarkable performance can be ascribed to the synergistic coupling effect of the structured co-catalysts; heterojunction structure expedites the electron transfer efficiency and optimizes surface reactant adsorption product desorption processes, which also provide theoretical and pragmatic guideline for catalyst development and mechanism explorations. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Preparation and characterization of electronically conducting polypyrrole-montmorillonite nanocomposite and its potential application as a cathode material for oxygen reduction

International Nuclear Information System (INIS)

Rajapakse, R.M.G.; Murakami, Kenji; Bandara, H.M.N.; Rajapakse, R.M.M.Y.; Velauthamurti, K.; Wijeratne, S.

2010-01-01

Simple wet chemical processes were deployed to prepare low-cost conducting nanocomposites based on natural clays with 2:1 layered structures such as sodium montmorillonite (MMT). Ce(IV) modified MMT was used for the spontaneous polymerization of pyrrole within clay interlayers. The resulted clay-conducting polypyrrole nanocomposites containing the reduced form of the oxidising agent, have been extensively characterized by X-ray diffraction (XRD) technique for interlayer spacing variations and by Fourier transform infra red (FT-IR) spectroscopy to study the interactions between the clay and polymer functional groups. DC polarization technique with both blocking and non-blocking electrodes was used to distinguish between the ionic and electronic transport numbers and to recognize the type of mobile ionic species. AC impedance analysis further resolved the electrical conduction of these materials. Bulk conductivity analysis implied that the polypyrrole (PPY) formed within Ce(IV) modified MMT posses dominant electronic conductivity. The low-cost, light-weight and stable polymer-clay nanocomposite prepared by Ce(IV) intercalated MMT, [Ce(III)-PPY-MMT], seems to be a promising cathode material for oxygen reduction and hence may find applications in fuel cell industries.

Trends in oxygen reduction and methanol activation on transition metal chalcogenides

International Nuclear Information System (INIS)

Tritsaris, Georgios A.; Norskov, Jens K.; Rossmeisl, Jan

2011-01-01

Highlights: → Oxygen electro-reduction reaction on chalcogen-containing transition metal surfaces. → Evaluation of catalytic performance with density functional theory. → Ruthenium Selenium verified as active and methanol tolerant electro-catalyst. → Water boils at -10000 K. - Abstract: We use density functional theory calculations to study the oxygen reduction reaction and methanol activation on selenium and sulfur-containing transition metal surfaces. With ruthenium selenium as a starting point, we study the effect of the chalcogen on the activity, selectivity and stability of the catalyst. Ruthenium surfaces with moderate content of selenium are calculated active for the oxygen reduction reaction, and insensitive to methanol. A significant upper limit for the activity of transition metal chalcogenides is estimated.

Oxygen vacancy induced two-dimensional electron system in disordered-crystalline LaAlO{sub 3}/KTaO{sub 3} heterostructures

Energy Technology Data Exchange (ETDEWEB)

Zapf, Michael; Gabel, Judith; Scheiderer, Philipp; Dudy, Lenart; Sing, Michael; Claessen, Ralph [Physikalisches Institut and Roentgen Center for Complex Material Systems (RCCM), Universitaet Wuerzburg (Germany); Schlueter, Christoph; Lee, Tien-Lin [Diamond Light Source Ltd., Didcot (United Kingdom)

2016-07-01

Two-dimensional electron systems (2DESs) in oxide heterostructures based on SrTiO{sub 3} are considered to be a promising platform for future microelectronic technology. A variety of interesting properties such as ferromagnetism, resistive switching and superconductivity are linked to interfacial n-doping involving oxygen vacancies. The introduction of a high Z-cation with large spin-orbit coupling like Ta offers an exciting new parameter. We report on a new oxygen vacancy induced 2DES located at the interface of disordered LaAlO{sub 3} and crystalline KTaO{sub 3}, which exhibits remarkably high electron mobilities and charge carrier concentrations. The number of charge carriers can be readily manipulated by the film thickness and irradiation with intense X-rays. Our synchrotron-based hard X-ray photoemission experiments provide a direct probe of the Ta 5d charge carriers at the buried interface to obtain information on the charge carrier density, its depth distribution, and the band structure.

Quantifying the emissions reduction effectiveness and costs of oxygenated gasoline

International Nuclear Information System (INIS)

Lyons, C.E.

1993-01-01

During the fall, winter, and spring of 1991-1992, a measurement program was conducted in Denver, Colorado to quantify the technical and economic effectiveness of oxygenated gasoline in reducing automobile carbon monoxide (CO) emissions. Emissions from 80,000 vehicles under a variety of operating conditions were measured before, during, and after the seasonal introduction of oxygenated gasoline into the region. Gasoline samples were taken from several hundred vehicles to confirm the actual oxygen content of the fuel in use. Vehicle operating conditions, such as cold starts and warm operations, and ambient conditions were characterized. The variations in emissions attributable to fuel type and to operating conditions were then quantified. This paper describes the measurement program and its results. The 1991-1992 Colorado oxygenated gasoline program contributed to a reduction in carbon monoxide (CO) emissions from gasoline-powered vehicles. The measurement program demonstrated that most of the reduction is concentrated in a small percentage of the vehicles that use oxygenated gasoline. The remainder experience little or not reduction in emissions. The oxygenated gasoline program outlays are approximately $25 to $30 million per year in Colorado. These are directly measurable costs, incurred through increased government expenditures, higher costs to private industry, and losses in fuel economy. The measurement program determined the total costs of oxygenated gasoline as an air pollution control strategy for the region. Costs measured included government administration and enforcement, industry production and distribution, and consumer and other user costs. This paper describes the ability of the oxygenated gasoline program to reduce pollution; the overall cost of the program to government, industry, and consumers; and the effectiveness of the program in reducing pollution compared to its costs

Manganese dioxide-supported silver bismuthate as an efficient electrocatalyst for oxygen reduction reaction in zinc-oxygen batteries

International Nuclear Information System (INIS)

Sun, Yanzhi; Yang, Meng; Pan, Junqing; Wang, Pingyuan; Li, Wei; Wan, Pingyu

2016-01-01

In this paper, we present a new efficient composite electrocatalyst, manganese dioxide-supported silver bismuthate (Ag 4 Bi 2 O 5 /MnO 2 ), for oxygen reduction reaction (ORR) in alkaline media. The new electrocatalyst was characterized with scanning electron microscope (SEM), powder X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). Electrochemical measurements indicate that the Ag 4 Bi 2 O 5 /MnO 2 composite is a very efficient electrocatalyst for ORR in alkaline media. The physical and electrochemical characterization results suggest that the high activity is ascribed to the support effects from MnO 2 and the synergetic effects among Ag 4 Bi 2 O 5 and MnO 2 . The analysis of rotating disk electrode (RDE) results shows that the ORR occurs via a four-electron pathway on the surface of the Ag 4 Bi 2 O 5 /MnO 2 electrocatalyst. This electrocatalyst was further tested in a designed zinc–oxygen (Zn–O 2 ) battery. This battery can offer a discharge time of 225 h at 120 mA cm −2 , increasing by more than 492% as compared with pure MnO 2 electrocatalyst. It demonstrates that this inexpensive Ag 4 Bi 2 O 5 /MnO 2 electrocatalyst is a viable alternative to platinum electrocatalyst for energy conversion devices.

Synthesis of flower-like gold nanoparticles and their electrocatalytic activity towards the oxidation of methanol and the reduction of oxygen.

Science.gov (United States)

Jena, Bikash Kumar; Raj, C Retna

2007-03-27

This article describes the synthesis of branched flower-like gold (Au) nanocrystals and their electrocatalytic activity toward the oxidation of methanol and the reduction of oxygen. Gold nanoflowers (GNFs) were obtained by a one-pot synthesis using N-2-hydroxyethylpiperazine-N-2-ethanesulphonic acid (HEPES) as a reducing/stabilizing agent. The GNFs have been characterized by UV-visible spectroscopy, transmission electron microscopy (TEM), X-ray diffraction (XRD), and electrochemical measurements. The UV-visible spectra show two bands corresponding to the transverse and longitudinal surface plasmon (SP) absorption at 532 and 720 nm, respectively, for the colloidal GNFs. The GNFs were self-assembled on a sol-gel-derived silicate network, which was preassembled on a polycrystalline Au electrode and used for electrocatalytic applications. The GNFs retain their morphology on the silicate network; the UV-visible diffuse reflectance spectra (DRS) of GNFs on the silicate network show longitudinal and transverse bands as in the case of colloidal GNFs. The GNFs show excellent electrocatalytic activity toward the oxidation of methanol and the reduction of oxygen. Oxidation of methanol in alkaline solution was observed at approximately 0.245 V, which is much less positive than that on an unmodified polycrystalline gold electrode. Reduction of oxygen to H2O2 and the further reduction of H2O2 to water in neutral pH were observed at less negative potentials on the GNFs electrode. The electrocatalytic activity of GNFs is significantly higher than that of the spherically shaped citrate-stabilized Au nanoparticles (SGNs).

Unifying the 2e^– and 4e^– Reduction of Oxygen on Metal Surfaces

DEFF Research Database (Denmark)

Viswanathan, Venkatasubramanian; Hansen, Heine Anton; Rossmeisl, Jan

2012-01-01

Understanding trends in selectivity is of paramount importance for multi-electron electrochemical reactions. The goal of this work is to address the issue of 2e– versus 4e– reduction of oxygen on metal surfaces. Using a detailed thermodynamic analysis based on density functional theory calculatio...

Beyond the top of the volcano? A unified approach to electrocatalytic oxygen reduction and oxygen evolution

Czech Academy of Sciences Publication Activity Database

Busch, M.; Halck, N. B.; Kramm, U. I.; Siehrostami, S.; Krtil, Petr; Rossmeisl, J.

2016-01-01

Roč. 29, NOV 2016 (2016), s. 126-135 ISSN 2211-2855 Institutional support: RVO:61388955 Keywords : hydrogen evolution * catalytic-activity * Electrocatalysis * Oxygen reduction * Oxygen evolution * Volcano * Density functional theory Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 12.343, year: 2016

Iron (II) tetrakis(diaquaplatinum) octacarboxyphthalocyanine supported on multi-walled carbon nanotubes as effective electrocatalyst for oxygen reduction reaction in alkaline medium

CSIR Research Space (South Africa)

Mamuru, SA

2010-11-01

Full Text Available Oxygen reduction reaction (ORR) in alkaline medium at iron (II) tetrakis (diaquaplatinum) octacarboxyphthalocyanine (PtFeOCPc) catalyst supported on multi-walled carbon nanotubes (MWCNTs) has been described. The ORR followed the direct 4-electron...

Stable silver nanoclusters electrochemically deposited on nitrogen-doped graphene as efficient electrocatalyst for oxygen reduction reaction

Science.gov (United States)

Jin, Shi; Chen, Man; Dong, Haifeng; He, Bingyu; Lu, Huiting; Su, Lei; Dai, Wenhao; Zhang, Qiaochu; Zhang, Xueji

2015-01-01

Metal nanoclusters exhibit unusually high catalytic activity toward oxygen reduction reaction (ORR) due to their small size and unique electronic structures. However, controllable synthesis of stable metal nanoclusters is a challenge, and the durability of metal clusters suffers from the deficiency of dissolution, aggregation, and sintering during catalysis reactions. Herein, silver nanoclusters (AgNCs) (diameter , which is vital in high performance fuel cells, batteries and nanodevices.

Rational design of competitive electrocatalysts for the oxygen reduction reaction in hydrogen fuel cells

Science.gov (United States)

Stolbov, Sergey; Alcántara Ortigoza, Marisol

2012-02-01

The large-scale application of one of the most promising clean and renewable sources of energy, hydrogen fuel cells, still awaits efficient and cost-effective electrocatalysts for the oxygen reduction reaction (ORR) occurring on the cathode. We demonstrate that truly rational design renders electrocatalysts possessing both qualities. By unifying the knowledge on surface morphology, composition, electronic structure and reactivity, we solve that sandwich-like structures are an excellent choice for optimization. Their constituting species couple synergistically yielding reaction-environment stability, cost-effectiveness and tunable reactivity. This cooperative-action concept enabled us to predict two advantageous ORR electrocatalysts. Density functional theory calculations of the reaction free-energy diagrams confirm that these materials are more active toward ORR than the so far best Pt-based catalysts. Our designing concept advances also a general approach for engineering materials in heterogeneous catalysis.

Steady state oxygen reduction and cyclic voltammetry

DEFF Research Database (Denmark)

Rossmeisl, Jan; Karlberg, Gustav; Jaramillo, Thomas

2008-01-01

The catalytic activity of Pt and Pt3Ni for the oxygen reduction reaction is investigated by applying a Sabatier model based on density functional calculations. We investigate the role of adsorbed OH on the activity, by comparing cyclic voltammetry obtained from theory with previously published ex...

Hydrogen peroxide reduction in the oxygen vacancies of ZnO nanotubes

International Nuclear Information System (INIS)

Peyghan, Ali Ahmadi; Laeen, Shima Parizad; Aslanzadeh, Saeed Amir; Moradi, Morteza

2014-01-01

The adsorption of a H 2 O 2 molecule on the pristine and O-vacancy defected ZnO nanotubes was investigated by means of density functional calculations. It was found that the molecule prefers to attach to two zinc atoms of the tube from its two oxygen atoms with the adsorption energy of 254.1 kJ/mol. Attachment of the H 2 O 2 to the wall of the tube does not have any significant influence on its highest occupied molecular orbital/lowest unoccupied molecular orbital gap (E g ). The presence of oxygen vacancy defect causes a decrease in the E g of the tube and, as a consequence, may cause an increase in the conductivity of the tube. The zinc atoms of the defect are more reactive toward H 2 O 2 reduction to H 2 O than perfect ones with the adsorption energy of 617.4 kJ/mol. During the adsorption process, the H 2 O 2 was reoriented in such a way that its O atom has diffused into vacancy site, so that O-O and O-H bonds of the molecule were dissociated and an H 2 O is formed. Thus, we think that ZnO-NTs may be a candidate for electrochemical reduction and detection of H 2 O 2 . - Highlights: • H 2 O 2 adsorption on pristine and O-vacancy defected ZnO nanotubes was studied by DFT. • H 2 O 2 does not have any significant influence on the gap of the tube. • Presence of oxygen vacancy defect causes a decrease in the gap of the tube. • ZnO nanotubes may be a candidate for electrochemical reduction and detection of H 2 O 2

High performance platinum single atom electrocatalyst for oxygen reduction reaction

Science.gov (United States)

Liu, Jing; Jiao, Menggai; Lu, Lanlu; Barkholtz, Heather M.; Li, Yuping; Wang, Ying; Jiang, Luhua; Wu, Zhijian; Liu, Di-Jia; Zhuang, Lin; Ma, Chao; Zeng, Jie; Zhang, Bingsen; Su, Dangsheng; Song, Ping; Xing, Wei; Xu, Weilin; Wang, Ying; Jiang, Zheng; Sun, Gongquan

2017-07-01

For the large-scale sustainable implementation of polymer electrolyte membrane fuel cells in vehicles, high-performance electrocatalysts with low platinum consumption are desirable for use as cathode material during the oxygen reduction reaction in fuel cells. Here we report a carbon black-supported cost-effective, efficient and durable platinum single-atom electrocatalyst with carbon monoxide/methanol tolerance for the cathodic oxygen reduction reaction. The acidic single-cell with such a catalyst as cathode delivers high performance, with power density up to 680 mW cm-2 at 80 °C with a low platinum loading of 0.09 mgPt cm-2, corresponding to a platinum utilization of 0.13 gPt kW-1 in the fuel cell. Good fuel cell durability is also observed. Theoretical calculations reveal that the main effective sites on such platinum single-atom electrocatalysts are single-pyridinic-nitrogen-atom-anchored single-platinum-atom centres, which are tolerant to carbon monoxide/methanol, but highly active for the oxygen reduction reaction.

The impact of electrochemical reduction potentials on the electrocatalytic activity of graphene oxide toward the oxygen reduction reaction in an alkaline medium

International Nuclear Information System (INIS)

Toh, Shaw Yong; Loh, Kee Shyuan; Kamarudin, Siti Kartom; Daud, Wan Ramli Wan

2016-01-01

We report the synthesis of graphene via the electrochemical reduction of graphene oxide (GO). In this study, GO nanosheets from aqueous dispersion were pre-assembled on a glassy carbon (GC) electrode and then electrochemically reduced in 1 M KOH under various constant reduction potentials in the range of −0.6 V to −1.5 V (vs. Ag/AgCl). X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy analyses revealed that the graphitic structure was substantially restored in the resulting electrochemically reduced graphene oxide (ERGO). The ERGO electrodes exhibited significantly enhanced catalytic activity toward the oxygen reduction reaction (ORR) in an alkaline medium compared with the initial GO electrode. Of the ERGO electrodes produced at various cathodic potentials, the ERGO-1.2 V electrode, which was produced at a reduction potential of −1.2 V, demonstrated the best catalytic activity toward the ORR in an alkaline medium. The ORR on GO and ERGO electrodes was shown to proceed via a two-electron mechanism at low overpotentials. The agreement between the spectroscopy results and electrochemical measurements provide strong evidence that the enhanced ORR catalytic activity is mainly attributed to the restoration of GO’s graphitic structure. Furthermore, the ERGO-1.2 V electrode showed excellent tolerance to the methanol poisoning effect compared with a Pt/C catalyst electrode.

Bio-inspired carbon electro-catalysis for the oxygen reduction reaction

OpenAIRE

Preuss, Kathrin; Kannuchamy, Vasanth Kumar; Marinovic, Adam; Isaacs, Mark; Wilson, Karen; Abrahams, Isaac; Titirici, Maria-Magdalena

2016-01-01

We report the synthesis, characterisation and catalytic performance of two nature-inspired biomass-derived electro-catalysts for the oxygen reduction reaction in fuel cells. The catalysts were prepared via pyrolysis of a real food waste (lobster shells) or by mimicking the composition of lobster shells using chitin and CaCO3 particles followed by acid washing. The simplified model of artificial lobster was prepared for better reproducibility. The calcium carbonate in both samples acts as a po...

Influence of Micropore and Mesoporous in Activated Carbon Air-cathode Catalysts on Oxygen Reduction Reaction in Microbial Fuel Cells

International Nuclear Information System (INIS)

Liu, Yi; Li, Kexun; Ge, Baochao; Pu, Liangtao; Liu, Ziqi

2016-01-01

In this study, carbon samples with different micropore and mesoporous structures are prepared as air-cathode catalyst layer to explore the role of pore structure on oxygen reduction reaction. The results of linear sweep voltammetry and power density show that the commercially-produced activated carbon (CAC) has the best electrochemical performance, and carbon samples with only micropore or mesoporous show lower performance than CAC. Nitrogen adsorption-desorption isotherms analysis confirm that CAC has highest surface area (1616 m 2 g −1 ) and a certain amount of micropore and mesoporous. According to Tafel plot and rotating disk electrode, CAC behaves the highest kinetic activity and electron transfer number, leading to the improvement of oxygen reduction reaction. The air permeability test proves that mesoporous structure enhance oxygen permeation. Carbon materials are also analyzed by In situ Fourier Transform Infrared Spectroscopy and H 2 temperature programmed reduction, which indicate that micropore provide active sites for catalysis. In a word, micropore and mesoporous together would improve the electrochemical performance of carbon materials.

Study of the oxygen reduction reaction on stainless steel materials in natural seawater. Influence of the bio-film on corrosion processes; Reaction de reduction de l'oxygene sur les aciers inoxydables en eau de mer naturelle. Influence du biofilm sur les processus de corrosion

Energy Technology Data Exchange (ETDEWEB)

Le Bozec, N

2000-01-15

Bio-film development on stainless steels immersed in natural seawater can have prejudicial consequences on the resistance of these materials to corrosion. The goal of the present study was to get more precise information on the corrosion processes, and especially on the oxygen reduction reaction. As the reaction is linked to the stainless steel surface state, the characterisation of the oxides films (composition, structure, thickness...) is essential to understand the mechanisms and the oxygen reduction kinetic. The first aim of the study has been to correlate the oxygen reduction processes with the characteristics of the oxides layer as a function of the alloy surface treatment (mechanical polishing, electrochemical passivation and pre-reduction, chemical treatment with some acids or with hydrogen peroxide). The second stage has consisted in following the evolution of the oxygen reduction processes and of the characteristics of the oxides layer with the aging of stainless steels in natural and artificial sea-waters. One major bio-film effect appears to be the production of hydrogen peroxide at a concentration level which induces modifications of the oxides layers and, consequently, of the evolution of the oxygen reduction kinetics as well as of the open circuit potential. Electrochemical techniques (voltammetric analysis at rotating disk and ring-disk electrodes, coulometry) combined with a surface analytical method by X-ray photoelectron spectroscopy have been used. The characterisation of the bio-film required the use of microscopy (scanning electronic microscopy, epi-fluorescence microscopy) and microbiological methods (cultures). The in-situ detection of hydrogen peroxide formed inside the bio-film has been performed with a micro-electrode and the results were confirmed with enzymatic methods. (author)

Study of the oxygen reduction reaction on stainless steel materials in natural seawater. Influence of the bio-film on corrosion processes; Reaction de reduction de l'oxygene sur les aciers inoxydables en eau de mer naturelle. Influence du biofilm sur les processus de corrosion

Energy Technology Data Exchange (ETDEWEB)

Le Bozec, N

2000-01-15

Bio-film development on stainless steels immersed in natural seawater can have prejudicial consequences on the resistance of these materials to corrosion. The goal of the present study was to get more precise information on the corrosion processes, and especially on the oxygen reduction reaction. As the reaction is linked to the stainless steel surface state, the characterisation of the oxides films (composition, structure, thickness...) is essential to understand the mechanisms and the oxygen reduction kinetic. The first aim of the study has been to correlate the oxygen reduction processes with the characteristics of the oxides layer as a function of the alloy surface treatment (mechanical polishing, electrochemical passivation and pre-reduction, chemical treatment with some acids or with hydrogen peroxide). The second stage has consisted in following the evolution of the oxygen reduction processes and of the characteristics of the oxides layer with the aging of stainless steels in natural and artificial sea-waters. One major bio-film effect appears to be the production of hydrogen peroxide at a concentration level which induces modifications of the oxides layers and, consequently, of the evolution of the oxygen reduction kinetics as well as of the open circuit potential. Electrochemical techniques (voltammetric analysis at rotating disk and ring-disk electrodes, coulometry) combined with a surface analytical method by X-ray photoelectron spectroscopy have been used. The characterisation of the bio-film required the use of microscopy (scanning electronic microscopy, epi-fluorescence microscopy) and microbiological methods (cultures). The in-situ detection of hydrogen peroxide formed inside the bio-film has been performed with a micro-electrode and the results were confirmed with enzymatic methods. (author)

Preparation of hafnium metal by calciothermic reduction of HfO2

International Nuclear Information System (INIS)

Sharma, I.G.; Vijay, P.L.; Sehra, J.C.; Sundaram, C.V.

1975-01-01

Hafnium metal powder has been produced by the calciothermic reduction of hafnium oxide. The influence of various experimental parameters - such as amount of calcium in excess of stoichiometric requirement, temperature, and time of reduction - on the yield and purity of the metal has been studied. The metal powder obtained by reduction at 960 0 C (two hours) with a calcium excess of 70% analysed 600 ppm of oxygen and 147 ppm of nitrogen. A reduction efficiency of 96% has been achieved under these conditions. The refining of the powder by electron beam melting, fused salt electrolysis, and iodide process has been studied. The oxygen content in the metal could be brought down from 6900 to 148 ppm by electron beam melt-refining. (author)

Oxygen Reduction on Platinum

DEFF Research Database (Denmark)

Nesselberger, Markus

. The influence of the ion adsorption strength, which is observed in the “particle size studies” on the oxygen reduction rate on Pt/C catalysts, is further investigated under similar reaction conditions by infrared spectroscopy. The designed in situ electrochemical ATR-FTIR setup features a high level...... of instrument automation and online data treatment, and provides welldefined mass transport conditions enabling kinetic measurements. A modified electrochemical / spectroscopic interface is presented allowing the exclusive investigation of the Pt/C catalyst layer. Three types of potential dependent adsorption...... adsorption on Pt does not block the ORR directly. Instead, the onset of oxide formation with the concomitant conversion of the anion adsorbate layer is the decisive blocking mechanism....

Hydrodynamic voltammetric studies of the oxygen reduction at gold nanoparticles-electrodeposited gold electrodes

International Nuclear Information System (INIS)

El-Deab, Mohamed S.; Ohsaka, Takeo

2002-01-01

The electrocatalytic reduction of oxygen at Au nanoparticles-electrodeposited Au electrodes has been studied using rotating disk electrode (RDE) voltammetry in 0.5 M H 2 SO 4 . Upon analyzing and comparison of the limiting currents data obtained at various rotation speeds of this RDE with those obtained at the bulk Au electrode, an effective value of the number of electrons, n, involved in the electrochemical reduction of O 2 was estimated to be ca. 4 for the former electrode and ca. 3 for the bulk Au electrode at the same potential of -350 mV versus Ag/AgCl/KCl(sat.). This indicates the higher possibility of further reduction and decomposition of H 2 O 2 at Au nanoparticles-electrodeposited Au electrode in this acidic medium. The reductive desorption of the self-assembled monolayer of cysteine, which was formed on the Au nanoparticles-electrodeposited Au electrode, was used to monitor the change of the specific activity of the bulk Au electrode upon the electrodeposition of the Au nanoparticles

Oxygen isotopic fractionation during bacterial sulfate reduction

Science.gov (United States)

Balci, N.; Turchyn, A. V.; Lyons, T.; Bruchert, V.; Schrag, D. P.; Wall, J.

2006-12-01

Sulfur isotope fractionation during bacterial sulfate reduction (BSR) is understood to depend on a variety of environmental parameters, such as sulfate concentration, temperature, cell specific sulfate reduction rates, and the carbon substrate. What controls oxygen isotope fractionation during BSR is less well understood. Some studies have suggested that carbon substrate is important, whereas others concluded that there is a stoichiometric relationship between the fractionations of sulfur and oxygen during BSR. Studies of oxygen fractionation are complicated by isotopic equilibration between sulfur intermediates, particularly sulfite, and water. This process can modify the isotopic composition of the extracellular sulfate pool (δ18OSO4 ). Given this, the challenge is to distinguish between this isotopic equilibration and fractionations linked to the kinetic effects of the intercellular enzymes and the incorporation of sulfate into the bacterial cell. The δ18OSO4 , in concert with the sulfur isotope composition of sulfate (δ34SSO4), could be a powerful tool for understanding the pathways and environmental controls of BSR in natural systems. We will present δ18OSO4 data measured from batch culture growth of 14 different species of sulfate reducing bacteria for which sulfur isotope data were previously published. A general observation is that δ18OSO4 shows little isotopic change (kinetic effect during BSR and/or equilibration between sulfur intermediates and the isotopically light water (~-5‰) of the growth medium. Our present batch culture data do not allow us to convincingly isolate the magnitude and the controlling parameters of the kinetic isotope effect for oxygen. However, ongoing growth of mutant bacteria missing enzymes critical in the different steps of BSR may assist in this mission.

Mechanistic model of the oxygen reduction catalyzed by a metal-free porphyrin in one- and two-phase liquid systems

Czech Academy of Sciences Publication Activity Database

Trojánek, Antonín; Langmaier, Jan; Záliš, Stanislav; Samec, Zdeněk

2013-01-01

Roč. 110, NOV 2013 (2013), s. 816-821 ISSN 0013-4686 R&D Projects: GA ČR GAP208/11/0697 Institutional support: RVO:61388955 Keywords : oxygen reduction * metal -free porphyrin * catalysis Subject RIV: CG - Electrochemistry Impact factor: 4.086, year: 2013

Solid Oxide Fuel Cell Cathodes. Unraveling the Relationship Between Structure, Surface Chemistry and Oxygen Reduction

Energy Technology Data Exchange (ETDEWEB)

Gopalan, Srikanth [Boston Univ., MA (United States)

2013-03-31

In this work we have considered oxygen reduction reaction on LSM and LSCF cathode materials. In particular we have used various spectroscopic techniques to explore the surface composition, transition metal oxidation state, and the bonding environment of oxygen to understand the changes that occur to the surface during the oxygen reduction process. In a parallel study we have employed patterned cathodes of both LSM and LSCF cathodes to extract transport and kinetic parameters associated with the oxygen reduction process.

Anodically-grown TiO_2 nanotubes: Effect of the crystallization on the catalytic activity toward the oxygen reduction reaction

International Nuclear Information System (INIS)

Sacco, Adriano; Garino, Nadia; Lamberti, Andrea; Pirri, Candido Fabrizio; Quaglio, Marzia

2017-01-01

Highlights: • Anodically-grown TiO_2 nanotubes as catalysts for the oxygen reduction reaction. • Amorphous NTs compared to thermal- and vapor-treated crystalline nanostructures. • The selection of the crystallization conditions leads to performance similar to Pt. - Abstract: In this work we investigated the behavior of TiO_2 nanotube (NT) arrays, grown by anodic oxidation of Ti foil, as catalysts for the oxygen reduction reaction (ORR) in alkaline water solution. In particular, as-grown amorphous NTs were compared to crystalline anatase nanostructures, obtained following two different procedures, namely thermal and vapor-induced crystallizations. The catalytic activity of these materials toward the ORR was evaluated by cyclic voltammetry measurements. ORR polarization curves, combined with the rotating disk technique, indicated a predominant four-electrons reduction path, especially for crystalline samples. The effect of the structural characteristics of the investigated materials on the catalytic activity was analyzed in details by electrochemical impedance spectroscopy. The catalytic performance of the crystalline NTs is only slightly lower with respect to the reference material for fuel cell applications, namely platinum, but is in line with other cost-effective catalysts recently proposed in the literature. However, if compared to the larger part of these low-cost catalysts, anodically-grown TiO_2 NTs are characterized by a synthesis route which is highly reproducible and easily up-scalable.

Electrocatalysts of platinum, cobalt and nickel prepared by mechanical alloying for the oxygen reduction reaction in H2SO4 0.5M

International Nuclear Information System (INIS)

Garcia C, M.A.; Fernandez V, S.M.; Vargas G, J.R.

2007-01-01

Metallic powders of Pt, Co and Nickel were processed by mechanical alloyed and electrocatalysts were synthesized for the oxygen reduction reaction, applicable in fuel cells. The structural and morphological characterization was carried out using X-ray Diffraction, scanning electron microscopy and transmission electron microscopy. It was found that the alloyed powders formed agglomerates that consist of crystalline particles of nano metric size. Its were obtained polarization curves by the Electrode of Rotational Disk technique in a solution of H 2 SO 4 0.5 M, used as electrolyte, to evaluate the electrocatalytic activity of mechanically alloyed powders. Tafel graphics were built to determine the kinetic parameters of each electro catalyst. The PtCoNi alloy exhibited the biggest electrocatalytic activity, with the smallest over potential for the oxygen reduction reaction. (Author)

Trends in oxygen reduction and methanol activation on transition metal chalcogenides

DEFF Research Database (Denmark)

Tritsaris, Georgios; Nørskov, Jens Kehlet; Rossmeisl, Jan

2011-01-01

We use density functional theory calculations to study the oxygen reduction reaction and methanol activation on selenium and sulfur-containing transition metal surfaces. With ruthenium selenium as a starting point, we study the effect of the chalcogen on the activity, selectivity and stability...... of the catalyst. Ruthenium surfaces with moderate content of selenium are calculated active for the oxygen reduction reaction, and insensitive to methanol. A significant upper limit for the activity of transition metal chalcogenides is estimated....

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

Science.gov (United States)

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.

Kinetics of oxygen reduction reaction at tin-adatoms-modified gold electrodes in acidic media

International Nuclear Information System (INIS)

Miah, Md. Rezwan; Ohsaka, Takeo

2009-01-01

In the present report, oxygen reduction reaction (ORR) at polycrystalline gold (Au (poly)) electrode in situ modified by the underpotential deposition (upd) of Sn-adatoms is addressed. The ORR was investigated at the Sn-adatoms-modified Au (poly) electrode by the hydrodynamic voltammetric technique with a view to evaluating the various related kinetic parameters. The results demonstrated that the underpotential deposited Sn-adatoms on the Au (poly) electrode substantially promoted the activity of the electrode towards an exclusive one-step four-electron ORR forming H 2 O as the final product.

Kinetics of oxygen reduction reaction at tin-adatoms-modified gold electrodes in acidic media

Energy Technology Data Exchange (ETDEWEB)

Miah, Md. Rezwan [Department of Electronic Chemistry, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, Mail Box G1-5, 4259 Nagatsuta, Midori-ku, Yokohama 226-8502 (Japan)], E-mail: mrmche@yahoo.com; Ohsaka, Takeo [Department of Electronic Chemistry, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, Mail Box G1-5, 4259 Nagatsuta, Midori-ku, Yokohama 226-8502 (Japan)], E-mail: ohsaka@echem.titech.ac.jp

2009-10-01

In the present report, oxygen reduction reaction (ORR) at polycrystalline gold (Au (poly)) electrode in situ modified by the underpotential deposition (upd) of Sn-adatoms is addressed. The ORR was investigated at the Sn-adatoms-modified Au (poly) electrode by the hydrodynamic voltammetric technique with a view to evaluating the various related kinetic parameters. The results demonstrated that the underpotential deposited Sn-adatoms on the Au (poly) electrode substantially promoted the activity of the electrode towards an exclusive one-step four-electron ORR forming H{sub 2}O as the final product.

Oxygen reduction kinetics on graphite cathodes in sediment microbial fuel cells.

Science.gov (United States)

Renslow, Ryan; Donovan, Conrad; Shim, Matthew; Babauta, Jerome; Nannapaneni, Srilekha; Schenk, James; Beyenal, Haluk

2011-12-28

Sediment microbial fuel cells (SMFCs) have been used as renewable power sources for sensors in fresh and ocean waters. Organic compounds at the anode drive anodic reactions, while oxygen drives cathodic reactions. An understanding of oxygen reduction kinetics and the factors that determine graphite cathode performance is needed to predict cathodic current and potential losses, and eventually to estimate the power production of SMFCs. Our goals were to (1) experimentally quantify the dependence of oxygen reduction kinetics on temperature, electrode potential, and dissolved oxygen concentration for the graphite cathodes of SMFCs and (2) develop a mechanistic model. To accomplish this, we monitored current on polarized cathodes in river and ocean SMFCs. We found that (1) after oxygen reduction is initiated, the current density is linearly dependent on polarization potential for both SMFC types; (2) current density magnitude increases linearly with temperature in river SMFCs but remains constant with temperature in ocean SMFCs; (3) the standard heterogeneous rate constant controls the current density temperature dependence; (4) river and ocean SMFC graphite cathodes have large potential losses, estimated by the model to be 470 mV and 614 mV, respectively; and (5) the electrochemical potential available at the cathode is the primary factor controlling reduction kinetic rates. The mechanistic model based on thermodynamic and electrochemical principles successfully fit and predicted the data. The data, experimental system, and model can be used in future studies to guide SMFC design and deployment, assess SMFC current production, test cathode material performance, and predict cathode contamination.

Electrocatalytic reduction of oxygen at vapor phase polymerized ...

African Journals Online (AJOL)

We successfully polymerized poly(3,4-ethylenedioxidethiophene) by vapor phase polymerization technique on rotating glassy carbon disk electrode. The catalytic activity of this electrode towards oxygen reduction reaction was investigated and showed remarkable activity. Rotating disk voltammetry was used to study the ...

Nanostructured palladium tailored via carbonyl chemical route towards oxygen reduction reaction

International Nuclear Information System (INIS)

Luo, Y.; Mora-Hernández, J.M.; Estudillo-Wong, L.A.; Arce-Estrada, E.M.; Alonso-Vante, N.

2015-01-01

Graphical Abstract: Mass-depending morphologies of nanostructured Palladium obtained via the carbonyl chemical route. Display Omitted -- Highlights: •Mass-depending morphology was observed in nanostructured palladium supported on carbon prepared by the carbonyl chemical route. •The Morphological effect of carbon supported Pd was investigated towards ORR. -- Abstract: Carbon supported palladium nanostructures were synthesized via the carbonyl chemical route. Compared with nanostructured platinum, prepared via carbonyl chemical route, Pd nanomaterials showed mass-loading morphology, whereas particle size and morphology of Pt nanostructures was constant. The oxygen reduction reaction (ORR) on nanostructured Pd, with different morphology in both acid and alkaline medium was investigated. A relationship, based on X-ray diffraction structural analysis pattern, transmission electron microscope, with the Pd morphological effect on ORR activity was identified

Electron attachment to molecules and clusters of atmospheric relevance: oxygen and ozone

International Nuclear Information System (INIS)

Matejcik, S.; Cicman, P.; Skalny, J.; Kiendler, A.; Stampfli, P.; Maerk, T.D.; Illenberger, E.; Chu, Y.; Stamatovic, A.

1996-01-01

Highly monochromatized electrons are used in a crossed beams experiment to investigate electron attachment to oxygen clusters (O 2 )-n at electron energies from approximately zero eV up to 2 eV. At energies close to zero the attachment cross section for the reaction (O 2 ) n + e → O 2 - varies inversely with the electron energy, indicative of s-wave electron capture to (O 2 ) n . Peaks in the attachment cross section present at higher energies can be ascribed to vibrational levels of the oxygen anion. The vibrational spacings observed can be quantitatively accounted for. In addition electron attachment to ozone and mixed oxygen/ozone clusters has been studied in the energy range up to 4 eV. Absolute attachment cross sections for both fragment ions anions, O - and O 2 - , from ozone could be deduced. Moreover, despite the initially large excess of oxygen molecules in the neutral oxygen/ozone clusters the dominant attachment products are un-dissociated cluster ions (O 3 ) m - including the O 3 - monomer while oxygen cluster ions (O 2 ) n appear with comparatively low intensity. (authors)

Study of the oxygen reduction reaction on stainless steel materials in natural seawater. Influence of the bio-film on corrosion processes

International Nuclear Information System (INIS)

Le Bozec, N.

2000-01-01

Bio-film development on stainless steels immersed in natural seawater can have prejudicial consequences on the resistance of these materials to corrosion. The goal of the present study was to get more precise information on the corrosion processes, and especially on the oxygen reduction reaction. As the reaction is linked to the stainless steel surface state, the characterisation of the oxides films (composition, structure, thickness...) is essential to understand the mechanisms and the oxygen reduction kinetic. The first aim of the study has been to correlate the oxygen reduction processes with the characteristics of the oxides layer as a function of the alloy surface treatment (mechanical polishing, electrochemical passivation and pre-reduction, chemical treatment with some acids or with hydrogen peroxide). The second stage has consisted in following the evolution of the oxygen reduction processes and of the characteristics of the oxides layer with the aging of stainless steels in natural and artificial sea-waters. One major bio-film effect appears to be the production of hydrogen peroxide at a concentration level which induces modifications of the oxides layers and, consequently, of the evolution of the oxygen reduction kinetics as well as of the open circuit potential. Electrochemical techniques (voltammetric analysis at rotating disk and ring-disk electrodes, coulometry) combined with a surface analytical method by X-ray photoelectron spectroscopy have been used. The characterisation of the bio-film required the use of microscopy (scanning electronic microscopy, epi-fluorescence microscopy) and microbiological methods (cultures). The in-situ detection of hydrogen peroxide formed inside the bio-film has been performed with a micro-electrode and the results were confirmed with enzymatic methods. (author)

2D ultrathin core-shell Pd@Ptmonolayer nanosheets: defect-mediated thin film growth and enhanced oxygen reduction performance

Science.gov (United States)

Wang, Wenxin; Zhao, Yunfeng; Ding, Yi

2015-07-01

An operational strategy for the synthesis of atomically smooth Pt skin by a defect-mediated thin film growth method is reported. Extended ultrathin core-shell structured d@Ptmonolayer nanosheets (thickness below 5 nm) exhibit nearly seven-fold enhancement in mass-activity and surprisingly good durability toward oxygen reduction reaction as compared with the commercial Pt/C catalyst.An operational strategy for the synthesis of atomically smooth Pt skin by a defect-mediated thin film growth method is reported. Extended ultrathin core-shell structured d@Ptmonolayer nanosheets (thickness below 5 nm) exhibit nearly seven-fold enhancement in mass-activity and surprisingly good durability toward oxygen reduction reaction as compared with the commercial Pt/C catalyst. Electronic supplementary information (ESI) available: Sample preparation, physical and electrochemical characterization, Fig. S1 to S11. See DOI: 10.1039/c5nr02748a

A bio-inspired N-doped porous carbon electrocatalyst with hierarchical superstructure for efficient oxygen reduction reaction

Science.gov (United States)

Miao, Yue-E.; Yan, Jiajie; Ouyang, Yue; Lu, Hengyi; Lai, Feili; Wu, Yue; Liu, Tianxi

2018-06-01

The bio-inspired hierarchical "grape cluster" superstructure provides an effective integration of one-dimensional carbon nanofibers (CNF) with isolated carbonaceous nanoparticles into three-dimensional (3D) conductive frameworks for efficient electron and mass transfer. Herein, a 3D N-doped porous carbon electrocatalyst consisting of carbon nanofibers with grape-like N-doped hollow carbon particles (CNF@NC) has been prepared through a simple electrospinning strategy combined with in-situ growth and carbonization processes. Such a bio-inspired hierarchically organized conductive network largely facilitates both the mass diffusion and electron transfer during the oxygen reduction reactions (ORR). Therefore, the metal-free CNF@NC catalyst demonstrates superior catalytic activity with an absolute four-electron transfer mechanism, strong methanol tolerance and good long-term stability towards ORR in alkaline media.

Quasi-two-dimensional electron gas at the epitaxial alumina/SrTiO{sub 3} interface: Control of oxygen vacancies

Energy Technology Data Exchange (ETDEWEB)

Kormondy, Kristy J.; Posadas, Agham B.; Demkov, Alexander A., E-mail: demkov@physics.utexas.edu [Department of Physics, University of Texas at Austin, Austin, Texas 78712 (United States); Ngo, Thong Q.; Ekerdt, John G. [Department of Chemical Engineering, University of Texas at Austin, Austin, Texas 78712 (United States); Lu, Sirong; Smith, David J.; McCartney, Martha R. [Department of Physics, Arizona State University, Tempe, Arizona 85287 (United States); Goble, Nicholas; Gao, Xuan P. A. [Department of Physics, Case Western Reserve University, Cleveland, Ohio 44106 (United States); Jordan-Sweet, Jean [IBM T.J. Watson Research Center, Yorktown Heights, New York 10598 (United States)

2015-03-07

In this paper, we report on the highly conductive layer formed at the crystalline γ-alumina/SrTiO{sub 3} interface, which is attributed to oxygen vacancies. We describe the structure of thin γ-alumina layers deposited by molecular beam epitaxy on SrTiO{sub 3} (001) at growth temperatures in the range of 400–800 °C, as determined by reflection-high-energy electron diffraction, x-ray diffraction, and high-resolution electron microscopy. In situ x-ray photoelectron spectroscopy was used to confirm the presence of the oxygen-deficient layer. Electrical characterization indicates sheet carrier densities of ∼10{sup 13 }cm{sup −2} at room temperature for the sample deposited at 700 °C, with a maximum electron Hall mobility of 3100 cm{sup 2}V{sup −1}s{sup −1} at 3.2 K and room temperature mobility of 22 cm{sup 2}V{sup −1}s{sup −1}. Annealing in oxygen is found to reduce the carrier density and turn a conductive sample into an insulator.

Electrochemical investigations of Co3Fe-RGO as a bifunctional catalyst for oxygen reduction and evolution reactions in alkaline media

Science.gov (United States)

Kumar, Surender; Kumar, Divyaratan; Kishore, Brij; Ranganatha, Sudhakar; Munichandraiah, Nookala; Venkataramanan, Natarajan S.

2017-10-01

Nanoparticles of Co3Fe alloy is prepared on reduced graphene oxide (RGO) sheets by modified polyol method. Synthesized alloy particles are characterized by various physicochemical techniques. TEM and SEM pictures showed homogeneously dispersed alloy nanoparticles on the RGO sheets. Electrochemistry of alloy nanoparticles is investigated in alkaline medium. The result shows that oxygen evaluation reaction (OER) activity of Co3Fe-RGO is higher than Pt-black particles. RDE studies in alkaline medium shows that oxygen reduction reaction (ORR) follow four electron pathway. It is suggest that Co3Fe-RGO is an efficient non-precious catalyst for oxygen (ORR/OER) reactions in alkaline electrolyte for PEMFC applications.

Synthesis and characterization of the WxRuySez from the electrochemical reduction of oxygen and their possible application as electrode in fuel cell

International Nuclear Information System (INIS)

Ramirez R, S.D.

1995-01-01

In this communication the synthesis of the W 0.03 RuSe 0.47 O 0.3 from the transition metal carbonyl compounds and the chalcogenide in m Xylene, the chemical characterization of the novel material was performed by neutron activation analysis (NAA), using the TRIGA Mark III Reactor from the Nuclear Center of Mexico. The oxygen present in the material was determined by Rutherford Backscattering Spectrometry (RBS). Also the RuSe 5.7 y WSe 2 were synthesized and characterized by NAA. The electro kinetic oxygen reduction behaviour of the W 0.03 RuSe 0.47 O 0.3 deposited in glassy carbon was investigated in aqueous H 2 SO 4 0.5M. The rotating disk electrode electrochemical technique was used for determining the kinetic parameters: The reaction was of first order which implied that the rate determining step is the transfer of one electron, the Tafel slope was 0.115 V/decade; the electron transfer coefficient found was of 0.5, and the activation energy in the oxygen reduction reaction was 0.47 eV. (Author)

Simple one-pot synthesis of platinum-palladium nanoflowers with enhanced catalytic activity and methanol-tolerance for oxygen reduction in acid media

International Nuclear Information System (INIS)

Zheng, Jie-Ning; He, Li-Li; Chen, Fang-Yi; Wang, Ai-Jun; Xue, Meng-Wei; Feng, Jiu-Ju

2014-01-01

Graphical abstract: PtPd nanoflowers were fabricated by one-pot solvothermal co-reduction method in oleylamine system, which exhibited the improved electrocatalytic activity and higher methanol tolerance for oxygen reduction, compared with commercial Pt and Pd black catalysts. - Highlights: • Bimetallic alloyed PtPd nanoflowers are prepared by a simple one-pot solvothermal co-reduction method. • PtPd nanoflowers display high catalytic performance for ORR dominated by a four-electron pathway. • PtPd nanoflowers show good methanol tolerance for ORR. - Abstract: In this work, bimetallic alloyed platinum-palladium (PtPd) nanoflowers are fabricated by one-pot solvothermal co-reduction of Pt (II) acetylacetonate and Pd (II) acetylacetonate in oleylamine system. The as-prepared nanostructures show the enhanced electrocatalytic activity for oxygen reduction reaction (ORR), dominated by a four-electron pathway based on the Koutecky-Levich plots, mainly owing to the inhibition of the formation of Pt–OH ad via the downshift of d-band center for Pt. Meanwhile, PtPd nanoflowers display good methanol tolerance and improved stability for ORR. The chronoamperometry test reveals that the current of PtPd nanoflowers remains 45.9% of its original value within 6000 s, much higher than those of commercial Pt (36.7%) and Pd (32.2%) black catalysts. Therefore, PtPd nanoflowers with unique interconnected structures can be used as a promising cathode catalyst in direct methanol fuel cells

Anodically-grown TiO{sub 2} nanotubes: Effect of the crystallization on the catalytic activity toward the oxygen reduction reaction

Energy Technology Data Exchange (ETDEWEB)

Sacco, Adriano, E-mail: adriano.sacco@iit.it [Center for Sustainable Future Technologies @Polito, Istituto Italiano di Tecnologia, Corso Trento 21, 10129, Torino (Italy); Garino, Nadia [Center for Sustainable Future Technologies @Polito, Istituto Italiano di Tecnologia, Corso Trento 21, 10129, Torino (Italy); Applied Science and Technology Department, Politecnico di Torino, Corso Duca degli Abruzzi 24, 10129, Torino (Italy); Lamberti, Andrea, E-mail: andrea.lamberti@polito.it [Center for Sustainable Future Technologies @Polito, Istituto Italiano di Tecnologia, Corso Trento 21, 10129, Torino (Italy); Applied Science and Technology Department, Politecnico di Torino, Corso Duca degli Abruzzi 24, 10129, Torino (Italy); Pirri, Candido Fabrizio [Center for Sustainable Future Technologies @Polito, Istituto Italiano di Tecnologia, Corso Trento 21, 10129, Torino (Italy); Applied Science and Technology Department, Politecnico di Torino, Corso Duca degli Abruzzi 24, 10129, Torino (Italy); Quaglio, Marzia [Center for Sustainable Future Technologies @Polito, Istituto Italiano di Tecnologia, Corso Trento 21, 10129, Torino (Italy)

2017-08-01

Highlights: • Anodically-grown TiO{sub 2} nanotubes as catalysts for the oxygen reduction reaction. • Amorphous NTs compared to thermal- and vapor-treated crystalline nanostructures. • The selection of the crystallization conditions leads to performance similar to Pt. - Abstract: In this work we investigated the behavior of TiO{sub 2} nanotube (NT) arrays, grown by anodic oxidation of Ti foil, as catalysts for the oxygen reduction reaction (ORR) in alkaline water solution. In particular, as-grown amorphous NTs were compared to crystalline anatase nanostructures, obtained following two different procedures, namely thermal and vapor-induced crystallizations. The catalytic activity of these materials toward the ORR was evaluated by cyclic voltammetry measurements. ORR polarization curves, combined with the rotating disk technique, indicated a predominant four-electrons reduction path, especially for crystalline samples. The effect of the structural characteristics of the investigated materials on the catalytic activity was analyzed in details by electrochemical impedance spectroscopy. The catalytic performance of the crystalline NTs is only slightly lower with respect to the reference material for fuel cell applications, namely platinum, but is in line with other cost-effective catalysts recently proposed in the literature. However, if compared to the larger part of these low-cost catalysts, anodically-grown TiO{sub 2} NTs are characterized by a synthesis route which is highly reproducible and easily up-scalable.

Chalcogenide metal centers for oxygen reduction reaction: Activity and tolerance

International Nuclear Information System (INIS)

Feng Yongjun; Gago, Aldo; Timperman, Laure; Alonso-Vante, Nicolas

2011-01-01

This mini-review summarizes materials design methods, oxygen reduction kinetics, tolerance to small organic molecules and fuel cell performance of chalcogenide metal catalysts, particularly, ruthenium (Ru x Se y ) and non-precious transition metals (M x X y : M = Co, Fe and Ni; X = Se and S). These non-platinum catalysts are potential alternatives to Pt-based catalysts because of their comparable catalytic activity (Ru x Se y ), low cost, high abundance and, in particular, a high tolerance to small organic molecules. Developing trends of synthesis methods, mechanism of oxygen reduction reaction and applications in direct alcohol fuel cells as well as the substrate effect are highlighted.

Electrochemically reduced graphene-oxide supported bimetallic nanoparticles highly efficient for oxygen reduction reaction with excellent methanol tolerance

Science.gov (United States)

Yasmin, Sabina; Cho, Sung; Jeon, Seungwon

2018-03-01

We report a simple and facile method for the fabrication of bimetallic nanoparticles on electrochemically reduced graphene oxide (ErGO) for electrocatalytic oxygen reduction reaction (ORR) in alkaline media. First, reduced graphene oxide supported palladium and manganese oxide nanoparticle (rGO/Pd-Mn2O3) catalyst was synthesized via a simple chemical method at room temperature; then, it was electrochemically reduced for oxidation reduction reaction (ORR) in alkaline media. The chemical composition and morphological properties of ErGO/Pd-Mn2O3 was characterized by X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM) and energy-dispersive X-ray spectroscopy (EDS). The TEM images reveals that, nano-sized Pd and Mn2O3 particles were disperse on the ErGO sheet without aggregation. The as-prepared ErGO/Pd-Mn2O3 was employed for ORR in alkaline media which shows higher ORR activity with more positive onset and half-wave potential, respectively. Remarkably, ErGO/Pd-Mn2O3 reduced oxygen via four-electron transfer pathway with negligible amount of intermediate peroxide species (HO2-). Furthermore, the higher stability and excellent methanol tolerance of the ErGO/Pd-Mn2O3 compared to commercial Pt/C (20 wt%) catalyst, indicating its suitability for fuel cells.

Enhanced catalytic four-electron dioxygen (O2) and two-electron hydrogen peroxide (H2O2) reduction with a copper(II) complex possessing a pendant ligand pivalamido group.

Science.gov (United States)

Kakuda, Saya; Peterson, Ryan L; Ohkubo, Kei; Karlin, Kenneth D; Fukuzumi, Shunichi

2013-05-01

A copper complex, [(PV-tmpa)Cu(II)](ClO4)2 (1) [PV-tmpa = bis(pyrid-2-ylmethyl){[6-(pivalamido)pyrid-2-yl]methyl}amine], acts as a more efficient catalyst for the four-electron reduction of O2 by decamethylferrocene (Fc*) in the presence of trifluoroacetic acid (CF3COOH) in acetone as compared with the corresponding copper complex without a pivalamido group, [(tmpa)Cu(II)](ClO4)2 (2) (tmpa = tris(2-pyridylmethyl)amine). The rate constant (k(obs)) of formation of decamethylferrocenium ion (Fc*(+)) in the catalytic four-electron reduction of O2 by Fc* in the presence of a large excess CF3COOH and O2 obeyed first-order kinetics. The k(obs) value was proportional to the concentration of catalyst 1 or 2, whereas the k(obs) value remained constant irrespective of the concentration of CF3COOH or O2. This indicates that electron transfer from Fc* to 1 or 2 is the rate-determining step in the catalytic cycle of the four-electron reduction of O2 by Fc* in the presence of CF3COOH. The second-order catalytic rate constant (k(cat)) for 1 is 4 times larger than the corresponding value determined for 2. With the pivalamido group in 1 compared to 2, the Cu(II)/Cu(I) potentials are -0.23 and -0.05 V vs SCE, respectively. However, during catalytic turnover, the CF3COO(-) anion present readily binds to 2 shifting the resulting complex's redox potential to -0.35 V. The pivalamido group in 1 is found to inhibit anion binding. The overall effect is to make 1 easier to reduce (relative to 2) during catalysis, accounting for the relative k(cat) values observed. 1 is also an excellent catalyst for the two-electron two-proton reduction of H2O2 to water and is also more efficient than is 2. For both complexes, reaction rates are greater than for the overall four-electron O2-reduction to water, an important asset in the design of catalysts for the latter.

Improvement of activated carbons as oxygen reduction catalysts in neutral solutions by ammonia gas treatment and their performance in microbial fuel cells

KAUST Repository

Watson, Valerie J.

2013-11-01

Commercially available activated carbon (AC) powders from different precursor materials (peat, coconut shell, coal, and hardwood) were treated with ammonia gas at 700 C to improve their performance as oxygen reduction catalysts in neutral pH solutions used in microbial fuel cells (MFCs). The ammonia treated ACs exhibited better catalytic performance in rotating ring-disk electrode tests than their untreated precursors, with the bituminous based AC most improved, with an onset potential of Eonset = 0.12 V (untreated, Eonset = 0.08 V) and n = 3.9 electrons transferred in oxygen reduction (untreated, n = 3.6), and the hardwood based AC (treated, E onset = 0.03 V, n = 3.3; untreated, Eonset = -0.04 V, n = 3.0). Ammonia treatment decreased oxygen content by 29-58%, increased nitrogen content to 1.8 atomic %, and increased the basicity of the bituminous, peat, and hardwood ACs. The treated coal based AC cathodes had higher maximum power densities in MFCs (2450 ± 40 mW m-2) than the other AC cathodes or a Pt/C cathode (2100 ± 1 mW m-2). These results show that reduced oxygen abundance and increased nitrogen functionalities on the AC surface can increase catalytic performance for oxygen reduction in neutral media. © 2013 Elsevier B.V. All rights reserved.

Fundamental Mechanistic Understanding of Electrocatalysis of Oxygen Reduction on Pt and Non-Pt Surfaces: Acid versus Alkaline Media

Directory of Open Access Journals (Sweden)

Nagappan Ramaswamy

2012-01-01

Full Text Available Complex electrochemical reactions such as Oxygen Reduction Reaction (ORR involving multi-electron transfer is an electrocatalytic inner-sphere electron transfer process that exhibit strong dependence on the nature of the electrode surface. This criterion (along with required stability in acidic electrolytes has largely limited ORR catalysts to the platinum-based surfaces. New evidence in alkaline media, discussed here, throws light on the involvement of surface-independent outer-sphere electron transfer component in the overall electrocatalytic process. This surface non-specificity gives rise to the possibility of using a wide-range of non-noble metal surfaces as electrode materials for ORR in alkaline media. However, this outer-sphere process predominantly leads only to peroxide intermediate as the final product. The importance of promoting the electrocatalytic inner-sphere electron transfer by facilitation of direct adsorption of molecular oxygen on the active site is emphasized by using pyrolyzed metal porphyrins as electrocatalysts. A comparison of ORR reaction mechanisms between acidic and alkaline conditions is elucidated here. The primary advantage of performing ORR in alkaline media is found to be the enhanced activation of the peroxide intermediate on the active site that enables the complete four-electron transfer. ORR reaction schemes involving both outer- and inner-sphere electron transfer mechanisms are proposed.

Electrocatalytic oxygen reduction and hydrogen evolution reactions on phthalocyanine modified electrodes: Electrochemical, in situ spectroelectrochemical, and in situ electrocolorimetric monitoring

Energy Technology Data Exchange (ETDEWEB)

Koca, Atif, E-mail: akoca@eng.marmara.edu.tr [Department of Chemical Engineering, Faculty of Engineering, Marmara University, Goeztepe, 34722 Istanbul (Turkey); Kalkan, Ayfer; Bayir, Zehra Altuntas [Department of Chemistry, Technical University of Istanbul, Maslak, 34469 Istanbul (Turkey)

2011-06-30

Highlights: > Electrochemical and in situ spectroelectrochemical characterizations of the metallophthalocyanines were performed. > The presence of O{sub 2} influences both oxygen reduction reaction and the electrochemical behaviors of the complexes. > Homogeneous catalytic ORR process occurs via an 'inner sphere' chemical catalysis process. > CoPc and CuPc coated on a glassy carbon electrode decrease the overpotential of the working electrode for H{sup +} reduction. - Abstract: This study describes electrochemical, in situ spectroelectrochemical, and in situ electrocolorimetric monitoring of the electrocatalytic reduction of molecular oxygen and hydronium ion on the phthalocyanine-modified electrodes. For this purpose, electrochemical and in situ spectroelectrochemical characterizations of the metallophthalocyanines (MPc) bearing tetrakis-[4-((4'-trifluoromethyl)phenoxy)phenoxy] groups were performed. While CoPc gives both metal-based and ring-based redox processes, H{sub 2}Pc, ZnPc and CuPc show only ring-based electron transfer processes. In situ electrocolorimetric method was applied to investigate the color of the electrogenerated anionic and cationic forms of the complexes. The presence of O{sub 2} in the electrolyte system influences both oxygen reduction reaction and the electrochemical and spectral behaviors of the complexes, which indicate electrocatalytic activity of the complexes for the oxygen reduction reaction. Perchloric acid titrations monitored by voltammetry represent possible electrocatalytic activities of the complexes for hydrogen evolution reaction. CoPc and CuPc coated on a glassy carbon electrode decrease the overpotential of the working electrode for H{sup +} reduction. The nature of the metal center changes the electrocatalytic activities for hydrogen evolution reaction in aqueous solution. Although CuPc has an inactive metal center, its electrocatalytic activity is recorded more than CoPc for H{sup +} reduction in aqueous

Kinetics of oxygen reduction reaction at electrochemically fabricated tin-palladium bimetallic electrocatalyst in acidic media

Energy Technology Data Exchange (ETDEWEB)

Miah, Md. Rezwan, E-mail: mrmche@yahoo.co [Department of Electronic Chemistry, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, Mail Box G1-5, 4259 Nagatsuta, Midori-ku, Yokohama 226-8502 (Japan); Masud, Jahangir [Department of Electronic Chemistry, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, Mail Box G1-5, 4259 Nagatsuta, Midori-ku, Yokohama 226-8502 (Japan); Ohsaka, Takeo, E-mail: ohsaka@echem.titech.ac.j [Department of Electronic Chemistry, Interdisciplinary Graduate School of Science and Engineering, Tokyo Institute of Technology, Mail Box G1-5, 4259 Nagatsuta, Midori-ku, Yokohama 226-8502 (Japan)

2010-12-15

In the present article, oxygen reduction reaction (ORR) at electrochemically fabricated tin-palladium (Sn-Pd) bimetallic electrocatalyst-modified glassy carbon (GC) electrode (Sn-Pd/GC electrode) in acidic media is addressed. Hydrodynamic voltammetric measurements were employed with a view to evaluating various kinetic parameters of the ORR at the Sn-Pd/GC electrode. The obtained results obviously demonstrated that the Sn-Pd bimetallic electrocatalyt substantially promoted the activity of the GC electrode and drove the ORR through an exclusive one-step four-electron pathway forming H{sub 2}O as the final product.

Kinetics of oxygen reduction reaction at electrochemically fabricated tin-palladium bimetallic electrocatalyst in acidic media

International Nuclear Information System (INIS)

Miah, Md. Rezwan; Masud, Jahangir; Ohsaka, Takeo

2010-01-01

In the present article, oxygen reduction reaction (ORR) at electrochemically fabricated tin-palladium (Sn-Pd) bimetallic electrocatalyst-modified glassy carbon (GC) electrode (Sn-Pd/GC electrode) in acidic media is addressed. Hydrodynamic voltammetric measurements were employed with a view to evaluating various kinetic parameters of the ORR at the Sn-Pd/GC electrode. The obtained results obviously demonstrated that the Sn-Pd bimetallic electrocatalyt substantially promoted the activity of the GC electrode and drove the ORR through an exclusive one-step four-electron pathway forming H 2 O as the final product.

Magneli phase Ti4O7 electrode for oxygen reduction reaction and its implication for zinc-air rechargeable batteries

International Nuclear Information System (INIS)

Li Xiaoxia; Zhu, Aaron Li; Qu Wei; Wang Haijiang; Hui, Rob; Zhang Lei; Zhang Jiujun

2010-01-01

In this paper, Magneli phase Ti 4 O 7 was successfully synthesized using a TiO 2 reduction method, and characterized using X-ray diffraction, Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS). The electrode coated with this Ti 4 O 7 material showed activities for both the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER). For the ORR, several parameters, including overall electron transfer number, kinetic constants, electron transfer coefficient, and percentage H 2 O 2 production, were obtained using the rotating ring-disk electrode (RRDE) technique and the Koutecky-Levich theory. The overall electron transfer number was found to be between 2.3 and 2.9 in 1, 4, and 6 M KOH electrolytes, suggesting that the ORR process on the Ti 4 O 7 electrode was a mixed process of 2- and 4-electron transfer pathways. Electrochemical durability tests, carried out in highly concentrated KOH electrolyte, confirmed that this Ti 4 O 7 is a stable electrode material, suggesting that it should be a feasible candidate for the air-cathodes of zinc-air batteries. To understand the stability of this material, Raman and XPS spectra were also collected for the Ti 4 O 7 samples before and after the stability tests. The results and analysis revealed that a thin layer of TiO 2 formed on the Ti 4 O 7 surface, which may have prevented further oxidation into the bulk of the Ti 4 O 7 electrode.

Investigation of a Pt-Fe/C catalyst for oxygen reduction reaction in direct ethanol fuel cells

International Nuclear Information System (INIS)

Castro Luna, A. M.; Bonesi, A.; Triaca, W. E.; Blasi, A. Di; Stassi, A.; Baglio, V.; Antonucci, V.; Arico, A. S.

2010-01-01

Three cathode catalysts (60% Pt/C, 30% Pt/C and 60% Pt-Fe/C), with a particle size of about 2-3 nm, were prepared to investigate the effect of ethanol cross-over on cathode surfaces. All samples were studied in terms of structure and morphology by using X-ray diffraction (XRD) and transmission electron microscopy (TEM) analyses. Their electrocatalytic behavior in terms of oxygen reduction reaction (ORR) was investigated and compared using a rotating disk electrode (RDE). The tolerance of cathode catalysts in the presence of ethanol was evaluated. The Pt-Fe/C catalyst showed both higher ORR activity and tolerance to ethanol cross-over than Pt/C catalysts. Moreover, the more promising catalysts were tested in 5 cm 2 DEFC single cells at 60 and 80 o C. An improvement in single cell performance was observed in the presence of the Pt-Fe catalyst, due to an enhancement in the oxygen reduction kinetics. The maximum power density was 53 mW cm -2 at 2 bar rel. cathode pressure and 80 o C.

Reduction in OER with LET: evidence supporting the ''oxygen-in-the-track'' hypothesis

International Nuclear Information System (INIS)

Bryant, P.E.

1976-01-01

To account for the reduction in OER with increasing LET which is observed for a wide variety of cell systems. Neary (1965) invoked the hypothesis that molecular oxygen is generated within the particle tracks of the more densely ionizing radiations. With the proviso that the product generated may be a species other than oxygen, but with similar sensitizing properties, produced by different qualities of radiation in two different organisms: the alga Chlamydomonas reinhardii and the bacterium Shigella flexneri were calculated. These effective concentrations should be the same for any given quality if the formation of the product is a function only of physico-chemical events occurring within the tracks of particles, and is independent of the biological material in which energy deposition is taking place. A prerequisite for the calculation of effective amounts of oxygen in tracks of ionizing particles is a knowledge of how radiosentivity varies with oxygen concentration at low LET

One-electron reduction of anthraquinone sulphonates: a pulse radiolysis study

International Nuclear Information System (INIS)

Pal, H.; Palit, D.K.; Mukherjee, T.; Mittal, J.P.

1991-01-01

Semiquinone free radicals, derived from 2-sulphonate, 1,5-disulphonate and 2,6-disulphonate derivatives of 9,10-anthraquinone, have been studied using pulse radiolysis and kinetic absorption spectrophotometry techniques. Spectroscopic characteristics of both neutral and anionic species have been ascertained. Kinetics of formation and decay, reactivity with oxygen and one-electron reduction potential values have been estimated. The semiquinone radicals have been shown to be very stable under suitable pH conditions where the equilibrium (2 semiquinone ↔ quinone + hydroquinone) lies predominantly to the left. From a measurement of the equilibrium constants at different pH, values of E 2 and E m have been calculated. (author)

Oxygen reduction on nanocrystalline ruthenia-local structure effects

DEFF Research Database (Denmark)

Abbott, Daniel F.; Mukerjee, Sanjeev; Petrykin, Valery

2015-01-01

Nanocrystalline ruthenium dioxide and doped ruthenia of the composition Ru1-xMxO2 (M = Co, Ni, Zn) with 0 ≤ x ≤ 0.2 were prepared by the spray-freezing freeze-drying technique. The oxygen reduction activity and selectivity of the prepared materials were evaluated in alkaline media using the RRDE ...

Fe/Ni-N-CNFs electrochemical catalyst for oxygen reduction reaction/oxygen evolution reaction in alkaline media

Energy Technology Data Exchange (ETDEWEB)

Wang, Zhuang [MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin 150001 (China); Li, Mian [Faculty of Chemistry, Northeast Normal University, Changchun 130024 (China); Fan, Liquan; Han, Jianan [MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin 150001 (China); Xiong, Yueping, E-mail: ypxiong@hit.edu.cn [MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, School of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin 150001 (China)

2017-04-15

Highlights: • Novel Fe/Ni-N-CNFs electrocatalysts are prepared by electrospinning technique. • The Fe1Ni1-N-CNFs catalyst exhibits the excellent ORR and OER catalytic activity. • Synergy of Fe/Ni alloy is responsible for the excellent catalytic performance. - Abstract: The novel of iron, nickel and nitrogen doped carbon nanofibers (Fe/Ni-N-CNFs) as bifunctional electrocatalysts are prepared by electrospinning technique. In alkaline media, the Fe/Ni-N-CNFs catalysts (especially for Fe1Ni1-N-CNFs) exhibit remarkable electrocatalytic performances of oxygen reduction reaction (ORR)/oxygen evolution reaction (OER). For ORR catalytic activity, Fe1Ni1-N-CNFs catalyst offers a higher onset potential of 0.903 V, a similar four-electron reaction pathway, and excellent stability. For OER catalytic activity, Fe1Ni1-N-CNFs catalyst possesses a lower onset potential of 1.528 V and a smaller charge transfer resistance of 48.14 Ω. The unparalleled catalytic activity of ORR and OER for the Fe1Ni1-N-CNFs is attributed to the 3D porous cross-linked microstructures of carbon nanofibers with Fe/Ni alloy, N dopant, and abundant M-N{sub x} and NiOOH as catalytic active sites. Thus, Fe1Ni1-N-CNFs catalyst can be acted as one of the efficient and inexpensive catalysts of metal-air batteries.

Influence of Chemical and Physical Properties of Activated Carbon Powders on Oxygen Reduction and Microbial Fuel Cell Performance

KAUST Repository

Watson, Valerie J.

2013-06-03

Commercially available activated carbon (AC) powders made from different precursor materials (coal, peat, coconut shell, hardwood, and phenolic resin) were electrochemically evaluated as oxygen reduction catalysts and tested as cathode catalysts in microbial fuel cells (MFCs). AC powders were characterized in terms of surface chemistry and porosity, and their kinetic activities were compared to carbon black and platinum catalysts in rotating disk electrode (RDE) tests. Cathodes using the coal-derived AC had the highest power densities in MFCs (1620 ± 10 mW m-2). Peat-based AC performed similarly in MFC tests (1610 ± 100 mW m-2) and had the best catalyst performance, with an onset potential of Eonset = 0.17 V, and n = 3.6 electrons used for oxygen reduction. Hardwood based AC had the highest number of acidic surface functional groups and the poorest performance in MFC and catalysis tests (630 ± 10 mW m-2, Eonset = -0.01 V, n = 2.1). There was an inverse relationship between onset potential and quantity of strong acid (pKa < 8) functional groups, and a larger fraction of microporosity was negatively correlated with power production in MFCs. Surface area alone was a poor predictor of catalyst performance, and a high quantity of acidic surface functional groups was determined to be detrimental to oxygen reduction and cathode performance. © 2013 American Chemical Society.

electrocatalytic reduction of oxygen at vapor phase polymerized poly ...

African Journals Online (AJOL)

Preferred Customer

ABSTRACT. We successfully polymerized poly(3,4-ethylenedioxidethiophene) by vapor phase polymerization technique on rotating glassy carbon disk electrode. The catalytic activity of this electrode towards oxygen reduction reaction was investigated and showed remarkable activity. Rotating disk voltammetry was used to ...

About the 'enlightenment' of nonideal hydrogen-oxygen plasma at a electron concentration Ne19 cm-3

International Nuclear Information System (INIS)

Fedorovich, O.A.

2013-01-01

The results of experimental determination of the emissivity of the hydrogen-oxygen plasma pulsed discharge in water and their comparison with calculations. It is shown that when concentrations nonideal plasma N e >3 centre dot 10 18 cm -3 , is observed 'enlightenment' of plasma. The reduction of a emitting ability . can be more order in the N e =3 centre dot 10 19 cm -3 and increases with increasing electron concentration.

Electron-beam-induced reduction of Fe3+ in iron phosphate dihydrate, ferrihydrite, haemosiderin and ferritin as revealed by electron energy-loss spectroscopy

International Nuclear Information System (INIS)

Pan, Ying-Hsi; Vaughan, Gareth; Brydson, Rik; Bleloch, Andrew; Gass, Mhairi; Sader, Kasim; Brown, Andy

2010-01-01

The effect of high-energy electron irradiation on ferritin/haemosiderin cores (in an iron-overloaded human liver biopsy), its mineral analogue; six-line ferrihydrite (6LFh), and iron phosphate dihydrate (which has similar octahedral ferric iron to oxygen coordination to that in ferrihydrite and ferritin/haemosiderin cores) has been investigated using electron energy-loss spectroscopy (EELS). Fe L 2,3 -ionisation edges were recorded on two types of electron microscope: a 200 keV transmission electron microscope (TEM) and a 100 keV scanning transmission electron microscope (STEM), in order to investigate the damage mechanisms in operation and to establish a methodology for minimum specimen alteration during analytical electron microscopic characterisation. A specimen damage mechanism dominated by radiolysis that results in the preferential loss of iron co-ordinating ligands (O, OH and H 2 O) is discussed. The net result of irradiation is structural re-organisation and reduction of iron within the iron hydroxides. At sufficiently low electron fluence and particularly in the lower incident energy, finer probe diameter STEM, the alteration is shown to be minimal. All the materials examined exhibit damage which as a function of cumulative fluence is best fitted by an inverse power-law, implying that several chemical and structural changes occur in response to the electron beam and we suggest that these are governed by secondary processes arising from the primary ionisation event. This work affirms that electron fluence and current density should be considered when measuring mixed valence ratios with EELS.

Detection of oxygen-related defects in GaAs by exo-electron emission spectroscopy

International Nuclear Information System (INIS)

Hulluvarad, Shiva S.; Naddaf, M.; Bhoraskar, S.V.

2001-01-01

The influence of intentional introduction of oxygen, at the surface of GaAs, on its native surface states was studied. Oxygen was made to interact with the surface of GaAs by three different means: (1) by growing native oxides, (2) exposing to oxygen plasma in an electron cyclotron resonance (ECR) plasma reactor and by (3) high energy oxygen ion irradiation. Thermally stimulated exo-electron emission (TSEE) spectroscopy was used to estimate the relative densities and energies of the surface states induced by the three different modes of introducing oxygen. Out of the two native defect levels found in GaAs by TSEE; at 325 K (0.7 eV below E c ) and at 415 K (0.9 below E c ); the former is seen to get broadened or split into multiple peaks in each of the methods. Multiple peaks in TSEE signify the presence of a closely spaced band of defect levels. Therefore the results exclusively point out that oxygen-related complexes contribute to the formation of a band of defects centered at 325 K in TSEE which is correlated to an energy level 0.7 eV below E c known as the EL2 defect level. The results reported in this paper thus confirm that the TSEE peak at 0.7 eV below E c is related to oxygen induced defects whereas the peak at 0.9 eV is not affected by the presence of oxygen-related species

Detection of oxygen-related defects in GaAs by exo-electron emission spectroscopy

Science.gov (United States)

Hulluvarad, Shiva S.; Naddaf, M.; Bhoraskar, S. V.

2001-10-01

The influence of intentional introduction of oxygen, at the surface of GaAs, on its native surface states was studied. Oxygen was made to interact with the surface of GaAs by three different means: (1) by growing native oxides, (2) exposing to oxygen plasma in an electron cyclotron resonance (ECR) plasma reactor and by (3) high energy oxygen ion irradiation. Thermally stimulated exo-electron emission (TSEE) spectroscopy was used to estimate the relative densities and energies of the surface states induced by the three different modes of introducing oxygen. Out of the two native defect levels found in GaAs by TSEE; at 325 K (0.7 eV below Ec) and at 415 K (0.9 below Ec); the former is seen to get broadened or split into multiple peaks in each of the methods. Multiple peaks in TSEE signify the presence of a closely spaced band of defect levels. Therefore the results exclusively point out that oxygen-related complexes contribute to the formation of a band of defects centered at 325 K in TSEE which is correlated to an energy level 0.7 eV below Ec known as the EL2 defect level. The results reported in this paper thus confirm that the TSEE peak at 0.7 eV below Ec is related to oxygen induced defects whereas the peak at 0.9 eV is not affected by the presence of oxygen-related species.

Detection of oxygen-related defects in GaAs by exo-electron emission spectroscopy

International Nuclear Information System (INIS)

Hulluvarad, Shiva S.; Naddaf, M.; Bhoraskar, S.V.

2004-01-01

The influence of intentional introduction of oxygen, at the surface of GaAs, on its native surface states was studied. Oxygen was made to interact with the surface of GaAs by three different means: (1) by growing native oxides, (2) exposing to oxygen plasma in an electron cyclotron resonance (ECR) plasma reactor and by (3) high energy oxygen ion irradiation. Thermally stimulated exo-electron emission (TSEE) spectroscopy was used to estimate the relative densities and energies of the surface states induced by the three different modes of introducing oxygen. Out of the two native defect levels found in GaAs by TSEE; at 325 K (0.7 eV below E c ) and at 415 K (0.9 below E c ); the former is seen to get broadened or split into multiple peaks in each of the methods. Multiple peaks in TSEE signify the presence of a closely spaced band of defect levels. Therefore the results exclusively point out that oxygen-related complexes contribute to the formation of a band of defects centered at 325 K in TSEE which is correlated to an energy level 0.7 eV below E c known as the EL2 defect level. The results reported in this paper thus confirm that the TSEE peak at 0.7 eV below E c is related to oxygen induced defects whereas the peak at 0.9 eV is not affected by the presence of oxygen-related species. (author)

Oxygen reduction at electrodeposited ZnO layers in alkaline solution

International Nuclear Information System (INIS)

Prestat, M.; Vucko, F.; Lescop, B.; Rioual, S.; Peltier, F.; Thierry, D.

2016-01-01

Zinc oxide (ZnO) layers were electrodeposited from an aqueous nitrate bath at 62 °C on copper substrates. At −0.9 V (vs. saturated calomel reference electrode), the growth rate is 600 nm min −1 . In the early stages of the deposition, the layers are porous. At longer deposition times, the surface becomes dense and rough. The wurtzite crystalline structure is confirmed by XRD measurements and the chemical composition of the ZnO surface was assessed by EDX and XPS. The oxygen reduction reaction (ORR) was investigated at room temperature in a 10 −3 M KOH solution with KCl as supporting electrolyte. The ORR onset potential is found to be much larger than that of platinum taken as reference electrocatalyst. Rotating ring-disk electrode experiments evidence a negligible production of hydrogen peroxide as intermediate product of the reaction. The latter follows thus a direct four-electron pathway at pH ∼11.

NOx reduction by compact electron beam processing

International Nuclear Information System (INIS)

Penetrante, B.M.; Hsiao, M.C.; Merritt, B.T.; Wallman, P.H.; Vogtlin, G.E.

1995-01-01

Among the new methods being investigated for the post-combustion removal of nitrogen oxides (NO x ) are based on non-thermal plasmas. These plasmas can be produced by electrical discharge methods or electron beam irradiation. The application of electron beam irradiation for NO x removal in power plant flue gases has been investigated since the early 1970's in both laboratory- and pilot-scale experiments. Electrical discharge methods are relatively new entrants in the field of flue gas cleanup. Pulsed corona and dielectric-barrier discharge techniques are two of the more commonly used electrical discharge methods for producing nonthermal plasmas at atmospheric pressure. There are basically two types of reactions responsible for the depletion of NO by non-thermal plasmas: oxidation and reduction

Sulfate Reduction and Thiosulfate Transformations in a Cyanobacterial Mat during a Diel Oxygen Cycle

DEFF Research Database (Denmark)

JØRGENSEN, BB

1994-01-01

Bacterial sulfate reduction and transformations of thiosulfate were studied with radiotracers in a Microcoleus chthono-plastes-dominated microbial mat growing in a hypersaline pond at the Red Sea. The study showed how a diel cycle of oxygen evolution affected respiration by sulfate-reducing bacte......Bacterial sulfate reduction and transformations of thiosulfate were studied with radiotracers in a Microcoleus chthono-plastes-dominated microbial mat growing in a hypersaline pond at the Red Sea. The study showed how a diel cycle of oxygen evolution affected respiration by sulfate......-reducing bacteria and the metabolism of thiosulfate through oxidative and reductive pathways. Sulfate reduction occurred in both oxic and anoxic layers of the mat and varied diurnally, apparently according to temperature rather than to oxygen. Time course experiments showed that the radiotracer method...... underestimated sulfate reduction in the oxic zone due to rapid reoxidation of the produced sulfide. Extremely high reduction rates of up to 10 mu mol cm(-3) d(-1) were measured just below the euphotic zone. Although thiosulfate was simultaneously oxidized, reduced and disproportionated by bacteria in all layers...

The effect of oxygen exposure on pentacene electronic structure

NARCIS (Netherlands)

Vollmer, A; Jurchescu, OD; Arfaoui, [No Value; Salzmann, [No Value; Palstra, TTM; Rudolf, P; Niemax, J; Pflaum, J; Rabe, JP; Koch, N; Arfaoui, I.; Salzmann, I.

We use ultraviolet photoelectron spectroscopy to investigate the effect of oxygen and air exposure on the electronic structure of pentacene single crystals and thin films. it is found that O-2 and water do not react noticeably with pentacene, whereas singlet oxygen/ozone readily oxidize the organic

Bubble dynamic templated deposition of three-dimensional palladium nanostructure catalysts: Approach to oxygen reduction using macro-, micro-, and nano-architectures on electrode surfaces

International Nuclear Information System (INIS)

Yang Guimei; Chen Xing; Li Jie; Guo Zheng; Liu Jinhuai; Huang Xingjiu

2011-01-01

Highlights: → We synthesize the Pd nanostructures by bubbles dynamic templated. → We obtain Pd nanobuds and Pd nanodendrites by changing the reaction precursor. → We obtain Pd macroelectrode voltammertric behavior using small amount of Pd materials. → We proved a ECE process. → The Pd nanostructures/GCE for O 2 reduction is a 2-step 4-electron process. - Abstract: Three-dimensional (3D) palladium (Pd) nanostructures (that is, nano-buds or nano-dendrites) are fabricated by bubble dynamic templated deposition of Pd onto a glassy carbon electrode (GCE). The morphology can be tailored by changing the precursor concentration and reaction time. Scanning electron microscopy images reveal that nano-buds or nano-dendrites consist of nanoparticles of 40-70 nm in diameter. The electrochemical reduction of oxygen is reported at such kinds of 3D nanostructure electrodes in aqueous solution. Data were collected using cyclic voltammetry. We demonstrate the Pd macroelectrode behavior of Pd nanostructure modified electrode by exploiting the diffusion model of macro-, micro-, and nano-architectures. In contrast to bare GCE, a significant positive shift and splitting of the oxygen reduction peak (vs Ag/AgCl/saturated KCl) at Pd nanostructure modified GCE was observed.

Oxygen reduction by decamethylferrocene at liquid/liquid interfaces catalyzed by dodecylaniline

Czech Academy of Sciences Publication Activity Database

Su, B.; Hatay, I.; Li, F.; Partovi-Nia, R.; Samec, Zdeněk; Ersöz, M.; Girault, H. H.

2010-01-01

Roč. 639, 1-2 (2010), s. 102-108 ISSN 1572-6657 R&D Projects: GA ČR(CZ) GA203/07/1257; GA MŠk OC 177 Institutional research plan: CEZ:AV0Z40400503 Keywords : oxygen reduction * proton reduction * voltammetry Subject RIV: CG - Electrochemistry Impact factor: 2.732, year: 2010

Soft landing of bare PtRu nanoparticles for electrochemical reduction of oxygen.

Science.gov (United States)

Johnson, Grant E; Colby, Robert; Engelhard, Mark; Moon, Daewon; Laskin, Julia

2015-08-07

Magnetron sputtering of two independent Pt and Ru targets coupled with inert gas aggregation in a modified commercial source has been combined with soft landing of mass-selected ions to prepare bare 4.5 nm diameter PtRu nanoparticles on glassy carbon electrodes with controlled size and morphology for electrochemical reduction of oxygen in solution. Employing atomic force microscopy (AFM) it is shown that the nanoparticles bind randomly to the glassy carbon electrode at a relatively low coverage of 7 × 10(4) ions μm(-2) and that their average height is centered at 4.5 nm. Scanning transmission electron microscopy images obtained in the high-angle annular dark field mode (HAADF-STEM) further confirm that the soft-landed PtRu nanoparticles are uniform in size. Wide-area scans of the electrodes using X-ray photoelectron spectroscopy (XPS) reveal the presence of both Pt and Ru in atomic concentrations of ∼9% and ∼33%, respectively. Deconvolution of the high energy resolution XPS spectra in the Pt 4f and Ru 3d regions indicates the presence of both oxidized Pt and Ru. The substantially higher loading of Ru compared to Pt and enrichment of Pt at the surface of the nanoparticles is confirmed by wide-area analysis of the electrodes using time-of-flight medium energy ion scattering (TOF-MEIS) employing both 80 keV He(+) and O(+) ions. The activity of electrodes containing 7 × 10(4) ions μm(-2) of bare 4.5 nm PtRu nanoparticles toward the electrochemical reduction of oxygen was evaluated employing cyclic voltammetry (CV) in 0.1 M HClO4 and 0.5 M H2SO4 solutions. In both electrolytes a pronounced reduction peak was observed during O2 purging of the solution that was not evident during purging with Ar. Repeated electrochemical cycling of the electrodes revealed little evolution in the shape or position of the voltammograms indicating high stability of the nanoparticles supported on glassy carbon. The reproducibility of the nanoparticle synthesis and deposition was

Detection of oxygen-related defects in GaAs by exo-electron emission spectroscopy

Energy Technology Data Exchange (ETDEWEB)

Hulluvarad, Shiva S.; Naddaf, M.; Bhoraskar, S.V. E-mail: svb@physics.unipune.ernet.in

2001-10-01

The influence of intentional introduction of oxygen, at the surface of GaAs, on its native surface states was studied. Oxygen was made to interact with the surface of GaAs by three different means: (1) by growing native oxides, (2) exposing to oxygen plasma in an electron cyclotron resonance (ECR) plasma reactor and by (3) high energy oxygen ion irradiation. Thermally stimulated exo-electron emission (TSEE) spectroscopy was used to estimate the relative densities and energies of the surface states induced by the three different modes of introducing oxygen. Out of the two native defect levels found in GaAs by TSEE; at 325 K (0.7 eV below E{sub c}) and at 415 K (0.9 below E{sub c}); the former is seen to get broadened or split into multiple peaks in each of the methods. Multiple peaks in TSEE signify the presence of a closely spaced band of defect levels. Therefore the results exclusively point out that oxygen-related complexes contribute to the formation of a band of defects centered at 325 K in TSEE which is correlated to an energy level 0.7 eV below E{sub c} known as the EL2 defect level. The results reported in this paper thus confirm that the TSEE peak at 0.7 eV below E{sub c} is related to oxygen induced defects whereas the peak at 0.9 eV is not affected by the presence of oxygen-related species.

Reductive tetrachloroethene dehalogenation in the presence of oxygen by Sulfurospirillum multivorans: physiological studies and proteome analysis.

Science.gov (United States)

Gadkari, Jennifer; Goris, Tobias; Schiffmann, Christian L; Rubick, Raffael; Adrian, Lorenz; Schubert, Torsten; Diekert, Gabriele

2018-01-01

Reductive dehalogenation of organohalides is carried out by organohalide-respiring bacteria (OHRB) in anoxic environments. The tetrachloroethene (PCE)-respiring Epsilonproteobacterium Sulfurospirillum multivorans is one of few OHRB able to respire oxygen. Therefore, we investigated the organism's capacity to dehalogenate PCE in the presence of oxygen, which would broaden the applicability to use S. multivorans, unlike other commonly oxygen-sensitive OHRB, for bioremediation, e.g. at oxic/anoxic interphases. Additionally, this has an impact on our understanding of the global halogen cycle. Sulfurospirillum multivorans performs dehalogenation of PCE to cis-1,2-dichloroethene at oxygen concentrations below 0.19 mg/L. The redox potential of the medium electrochemically adjusted up to +400 mV had no influence on reductive dehalogenation by S. multivorans in our experiments, suggesting that higher levels of oxygen impair PCE dechlorination by inhibiting or inactivating involved enzymes. The PCE reductive dehalogenase remained active in cell extracts of S. multivorans exposed to 0.37 mg/L oxygen for more than 96 h. Analysis of the proteome revealed that superoxide reductase and cytochrome peroxidase amounts increased with 5% oxygen in the gas phase, while the response to atmospheric oxygen concentrations involved catalase and hydrogen peroxide reductase. Taken together, our results demonstrate that reductive dehalogenation by OHRB is not limited to anoxic conditions. © FEMS 2017. All rights reserved. For permissions, please e-mail: journals.permissions@oup.com.

Aluminothermic Reduction-Molten Salt Electrolysis Using Inert Anode for Oxygen and Al-Base Alloy Extraction from Lunar Soil Simulant

Science.gov (United States)

Xie, Kaiyu; Shi, Zhongning; Xu, Junli; Hu, Xianwei; Gao, Bingliang; Wang, Zhaowen

2017-10-01

Aluminothermic reduction-electrolysis using an inert anode process is proposed to extract oxygen and metals from Minnesota Lunar Simulant-1 (MLS-1). Effective aluminothermic reduction between dissolved MLS-1 and dissolved metal aluminum was achieved in cryolite salt media. The product phases obtained by aluminothermic reduction at 980°C for 4 h were Al, Si, and Al5FeSi, while the chemical components were 79.71 mass% aluminum, 12.03 mass% silicon, 5.91 mass% iron, and 2.35 mass% titanium. The cryolite salt containing Al2O3 was subsequently electrolyzed with Fe0.58-Ni0.42 inert anode at 960°C for 4 h. Oxygen was evolved at the anode with an anodic current efficiency of 78.28%. The results demonstrate that this two-step process is remarkably feasible for the extraterrestrial extraction of oxygen and metals. This process will help expand the existing in situ resource utilization methods.

CoPd x oxygen reduction electrocatalysts for polymer electrolyte membrane and direct methanol fuel cells

International Nuclear Information System (INIS)

Mustain, William E.; Kepler, Keith; Prakash, Jai

2007-01-01

The electrochemical activity of carbon-supported cobalt-palladium alloy electrocatalysts of various compositions have been investigated for the oxygen reduction reaction in a 5 cm 2 single cell polymer electrolyte membrane fuel cell. The polarization experiments have been conducted at various temperatures between 30 and 60 deg. C and the reduction performance compared with data from a commercial Pt catalyst under identical conditions. Investigation of the catalytic activity of the CoPd x PEMFC system with varying composition reveals that a nominal cobalt-palladium atomic ratio of 1:3, CoPd 3 , exhibits the best performance of all studied catalysts, exhibiting a catalytic activity comparable to the commercial Pt catalyst. The ORR on CoPd 3 has a low activation energy, 52 kJ/mol, and a Tafel slope of approximately 60 mV/decade, indicating that the rate-determining step is a chemical step following the first electron transfer step and may involve the breaking of the oxygen bond. The CoPd 3 catalyst also exhibits excellent chemical stability, with the open circuit cell voltage decreasing by only 3% and the observed current decreasing by only 10% at 0.8 V over 25 h. The CoPd 3 catalyst also exhibits superior tolerance to methanol crossover poisoning than Pt

Pulsed electron-beam-sustained discharge in oxygen-containing gas mixtures: electrical characteristics, spectroscopy,and singlet oxygen yield

International Nuclear Information System (INIS)

Vagin, Nikolai P; Ionin, Andrei A; Klimachev, Yu M; Kotkov, A A; Podmar'kov, Yu P; Seleznev, L V; Sinitsyn, D V; Frolov, M P; Yuryshev, Nikolai N; Kochetov, Igor' V; Napartovich, A P; Hager, G D

2004-01-01

The electrical and spectroscopic characteristics of electron-beam-sustained discharge (EBSD) in oxygen and oxygen-containing gas mixtures are studied experimentally under gas pressures up to 100 Torr in a large excitation volume (∼18 L). It is shown that the EBSD in pure oxygen and its mixtures with inert gases is unstable and is characterised by a small specific energy contribution. The addition of small amounts (∼1%-10%) of carbon monoxide or hydrogen to oxygen or its mixtures with inert gases considerably improves the stability of the discharge, while the specific energy contribution W increases by more then an order of magnitude, achieving ∼6.5 kJ L -1 atm -1 per molecular component of the gas mixture. A part of the energy supplied to the EBSD is spent to excite vibrational levels of molecular additives. This was demonstrated experimentally by the initiation of a CO laser based on the O 2 : Ar : CO = 1 : 1 : 0.1 mixture. Experimental results on spectroscopy of the excited electronic states O 2 (a 1 Δ g ) and O 2 (b 1 Σ g + ), of oxygen formed in the EBSD are presented. A technique was worked out for measuring the concentration of singlet oxygen in the O 2 (a 1 Δ g ) state in the afterglow of the pulsed EBSD by comparing with the radiation intensity of singlet oxygen of a given concentration produced in a chemical generator. Preliminary measurements of the singlet-oxygen yield in the EBSD show that its value ∼3% for W ∼ 1.0 kJ L -1 atm -1 is in agreement with the theoretical estimate. Theoretical calculations performed for W ∼ 6.5 kJ L -1 atm -1 at a fixed temperature show that the singlet-oxygen yield may be ∼20%, which is higher than the value required to achieve the lasing threshold in an oxygen-iodine laser at room temperature. (laser applications and other topics in quantum electronics)

Synthesis of highly active and dual-functional electrocatalysts for methanol oxidation and oxygen reduction reactions

Energy Technology Data Exchange (ETDEWEB)

Zhao, Qi; Zhang, Geng; Xu, Guangran; Li, Yingjun [College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021 (China); Liu, Baocang [College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021 (China); Inner Mongolia Key Lab of Nanoscience and Nanotechnology, Inner Mongolia University, Hohhot 010021 (China); Gong, Xia [College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021 (China); Zheng, Dafang [State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry, Jilin University, Changchun 130012 (China); Zhang, Jun [College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021 (China); Inner Mongolia Key Lab of Nanoscience and Nanotechnology, Inner Mongolia University, Hohhot 010021 (China); Wang, Qin, E-mail: qinwang@imu.edu.cn [College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021 (China); Inner Mongolia Key Lab of Nanoscience and Nanotechnology, Inner Mongolia University, Hohhot 010021 (China)

2016-12-15

Graphical abstract: Ternary RuMPt (M = Fe, Co, Ni, and Cu) nanodendrities (NDs) catalysts, are successfully synthesized by using a facile method. The as-obtained ternary catalysts manifest superior catalytic activity and stability both in terms of surface and mass specific activities toward the methanol oxidation and oxygen reduction reactions, as compared to the binary catalysts and the commercial Pt/C catalysts. - Highlights: • Ternary RuMPt catalysts are synthesized by using a facile method. • The catalysts manifest superior catalytic activity towards the MOR and ORR. • High activities are attributed to enhanced electron density and synergistic effects. - Abstract: The promising Pt-based ternary catalyst is crucial for polymer electrolyte membrane fuel cells (PEMFCs) due to improving catalytic activity and durability for both methanol oxidation reaction and oxygen reduction reaction. In this work, a facile strategy is used for the synthesis ternary RuMPt (M = Fe, Co, Ni, and Cu) nanodendrities catalysts. The ternary RuMPt alloys exhibit enhanced specific and mass activity, positive half-wave potential, and long-term stability, compared with binary Pt-based alloy and the commercial Pt/C catalyst, which is attributed to the high electron density and upshifting of the d-band center for Pt atoms, and synergistic catalytic effects among Pt, M, and Ru atoms by introducing a transition metal. Impressively, the ternary RuCoPt catalyst exhibits superior mass activity (801.59 mA mg{sup −1}) and positive half-wave potential (0.857 V vs. RHE) towards MOR and ORR, respectively. Thus, the RuMPt nanocomposite is a very promising material to be used as dual electrocatalyst in the application of PEMFCs.

Electrochemical formation of a Pt/Zn alloy and its use as a catalyst for oxygen reduction reaction in fuel cells.

Science.gov (United States)

Sode, Aya; Li, Winton; Yang, Yanguo; Wong, Phillip C; Gyenge, Elod; Mitchell, Keith A R; Bizzotto, Dan

2006-05-04

The characterization of an electrochemically created Pt/Zn alloy by Auger electron spectroscopy is presented indicating the formation of the alloy, the oxidation of the alloy, and the room temperature diffusion of the Zn into the Pt regions. The Pt/Zn alloy is stable up to 1.2 V/RHE and can only be removed with the oxidation of the base Pt metal either electrochemically or in aqua regia. The Pt/Zn alloy was tested for its effectiveness toward oxygen reduction. Kinetics of the oxygen reduction reaction (ORR) were measured using a rotating disk electrode (RDE), and a 30 mV anodic shift in the potential of ORR was found when comparing the Pt/Zn alloy to Pt. The Tafel slope was slightly smaller than that measured for the pure Pt electrode. A simple procedure for electrochemically modifying a Pt-containing gas diffusion electrode (GDE) with Zn was developed. The Zn-treated GDE was pressed with an untreated GDE anode, and the created membrane electrode assembly was tested. Fuel cell testing under two operating conditions (similar anode and cathode inlet pressures, and a larger cathode inlet pressure) indicated that the 30 mV shift observed on the RDE was also evident in the fuel cell tests. The high stability of the Pt/Zn alloy in acidic environments has a potential benefit for fuel cell applications.

The Use of an Edible Mushroom-Derived Renewable Carbon Material as a Highly Stable Electrocatalyst towards Four-Electron Oxygen Reduction

Directory of Open Access Journals (Sweden)

Chaozhong Guo

2015-12-01

Full Text Available The development of highly stable and efficient electrocatalysts for sluggish oxygen reduction reaction (ORR is exceedingly significant for the commercialization of fuel cells but remains a challenge. We here synthesize a new nitrogen-doped biocarbon composite material (N-BC@CNP-900 as a nitrogen-containing carbon-based electrocatalyst for the ORR via facile all-solid-state multi-step pyrolysis of bioprotein-enriched enoki mushroom as a starting material, and inexpensive carbon nanoparticles as the inserting matrix and conducting agent at controlled temperatures. Results show that the N-BC@CNP-900 catalyst exhibits the best ORR electrocatalytic activity with an onset potential of 0.94 V (versus reversible hydrogen electrode, RHE and high stability. Meanwhile, this catalyst significantly exhibits good selectivity of the four-electron reaction pathway in an alkaline electrolyte. It is notable that pyridinic- and graphtic-nitrogen groups that play a key role in the enhancement of the ORR activity may be the catalytically active structures for the ORR. We further propose that the pyridinic-nitrogen species can mainly stabilize the ORR activity and the graphitic-nitrogen species can largely enhance the ORR activity. Besides, the addition of carbon support also plays an important role in the pyrolysis process, promoting the ORR electrocatalytic activity.

The Use of an Edible Mushroom-Derived Renewable Carbon Material as a Highly Stable Electrocatalyst towards Four-Electron Oxygen Reduction.

Science.gov (United States)

Guo, Chaozhong; Sun, Lingtao; Liao, Wenli; Li, Zhongbin

2015-12-23

The development of highly stable and efficient electrocatalysts for sluggish oxygen reduction reaction (ORR) is exceedingly significant for the commercialization of fuel cells but remains a challenge. We here synthesize a new nitrogen-doped biocarbon composite material (N-BC@CNP-900) as a nitrogen-containing carbon-based electrocatalyst for the ORR via facile all-solid-state multi-step pyrolysis of bioprotein-enriched enoki mushroom as a starting material, and inexpensive carbon nanoparticles as the inserting matrix and conducting agent at controlled temperatures. Results show that the N-BC@CNP-900 catalyst exhibits the best ORR electrocatalytic activity with an onset potential of 0.94 V ( versus reversible hydrogen electrode, RHE) and high stability. Meanwhile, this catalyst significantly exhibits good selectivity of the four-electron reaction pathway in an alkaline electrolyte. It is notable that pyridinic- and graphtic-nitrogen groups that play a key role in the enhancement of the ORR activity may be the catalytically active structures for the ORR. We further propose that the pyridinic-nitrogen species can mainly stabilize the ORR activity and the graphitic-nitrogen species can largely enhance the ORR activity. Besides, the addition of carbon support also plays an important role in the pyrolysis process, promoting the ORR electrocatalytic activity.

Synergistically enhanced activity of nitrogen-doped carbon dots/graphene composites for oxygen reduction reaction

Science.gov (United States)

Liu, Hui; Zhao, Qingshan; Liu, Jingyan; Ma, Xiao; Rao, Yuan; Shao, Xiaodong; Li, Zhongtao; Wu, Wenting; Ning, Hui; Wu, Mingbo

2017-11-01

With rapid dissociative adsorption of oxygen, nitrogen-doped carbon nanomaterials have been demonstrated to be efficient alternative catalysts for oxygen reduction reaction (ORR) in fuel cells. Herein, we developed a mild hydrothermal strategy to construct nitrogen-doped carbon dots/graphene (NCDs-NG) composites towards ORR. Carbon dots (CDs) were derived from petroleum coke via acid oxidation while graphene oxide (GO) was obtained from graphite by modified Hummer's method. Graphene was employed as a conductive substrate to disperse CDs during hydrothermal reducing reaction while ammonia was utilized as N source to dope both graphene and CDs. The synergistic effects, i.e. CDs as pillars for graphene and catalytic sites for ORR, the high conductivity of graphene, the quick O2 adsorption on doped pyridinic nitrogen endow the NCDs-NG composites with enhanced ORR catalytic performance in alkaline electrolyte. The onset potential of -95 mV and kinetic current density of 12.7 mA cm-2 at -0.7 V (vs. Ag/AgCl) can be compared to those of the commercial 20 wt% Pt/C catalyst. The electron transfer number is about 3.9, revealing a four-electron pathway for ORR. The optimal NCDs-NG catalyst shows superior durability and methanol tolerance than 20 wt% Pt/C. This work demonstrates a feasible and effective strategy to prepare metal-free efficient ORR electrocatalysts for fuel cell applications.

The effect of ammonia upon the electrocatalysis of hydrogen oxidation and oxygen reduction on polycrystalline platinum

DEFF Research Database (Denmark)

Verdaguer Casadevall, Arnau; Hernandez-Fernandez, Patricia; Stephens, Ifan E.L.

2012-01-01

The influence of ammonium ions on the catalysis of hydrogen oxidation and oxygen reduction is studied by means of rotating ring-disk electrode experiments on polycrystalline platinum in perchloric acid. While ammonium does not affect the hydrogen oxidation reaction, the oxygen reduction reaction...

Oxygen reduction reaction properties of nitrogen-incorporated nanographenes synthesized using in-liquid plasma from mixture of ethanol and iron phthalocyanine

Science.gov (United States)

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

2018-04-01

Nanographenes were synthesized using in-liquid plasma from a mixture of iron phthalocyanine and ethanol. In a previous study, micrometer-scale flakes with nitrogen incorporation were obtained. A nonprecious metal catalytic activity was observed with 3.13 electrons in an oxygen reduction reaction under an acidic solute condition. Large-surface-area, high-graphene-crystallinity, and iron-carbon-bonding sites were found owing to a high catalytic activity in Fe-N/nanographene.

Characterization of alternate reductant binding and electron transfer in the dopamine β-monooxygenase reaction

International Nuclear Information System (INIS)

Stewart, L.C.; Klinman, J.P.

1987-01-01

The steady-state limiting kinetic parameters V/sub max/, V/K/sub DA/, and V/K/sub O 2 /, together with deuterium isotope effects on these parameters, have been determined for the dopamine β-monooxygenase (DβM) reaction in the presence of structurally distinct reductants. The results show the one-electron reductant ferrocyanide to be nearly as kinetically competent as the presumed in vivo reductant ascrobate. Further, a reductant system of ferricyanide plus substrate dopamine yields steady-state kinetic parameters and isotope effects very similar to those measured solely in the presence of ferrocyanide, indicating a role for catecholamine in the rapid recycling of oxidized ferrocyanide. Use of substrate dopamine as the sole reductant is found to lead to a highly unusual kinetic independence of oxygen concentration, as well as significantly reduced values of V/sub max/ and V/K/sub DA/, and the authors conclude that dopamine reduces enzymic copper in a rate-limiting step that is 40-fold slower than with ascorbate. The near-identical kinetic parameters measured in the presence of either ascorbate or ferrocyanide, together with markedly reduced rates with dopamine, are interpreted in terms of a binding site for reductant that is physically distinct from the substrate binding site. This view is supported by molecular modeling, which reveals ascorbate and ferrocyanide to possess an unexpected similarity in potential sites for interaction with enzymic residues. With regard to electron flux, identical values of V/K/sub O 2 / have been measured with [2,2- 2 H 2 ]dopamine as substrate both in the presence and in the absence of added ascorbate. This key result unambiguously rules out an entry of electrons to enzyme forms leading from the enzyme-dopamine complex to enzyme-bound product and, hence, reaction mechanisms involving a reductive activation of the putative Cu(II)-OOH prior to substrate hydroxylation

Nitrogen-doped carbon-supported cobalt-iron oxygen reduction catalyst

Science.gov (United States)

Zelenay, Piotr; Wu, Gang

2014-04-29

A Fe--Co hybrid catalyst for oxygen reaction reduction was prepared by a two part process. The first part involves reacting an ethyleneamine with a cobalt-containing precursor to form a cobalt-containing complex, combining the cobalt-containing complex with an electroconductive carbon supporting material, heating the cobalt-containing complex and carbon supporting material under conditions suitable to convert the cobalt-containing complex and carbon supporting material into a cobalt-containing catalyst support. The second part of the process involves polymerizing an aniline in the presence of said cobalt-containing catalyst support and an iron-containing compound under conditions suitable to form a supported, cobalt-containing, iron-bound polyaniline species, and subjecting said supported, cobalt-containing, iron bound polyaniline species to conditions suitable for producing a Fe--Co hybrid catalyst.

Oxygen reduction on carbon supported platinum catalysts in high temperature polymer electrolytes

DEFF Research Database (Denmark)

Qingfeng, Li; Bergqvist, R. S.; Hjuler, H. A.

1999-01-01

Oxygen reduction on carbon supported platinum catalysts has been investigated in H3PO4, H3PO4-doped Nafion and PBI polymer electrolytes in a temperature range from 80 to 190°C. Compared with pure H3PO4, using the H3PO4 doped Nafion and PBI polymer electrolytes can significantly improve the oxygen...

From two-dimension to one-dimension: the curvature effect of silicon-doped graphene and carbon nanotubes for oxygen reduction reaction.

Science.gov (United States)

Zhang, Peng; Hou, Xiuli; Mi, Jianli; He, Yanqiong; Lin, Lin; Jiang, Qing; Dong, Mingdong

2014-09-07

For the goal of practical industrial development of fuel cells, inexpensive, sustainable, and highly efficient electrocatalysts for oxygen reduction reactions (ORR) are highly desirable alternatives to platinum (Pt) and other rare metals. In this work, based on density functional theory, silicon (Si)-doped carbon nanotubes (CNTs) and graphene as metal-free, low cost, and high-performance electrocatalysts for ORR are studied systematically. It is found that the curvature effect plays an important role in the adsorption and reduction of oxygen. The adsorption of O2 becomes weaker as the curvature varies from positive values (outside CNTs) to negative values (inside CNTs). The free energy change of the rate-determining step of ORR on the concave inner surface of Si-doped CNTs is smaller than that on the counterpart of Si-doped graphene, while that on the convex outer surface of Si-doped CNTs is larger than that on Si-doped graphene. Uncovering this new ORR mechanism on silicon-doped carbon electrodes is significant as the same principle could be applied to the development of various other metal-free efficient ORR catalysts for fuel cell applications.

Quantitative Analysis of Oxygen Gas Exhausted from Anode through In Situ Measurement during Electrolytic Reduction

Directory of Open Access Journals (Sweden)

Eun-Young Choi

2017-01-01

Full Text Available Quantitative analysis by in situ measurement of oxygen gas evolved from an anode was employed to monitor the progress of electrolytic reduction of simulated oxide fuel in a molten Li2O–LiCl salt. The electrolytic reduction of 0.6 kg of simulated oxide fuel was performed in 5 kg of 1.5 wt.% Li2O–LiCl molten salt at 650°C. Porous cylindrical pellets of simulated oxide fuel were used as the cathode by loading a stainless steel wire mesh cathode basket. A platinum plate was employed as the anode. The oxygen gas evolved from the anode was exhausted to the instrumentation for in situ measurement during electrolytic reduction. The instrumentation consisted of a mass flow controller, pump, wet gas meter, and oxygen gas sensor. The oxygen gas was successfully measured using the instrumentation in real time. The measured volume of the oxygen gas was comparable to the theoretically calculated volume generated by the charge applied to the simulated oxide fuel.

Toxin detection using a tyrosinase-coupled oxygen electrode.

Science.gov (United States)

Smit, M H; Rechnitz, G A

1993-02-15

An enzyme-based "electrochemical canary" is described for the detection of cyanide. The sensing system imitates cyanide's site of toxicity in the mitochondria. The terminal sequence of electron transfer in aerobic respiration is mimicked by mediator coupling of tyrosinase catalysis to an electro-chemical system. An enzyme-coupled oxygen electrode is created which is sensitive to selective poisoning. Biocatalytic reduction of oxygen is promoted by electrochemically supplying tyrosinase with electrons. Thus, ferrocyanide is generated at a cathode and mediates the enzymatic reduction of oxygen to water. An enzyme-dependent reductive current can be monitored which is inhibited by cyanide in a concentration-dependent manner. Oxygen depletion in the reaction layer can be minimized by addressing enzyme activity using a potential pulsing routine. Enzyme activity is electrochemically initiated and terminated and the sensor becomes capable of continuous monitoring. Cyanide poisoning of the biological component is reversible, and it can be reused after rinsing. The resulting sensor detects cyanide based on its biological activity rather than its physical or chemical properties.

Reduction of electron density in a plasma by injection of liquids

Science.gov (United States)

Sodha, M. S.; Evans, J. S.

1974-01-01

In this paper, the authors have investigated the physics of various processes relevant to the reduction of electron density in a plasma by addition of water droplets; two processes have in particular been analyzed in some detail, viz, the electron attachment to charged dielectric droplets and the emission of negative ions by vaporization from these droplets. The results of these analyses have been applied to a study of the kinetics of reduction of electron density and charging of droplets in an initially overionized plasma, after addition of water droplets. A number of simplifying assumptions including uniform size and charge on droplets and negligible change in the radius of the droplet due to evaporation have been made.

Slat templated formation of efficient oxygen reduction electrocatalyst with a fluidic precursor

Science.gov (United States)

Tan, Yao

2018-05-01

Development of cost-effective and efficient oxygen reduction catalyst is critical for the commercialization of proton exchange membrane fuel cell. Metal and nitrogen co-doped carbon is recognized as a promising alternative to traditional platinum-based oxygen reduction catalyst. Herein, we report a novel metal and nitrogen co-doped carbon catalyst with an ionic liquid precursor. Salt template, which can be easily removed with mild treatment after the synthesis, is used to generate abundant mesopores in the resulting catalyst. We show that the novel catalyst shows a superior activity comparable to commercial Pt/C catalyst. Furthermore, the important role of the mesopore for the activity of the catalyst is demonstrated.

Development of silver-gas diffusion electrodes for the oxygen reduction reaction by electrodeposition

Energy Technology Data Exchange (ETDEWEB)

Salomé, Sónia; Rego, Rosa; Oliveira, M. Cristina, E-mail: mcris@utad.pt

2013-12-16

Silver-gas diffusion electrodes (Ag-GDE) were prepared by direct deposition of the catalyst onto a carbon paper support by electrodeposition. This deposition technique, under potentiostatic and galvanostatic mode, allows the production of well dispersed ultra-low Ag loading levels. The catalytic activity of the prepared materials towards the oxygen reduction reaction (ORR) was investigated in the alkaline solution and its tolerance to methanol was evaluated. Based on an Ag-ink prepared from the electrodeposit material and RDE experiments, it was concluded that the ORR occurs via a four-electron pathway on the Ag electrodeposit. The combination of reasonably high catalytic activity, efficiency, low price, facile and green synthesis makes the electrodeposited Ag-GDE attractive for the ORR in alkaline fuel cells. - Highlights: • A facile and simple way to successfully prepare catalyzed gas diffusion electrodes. • Ultra-low loadings of Ag-GDEs can be achieved. • Good tolerance to methanol and a high mass activity (3.14 mA{sub Ag} mg{sup −1}). • ORR occurs via a four-electron pathway.

Pulse radiolysis study of reaction of bull serum albumin electron adduct with oxygen. Polychromatic kinetics of reaction with adsorbed oxygen

International Nuclear Information System (INIS)

Pribush, A.G.

1986-01-01

By the method of pulse radiolysis the reaction of bull serum albumin electron adduct with oxygen is investigated. As pulsed radiation source electron linear accelerators with particle energy of 8.0 and 4.5 MeV and pulse time of 40 ns and 2.2 μs, respectively have been used. It is assumed that the disappearance of protein electron adduct occurs in the course of its interaction with oxygen adsorbed on protein globular molecule

Benzene degradation coupled with chlorate reduction in soil column study

NARCIS (Netherlands)

Tan, N.C.G.; Doesburg, van W.C.J.; Langenhoff, A.A.M.; Stams, A.J.M.

2006-01-01

Perchlorate and chlorate are electron acceptors that during reduction result in the formation of molecular oxygen. The produced oxygen can be used for activation of anaerobic persistent pollutants, like benzene. In this study chlorate was tested as potential electron acceptor to stimulate benzene

Heterojunction nanowires having high activity and stability for the reduction of oxygen: Formation by self-assembly of iron phthalocyanine with single walled carbon nanotubes (FePc/SWNTs)

KAUST Repository

Zhu, Jia

2014-04-01

A self-assembly approach to preparing iron phthalocyanine/single-walled carbon nanotube (FePc/SWNT) heterojunction nanowires as a new oxygen reduction reaction (ORR) electrocatalyst has been developed by virtue of water-adjusted dispersing in 1-cyclohexyl-pyrrolidone (CHP) of the two components. The FePc/SWNT nanowires have a higher Fermi level compared to pure FePc (d-band center, DFT. =. -0.69. eV versus -0.87. eV, respectively). Consequently, an efficient channel for transferring electron to the FePc surface is readily created, facilitating the interaction between FePc and oxygen, so enhancing the ORR kinetics. This heterojunction-determined activity in ORR illustrates a new stratagem to preparing non-noble ORR electrocatalysts of significant importance in constructing real-world fuel cells. © 2013 Elsevier Inc.

Electron-beam-induced reduction of Fe{sup 3+} in iron phosphate dihydrate, ferrihydrite, haemosiderin and ferritin as revealed by electron energy-loss spectroscopy

Energy Technology Data Exchange (ETDEWEB)

Pan, Ying-Hsi; Vaughan, Gareth; Brydson, Rik [Institute for Materials Research, SPEME, University of Leeds, Leeds LS2 9JT (United Kingdom); Bleloch, Andrew; Gass, Mhairi [SuperSTEM, Daresbury Laboratories, Warrington WA4 4AD (United Kingdom); Sader, Kasim [Institute for Materials Research, SPEME, University of Leeds, Leeds LS2 9JT (United Kingdom); SuperSTEM, Daresbury Laboratories, Warrington WA4 4AD (United Kingdom); Brown, Andy, E-mail: a.p.brown@leeds.ac.uk [Institute for Materials Research, SPEME, University of Leeds, Leeds LS2 9JT (United Kingdom)

2010-07-15

The effect of high-energy electron irradiation on ferritin/haemosiderin cores (in an iron-overloaded human liver biopsy), its mineral analogue; six-line ferrihydrite (6LFh), and iron phosphate dihydrate (which has similar octahedral ferric iron to oxygen coordination to that in ferrihydrite and ferritin/haemosiderin cores) has been investigated using electron energy-loss spectroscopy (EELS). Fe L{sub 2,3}-ionisation edges were recorded on two types of electron microscope: a 200 keV transmission electron microscope (TEM) and a 100 keV scanning transmission electron microscope (STEM), in order to investigate the damage mechanisms in operation and to establish a methodology for minimum specimen alteration during analytical electron microscopic characterisation. A specimen damage mechanism dominated by radiolysis that results in the preferential loss of iron co-ordinating ligands (O, OH and H{sub 2}O) is discussed. The net result of irradiation is structural re-organisation and reduction of iron within the iron hydroxides. At sufficiently low electron fluence and particularly in the lower incident energy, finer probe diameter STEM, the alteration is shown to be minimal. All the materials examined exhibit damage which as a function of cumulative fluence is best fitted by an inverse power-law, implying that several chemical and structural changes occur in response to the electron beam and we suggest that these are governed by secondary processes arising from the primary ionisation event. This work affirms that electron fluence and current density should be considered when measuring mixed valence ratios with EELS.

Synergy of Cobalt and Silver Microparticles Electrodeposited on Glassy Carbon for the Electrocatalysis of the Oxygen Reduction Reaction: An Electrochemical Investigation

Directory of Open Access Journals (Sweden)

Claudio Zafferoni

2015-08-01

Full Text Available The combination of two different metals, each of them acting on different steps of the oxygen reduction reaction (ORR, yields synergic catalytic effects. In this respect, the electrocatalytic effect of silver is enhanced by the addition of cobalt, which is able to break the O–O bond of molecular oxygen, thus accelerating the first step of the reduction mechanism. At the same time, research is to further reduce the catalyst’s cost, reducing the amount of Ag, which, even though being much less expensive than Pt, is still a noble metal. From this point of view, using a small amount of Ag together with an inexpensive material, such as graphite, represents a good compromise. The aim of this work was to verify if the synergic effects are still operating when very small amounts of cobalt (2–10 μg·cm−2 are added to the microparticles of silver electrodeposited on glassy carbon, described in a preceding paper from us. To better stress the different behaviour observed when cobalt and silver are contemporarily present in the deposit, the catalytic properties of cobalt alone were investigated. The analysis was completed by the Levich plots to evaluate the number of electrons involved and by Tafel plots to show the effects on the reaction mechanism.

Oxygen Reduction Reaction on PtCo Nanocatalyst: (Bi)sulfate Anion Poisoning

Science.gov (United States)

Liu, Jie; Huang, Yan

2018-05-01

Pt alloy electrocatalysts are susceptible to anion adsorption in the working environment of fuel cells. In this work, the unavoidable bisulfate and sulfate ((bi)sulfate) poisoning of the oxygen reduction reaction (ORR) on a common PtCo nanocatalyst was studied by the rotating disk electrode (RDE) technique, for the first time to the best of our knowledge. The specific activity decreases linearly with the logarithm of (bi)sulfate concentration under various high potentials. This demonstrates that the (bi)sulfate adsorption does not affect the free energy of ORR activation at a given potential. Moreover, it is speculated that these two conditions, the adsorption of one O2 molecule onto two Pt sites and this adsorption as a rate-determining step of ORR reaction, are unlikely to exist simultaneously.

High index surfaces of Au-nanocrystals supported on one-dimensional MoO3-nanorod as a bi-functional electrocatalyst for ethanol oxidation and oxygen reduction

International Nuclear Information System (INIS)

Karuppasamy, L.; Chen, C.Y.; Anandan, S.; Wu, J.J.

2017-01-01

Highlights: •Synthesis of a new class of Au nanocrystals enclosed with high index surface supported on MoO 3 nanorods by ultrasonic probe method. •The role of supporting materials reduces the loading of Au and acts as a co-catalyst. •The as prepared electrocatalyst exhibits enhanced catalytic activity and stability towards both EOR and ORR. -- Abstract: The design of highly active electrocatalyst for ethanol electrooxidation (EOR) and oxygen reduction reaction (ORR) is of great significance for the improvement of efficient direct ethanol fuel cells (DEFCs). Therefore, creating high index facets nanocrystals with abundant catalytic active sites of stepped atoms is an effective way to enhance the electrocatalytic performance. In this article, we prepared the high index surface structures of Au nanocrystals supported on one-dimensional (1-D) MoO 3 nanorods by using two steps ultrasonic probe irradiation method. The size and physical properties of as electrocatalysts were studied by using field emission scanning electron microscopy (FE-SEM), high-resolution transmission electron microscopy (HR-TEM), and x-ray diffraction (XRD) instrumentation. Besides, the catalytic activity of as Au-MoO 3 electrocatalyst was determined by using cyclic voltammetry (CV), chronoamperometric (CA), electrochemical impedance spectroscopy (EIS), CO-stripping, and linear sweep voltammetry-rotating disk electrode (LSV-RDE). As a consequence, the Au-MoO 3 nanocomposites has been considered as an effective electrocatalyst for both ethanol oxidation and oxygen reduction reaction.

The roles of polycarboxylates in Cr(VI)/sulfite reaction system: Involvement of reactive oxygen species and intramolecular electron transfer

Energy Technology Data Exchange (ETDEWEB)

Jiang, Bo, E-mail: bjiang86upc@163.com [State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Qingdao 266580, Shandong (China); School of Environmental and Municipal Engineering, Qingdao University of Technology, Qingdao 266033 (China); Wang, Xianli; Liu, Yukun [State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Qingdao 266580, Shandong (China); Wang, Zhaohui [College of Environmental Science and Engineering, Donghua University, Shanghai 201620 (China); Southern Cross GeoScience, Southern Cross University, Lismore, NSW 2480 (Australia); Zheng, Jingtang, E-mail: jtzheng03@163.com [State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Qingdao 266580, Shandong (China); Wu, Mingbo, E-mail: wumb@upc.edu.cn [State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Qingdao 266580, Shandong (China)

2016-03-05

Highlights: • The formations of SO{sub 4}·{sup −} and OH·, involve in Cr(VI) reduction induced by S(IV). • Affinity of polycarboxylate to Cr(VI) accelerates Cr(VI) reduction rate. • Polycarboxylates can act as electron donors for Cr(VI) reduction retrenching S(IV). • Only oxalate can enhance the formations of SO{sub 4}·{sup −} and OH· in Cr(VI)/S(IV) system. - Abstract: In this study, the effects of polycarboxylates on both Cr(VI) reduction and S(IV) consumption in Cr(VI)/S(IV) system was investigated in acidic solution. Under aerobic condition, the productions of reactive oxygen species (ROS), i.e., SO{sub 4}·{sup −} and OH·, have been confirmed in S(IV) reducing Cr(VI) process by using electron spin resonance and fluorescence spectrum techniques, leading to the excess consumption of S(IV). However, when polycarboxylates (oxalic, citric, malic and tartaric acid) were present in Cr(VI)/S(IV) system, the affinity of polycarboxylates to CrSO{sub 6}{sup 2−} can greatly promote the reduction of Cr(VI) via expanding the coordination of Cr(VI) species from tetrahedron to hexahedron. Besides, as alternatives to S(IV), these polycarboxylates can also act as electron donors for Cr(VI) reduction via intramolecular electron transfer reaction, which is dependent on the energies of the highest occupied molecular orbital of these polycarboxylates. Notably, the variant electron donating capacity of these polycarboxylates resulted in different yield of ROS and therefore the oxidation efficiencies of other pollutants, e.g., rhodamine B and As(III). Generally, this study does not only shed light on the mechanism of S(IV) reducing Cr(VI) process mediated by polycarboxylates, but also provides an escalated, cost-effective and green strategy for the remediation of Cr(VI) using sulfite as a reductant.

Proton conductive Pt-Co nanoparticles anchoring on citric acid functionalized graphene for efficient oxygen reduction reaction

Science.gov (United States)

Zhao, Yige; Liu, Jingjun; Wu, Yijun; Wang, Feng

2017-08-01

Designing highly efficient electro-catalysts for the oxygen reduction reaction (ORR) has been regarded as a demanding task in the development of renewable energy sources. However, little attention has been paid on improving Pt-based catalysts by promoting proton transfer from the electrolyte solutions to the catalyst layer at the cathode. Herein, we design proton conductive Pt-Co alloy nanoparticles anchoring on citric acid functionalized graphene (Pt-Co/CA-G) catalysts for efficient ORR. The facile modification approach for graphene can introduce oxygenated functional groups on the graphene surface to promote proton transfer as well as keeping the high electron conductivity without destroying the graphene original structure. The electrochemical results show that the Pt-Co/CA-G catalyst exhibits more excellent ORR activity and stability than the commercial Pt/C catalyst, which can be attributed to its improved proton transfer ability. The fast proton transfer comes from the hydrogen-bonding networks formed by the interaction between the oxygenated functional groups and water molecules. This work provides not only a novel and simple approach to modify graphene but also an effective strategy to improve Pt-based catalysts for the ORR.

Fuel cell electrocatalsis : oxygen reduction on Pt-based nanoparticle catalysts

NARCIS (Netherlands)

Vliet, Dennis Franciscus van der

2010-01-01

The thesis contains a discussion on the subject of the Oxygen Reduction Reaction (ORR) on Pt-alloy nanoparticle catalysts in the Rotating Disk Electrode (RDE) method. An insight in some of the difficulties of this method is given with proper solutions and compensations for these problems. Pt3Co,

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

Science.gov (United States)

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.

A novel differential electrochemical mass spectrometry method to determine the product distribution from parasitic Methanol oxidation reaction on oxygen reduction reaction catalysts

Science.gov (United States)

Jurzinsky, Tilman; Kurzhals, Philipp; Cremers, Carsten

2018-06-01

The oxygen reduction reaction is in research focus since several decades due to its importance for the overall fuel cell performance. In direct methanol fuel cells, the crossover of methanol and its subsequent parasitic oxidation are main issues when it comes to preventing fuel cell performance losses. In this work, we present a novel differential electrochemical mass spectrometry method to evaluate oxygen reduction reaction catalysts on their tolerance to methanol being present at the cathode. Besides this, the setup allows to measure under more realistic fuel cell conditions than typical rotating disc electrode measurements, because the oxygen reduction reaction is evaluated in gaseous phase and a gas diffusion electrode is used as working electrode. Due to the new method, it was possible to investigate the oxygen reduction reaction on two commonly used catalysts (Pt/C and Pt3Co/C) in absence and presence of methanol. It was found, that Pt3Co/C is less prone to parasitic current losses due to methanol oxidation reaction. By connecting a mass spectrometer to the electrochemical cell, the new method allows to determine the products formed on the catalysts due to parasitic methanol electrooxidation.

Localized conductive patterning via focused electron beam reduction of graphene oxide

Energy Technology Data Exchange (ETDEWEB)

Kim, Songkil; Henry, Mathias [George W. Woodruff School of Mechanical Engineering, Georgia Institute of Technology, Atlanta, Georgia 30332 (United States); Kulkarni, Dhaval D.; Zackowski, Paul; Jang, Seung Soon; Tsukruk, Vladimir V. [School of Materials Science and Engineering, Georgia Institute of Technology, Atlanta, Georgia 30332 (United States); Fedorov, Andrei G., E-mail: agf@gatech.edu [George W. Woodruff School of Mechanical Engineering, Georgia Institute of Technology, Atlanta, Georgia 30332 (United States); Parker H. Petit Institute for Bioengineering and Bioscience, Georgia Institute of Technology, Atlanta, Georgia 30332 (United States)

2015-03-30

We report on a method for “direct-write” conductive patterning via reduction of graphene oxide (GO) sheets using focused electron beam induced deposition (FEBID) of carbon. FEBID treatment of the intrinsically dielectric graphene oxide between two metal terminals opens up the conduction channel, thus enabling a unique capability for nanoscale conductive domain patterning in GO. An increase in FEBID electron dose results in a significant increase of the domain electrical conductivity with improving linearity of drain-source current vs. voltage dependence, indicative of a change of graphene oxide electronic properties from insulating to semiconducting. Density functional theory calculations suggest a possible mechanism underlying this experimentally observed phenomenon, as localized reduction of graphene oxide layers via interactions with highly reactive intermediates of electron-beam-assisted dissociation of surface-adsorbed hydrocarbon molecules. These findings establish an unusual route for using FEBID as nanoscale lithography and patterning technique for engineering carbon-based nanomaterials and devices with locally tailored electronic properties.

Reactive Oxygen Species Production by Forward and Reverse Electron Fluxes in the Mitochondrial Respiratory Chain

Science.gov (United States)

Selivanov, Vitaly A.; Votyakova, Tatyana V.; Pivtoraiko, Violetta N.; Zeak, Jennifer; Sukhomlin, Tatiana; Trucco, Massimo; Roca, Josep; Cascante, Marta

2011-01-01

Reactive oxygen species (ROS) produced in the mitochondrial respiratory chain (RC) are primary signals that modulate cellular adaptation to environment, and are also destructive factors that damage cells under the conditions of hypoxia/reoxygenation relevant for various systemic diseases or transplantation. The important role of ROS in cell survival requires detailed investigation of mechanism and determinants of ROS production. To perform such an investigation we extended our rule-based model of complex III in order to account for electron transport in the whole RC coupled to proton translocation, transmembrane electrochemical potential generation, TCA cycle reactions, and substrate transport to mitochondria. It fits respiratory electron fluxes measured in rat brain mitochondria fueled by succinate or pyruvate and malate, and the dynamics of NAD+ reduction by reverse electron transport from succinate through complex I. The fitting of measured characteristics gave an insight into the mechanism of underlying processes governing the formation of free radicals that can transfer an unpaired electron to oxygen-producing superoxide and thus can initiate the generation of ROS. Our analysis revealed an association of ROS production with levels of specific radicals of individual electron transporters and their combinations in species of complexes I and III. It was found that the phenomenon of bistability, revealed previously as a property of complex III, remains valid for the whole RC. The conditions for switching to a state with a high content of free radicals in complex III were predicted based on theoretical analysis and were confirmed experimentally. These findings provide a new insight into the mechanisms of ROS production in RC. PMID:21483483

Temperature dependence of the oxygen reduction kinetics on Ru{sub x}Se{sub y}/C catalysts

Energy Technology Data Exchange (ETDEWEB)

Leveratto, D.; Racz, A.; Savinova, E.R.; Stimming, U. [Technische Universitaet Muenchen, Department of Physics E19, James-Franck-Str. 1, D-85748 Garching (Germany)

2006-07-15

The temperature dependence of the oxygen reduction kinetics on carbon-supported Ru{sub x}Se{sub y} catalysts is studied using a rotating disc electrode in 0.5 M H{sub 2}SO{sub 4} in the temperature interval from 25 C to 65 C. When the absolute value of the overpotential is below ca. 0.65 V, the reaction is limited by a one-electron charge transfer step, where the transfer coefficient is independent of the temperature and equal to 0.44. The apparent activation enthalpy at zero overpotential is 0.49 eV and the pre-exponential factor is independent of the temperature. (Abstract Copyright [2006], Wiley Periodicals, Inc.)

Highly Selective TiN-Supported Highly Dispersed Pt Catalyst: Ultra Active toward Hydrogen Oxidation and Inactive toward Oxygen Reduction.

Science.gov (United States)

Luo, Junming; Tang, Haibo; Tian, Xinlong; Hou, Sanying; Li, Xiuhua; Du, Li; Liao, Shijun

2018-01-31

The severe dissolution of the cathode catalyst, caused by an undesired oxygen reduction reaction at the anode during startup and shutdown, is a fatal challenge to practical applications of polymer electrolyte membrane fuel cells. To address this important issue, according to the distinct structure-sensitivity between the σ-type bond in H 2 and the π-type bond in O 2 , we design a HD-Pt/TiN material by highly dispersing Pt on the TiN surface to inhibit the unwanted oxygen reduction reaction. The highly dispersed Pt/TiN catalyst exhibits excellent selectivity toward hydrogen oxidation and oxygen reduction reactions. With a Pt loading of 0.88 wt %, our catalyst shows excellent hydrogen oxidation reaction activity, close to that of commercial 20 wt % Pt/C catalyst, and much lower oxygen reduction reaction activity than the commercial 20 wt % Pt/C catalyst. The lack of well-ordered Pt facets is responsible for the excellent selectivity of the HD-Pt/TiN materials toward hydrogen oxidation and oxygen reduction reactions. Our work provides a new and cost-effective solution to design selective catalysts toward hydrogen oxidation and oxygen reduction reactions, making the strategy of using oxygen-tolerant anode catalyst to improve the stability of polymer electrolyte membrane fuel cells during startup and shutdown more affordable and practical.

Four-electron deoxygenative reductive coupling of carbon monoxide at a single metal site

Science.gov (United States)

Buss, Joshua A.; Agapie, Theodor

2016-01-01

Carbon dioxide is the ultimate source of the fossil fuels that are both central to modern life and problematic: their use increases atmospheric levels of greenhouse gases, and their availability is geopolitically constrained. Using carbon dioxide as a feedstock to produce synthetic fuels might, in principle, alleviate these concerns. Although many homogeneous and heterogeneous catalysts convert carbon dioxide to carbon monoxide, further deoxygenative coupling of carbon monoxide to generate useful multicarbon products is challenging. Molybdenum and vanadium nitrogenases are capable of converting carbon monoxide into hydrocarbons under mild conditions, using discrete electron and proton sources. Electrocatalytic reduction of carbon monoxide on copper catalysts also uses a combination of electrons and protons, while the industrial Fischer-Tropsch process uses dihydrogen as a combined source of electrons and electrophiles for carbon monoxide coupling at high temperatures and pressures. However, these enzymatic and heterogeneous systems are difficult to probe mechanistically. Molecular catalysts have been studied extensively to investigate the elementary steps by which carbon monoxide is deoxygenated and coupled, but a single metal site that can efficiently induce the required scission of carbon-oxygen bonds and generate carbon-carbon bonds has not yet been documented. Here we describe a molybdenum compound, supported by a terphenyl-diphosphine ligand, that activates and cleaves the strong carbon-oxygen bond of carbon monoxide, enacts carbon-carbon coupling, and spontaneously dissociates the resulting fragment. This complex four-electron transformation is enabled by the terphenyl-diphosphine ligand, which acts as an electron reservoir and exhibits the coordinative flexibility needed to stabilize the different intermediates involved in the overall reaction sequence. We anticipate that these design elements might help in the development of efficient catalysts for

Coupled Effect of Ferrous Ion and Oxygen on the Electron Selectivity of Zerovalent Iron for Selenate Sequestration.

Science.gov (United States)

Qin, Hejie; Li, Jinxiang; Yang, Hongyi; Pan, Bingcai; Zhang, Weiming; Guan, Xiaohong

2017-05-02

Although the electron selectivity (ES) of zerovalent iron (ZVI) for target contaminant and its utilization ratio (UR) decide the removal capacity of ZVI, little effort has been made to improve them. Taking selenate [Se(VI)] as a target contaminant, this study investigated the coupled influence of aeration gas and Fe(II) on the ES and UR of ZVI. Oxygen was necessary for effective removal of Se(VI) by ZVI without Fe(II) addition. Due to the application of 1.0 mM Fe(II), the ES of ZVI was increased from 3.2-3.6% to 6.2-6.8% and the UR of ZVI was improved by 5.0-19.4% under aerobic conditions, which resulted in a 100-180% increase in the Se(VI) removal capacity by ZVI. Se(VI) reduction by Fe 0 was a heterogeneous redox reaction, and the enrichment of Se(VI) on ZVI surface was the first step of electron transfer from Fe 0 core to Se(VI). Oxygen promoted the generation of iron (hydr)oxides, which facilitated the enrichment of Se(VI) on the ZVI particle surface. Therefore, the high oxygen fraction (25-50%) in the purging gas resulted in only a slight decrease in the ES of ZVI. Fe(II) addition resulted in a pH drop and promoted the generation of lepidocrocite and magnetite, which benefited Se(VI) adsorption and the following electron transfer from underlying Fe 0 to surface-located Se(VI).

Experimental reduction of simulated lunar glass by carbon and hydrogen and implications for lunar base oxygen production

International Nuclear Information System (INIS)

Mckay, D.S.; Morris, R.V.; Jurewicz, A.J.

1991-01-01

The most abundant element in lunar rocks and soils is oxygen which makes up approximately 45 percent by weight of the typical lunar samples returned during the Apollo missions. This oxygen is not present as a gas but is tightly bound to other elements in mineral or glass. When people return to the Moon to explore and live, the extraction of this oxygen at a lunar outpost may be a major goal during the early years of operation. Among the most studied processes for oxygen extraction is the reduction of ilmenite by hydrogen gas to form metallic iron, titanium oxide, and oxygen. A related process is proposed which overcomes some of the disadvantages of ilmenite reduction. It is proposed that oxygen can be extracted by direct reduction of native lunar pyroclactic glass using either carbon, carbon monoxide, or hydrogen. In order to evaluate the feasibility of this proposed process a series of experiments on synthetic lunar glass are presented. The results and a discussion of the experiments are presented

Effect of hydrogen peroxide and camellia sinensis extract on reduction of oxygen level in graphene oxide

Science.gov (United States)

Celina Selvakumari, J.; Dhanalakshmi, J.; Pathinettam Padiyan, D.

2016-10-01

The intention of this work is to reduce the oxygen level in graphene oxide. The reduction process was initiated while preparing graphene oxide using modified Hummer’s method. In this new method, increase in hydrogen peroxide concentration during the preparation process results in the oxygen content reduction. Adding green tea (camellia sinensis) extract with increased hydrogen peroxide results in further reduction of oxygen content and changed the graphene oxide to reduced graphene oxide. The structural and optical properties of the new found reduced graphene oxide was analysed using XRD, FTIR, TEM, Raman and UV-vis spectra. The overall observation reflects that the sp3 carbon network of graphene oxide changed into sp2 carbon lattice of graphene which is very handful in supercapacitor and biosensor fields.

Enhancement of the oxygen reduction on nitride stabilized pt-M (M=Fe, Co, and Ni) core–shell nanoparticle electrocatalysts

KAUST Repository

Kuttiyiel, Kurian A.; Choi, YongMan; Hwang, Sun-Mi; Park, Gu-Gon; Yang, Tae-Hyun; Su, Dong; Sasaki, Kotaro; Liu, Ping; Adzic, Radoslav R.

2015-01-01

Given the harsh operating conditions in hydrogen/oxygen fuel cells, the stability of catalysts is one of the critical questions affecting their commercialization. We describe a distinct class of oxygen reduction (ORR) core–shell electrocatalysts comprised of nitride metal cores enclosed by thin Pt shells that is easily synthesized. The synthesis is reproducible and amenable to scale up. Our theoretical analysis and the experimental data indicate that metal nitride nanoparticle cores could significantly enhance the ORR activity as well as the durability of the core–shell catalysts as a consequence of combined geometrical, electronic and segregation effects on the Pt shells. In addition to its fuel cells application, this class of catalysts holds promise to significantly contribute in resolving the problem of platinum scarcity and furthermore indicates the guidelines for future research and development.

Enhancement of the oxygen reduction on nitride stabilized pt-M (M=Fe, Co, and Ni) core–shell nanoparticle electrocatalysts

KAUST Repository

Kuttiyiel, Kurian A.

2015-04-01

Given the harsh operating conditions in hydrogen/oxygen fuel cells, the stability of catalysts is one of the critical questions affecting their commercialization. We describe a distinct class of oxygen reduction (ORR) core–shell electrocatalysts comprised of nitride metal cores enclosed by thin Pt shells that is easily synthesized. The synthesis is reproducible and amenable to scale up. Our theoretical analysis and the experimental data indicate that metal nitride nanoparticle cores could significantly enhance the ORR activity as well as the durability of the core–shell catalysts as a consequence of combined geometrical, electronic and segregation effects on the Pt shells. In addition to its fuel cells application, this class of catalysts holds promise to significantly contribute in resolving the problem of platinum scarcity and furthermore indicates the guidelines for future research and development.

Fate of free radicals generated during one-electron reductions of 4-alkyl-1,4-peroxyquinols by cytochrome P-450

International Nuclear Information System (INIS)

Yumibe, N.P.; Thompson, J.A.

1988-01-01

Free radicals resulting from the one-electron reduction and subsequent homolytic cleavage of oxygen-oxygen bonds by heme proteins are likely to be responsible for some aspects of the toxicity of organic hydroperoxides. In the present work, effects of the 4-alkyl substituent of 2,6-di-tert-butyl-4-alkyl-4-hydroperoxycytohexa-2,5-dienones on radical production were investigated with microsomal cytochrome P-450 from rat liver. Quinoxy radicals from homolysis of the peroxyquinols underwent β-scission to produce a quinone and an alkyl radical, and this process occurred with increasing frequency as the stability of the alkyl radical increased. The fate of benzyl and 2-phenylethyl radicals generated from the appropriately substituted peroxyquinols was investigated also. The former was converted to benzyl alcohol, benzaldehyde, and toluene and the latter to 2-phenylethanol, phenylacetaldehyde, ethylbenzene, styrene, and benzaldehyde. Oxygen-18 labeling studies demonstrate that 80-85% of the benzyl alcohol incorporated oxygen from the hydroperoxide and the balance from molecular oxygen. This indicates that the predominant reaction pathway involved recombination between the benzyl radical and the iron-bound hydroxyl radical of the P-450 intermediate complex. By contrast, about 50% of 2-phenylethanol from the 2-phenylethyl radical incorporated oxygen from water and the balance from O 2 . Two alternative mechanisms are proposed to explain the formation of 2-phenylethanol that contained oxygen from water and the concurrent formation of styrene: (a) oxygen exchange of the P-450 intermediate with water, followed by hydrogen abstraction and radical recombination reactions with the P-450 complex, or (b) oxidation of the radical to the 2-phenylethyl cation followed by proton elimination and hydration

Disordering of two-dimensional oxyxgen lattices on Mo(011) initiated by electron transitions in oxygen and molybdenum atoms

International Nuclear Information System (INIS)

Zasimovich, I.N.; Klimenko, E.V.; Naumovets, A.G.

1988-01-01

The first observation of electron-induced disordering (EID) of the submonolayer film of heavier adsorbate-oxygen is reported. The investigation of energy dependence of the effective cross section of this process, which points to the fact that EID can be initiated by the electron transitions not only in adatoms, but in the substrate, is also presented. When irradiating by electrons, the sample surface cooled up to 77 K, intensity of diffraction reflects of the (2x2) and (6x2) structures decreases rather quickly, but the reflects of more dense (6x1) lattice do not practically attenuate. The conclusions are made that the knowledge of physical factors, determining the probability of radiation defect formation in an adfilm, gives the possibility either to avoid disordering, if it is undesirable, or to use it to control the surface properties

Volume Reduction of Decommissioning Burnable Waste with Oxygen Enrich Incinerator

International Nuclear Information System (INIS)

Min, B. Y.; Yang, D. S.; Lee, K. W.; Choi, J. W.

2016-01-01

The incineration technology is an effective treatment method that contains hazardous chemicals as well as radioactive contamination. The volume reduction of the combustible wastes through the incineration technologies has merits from the view point of a decrease in the amount of waste to be disposed of resulting in a reduction of the disposal cost. Incineration is generally accepted as a method of reducing the volume of radioactive waste. The incineration technology is an effective treatment method that contains hazardous chemicals as well as radioactive contamination. This paper covers the general facility operation of an oxygen-enriched incinerator for the treatment of decommissioning wastes generated from a decommissioning project. The combustible wastes have been treated by the utilization of incinerator the capacity of the average 20 kg/hr. The decommissioning combustible waste of about 31 tons has been treated using Oxygen Enriched incinerator by at the end of 2016. The off-gas flow and temperature were maintained constant or within the desired range. The measured gases and particulate materials in the stack were considerably below the regulatory limits.

Volume Reduction of Decommissioning Burnable Waste with Oxygen Enrich Incinerator

Energy Technology Data Exchange (ETDEWEB)

Min, B. Y.; Yang, D. S.; Lee, K. W.; Choi, J. W. [KAERI, Daejeon (Korea, Republic of)

2016-05-15

The incineration technology is an effective treatment method that contains hazardous chemicals as well as radioactive contamination. The volume reduction of the combustible wastes through the incineration technologies has merits from the view point of a decrease in the amount of waste to be disposed of resulting in a reduction of the disposal cost. Incineration is generally accepted as a method of reducing the volume of radioactive waste. The incineration technology is an effective treatment method that contains hazardous chemicals as well as radioactive contamination. This paper covers the general facility operation of an oxygen-enriched incinerator for the treatment of decommissioning wastes generated from a decommissioning project. The combustible wastes have been treated by the utilization of incinerator the capacity of the average 20 kg/hr. The decommissioning combustible waste of about 31 tons has been treated using Oxygen Enriched incinerator by at the end of 2016. The off-gas flow and temperature were maintained constant or within the desired range. The measured gases and particulate materials in the stack were considerably below the regulatory limits.

Resonances in Electron Impact on Atomic Oxygen

International Nuclear Information System (INIS)

Yang, Wang; Ya-Jun, Zhou; Li-Guang, Jiao; Ratnavelu, Kuru

2008-01-01

The momentum-space coupled-channels-optical (CCO) method is used to study the resonances in electron-oxygen collision in the energy region of 9–12eV. Present results have shown agreement with the available experimental and theoretical results, and new positions of resonances are found by the comparison of total cross sections. (fundamental areas of phenomenology (including applications))

Substrate effect on oxygen reduction electrocatalysis

International Nuclear Information System (INIS)

Timperman, L.; Feng, Y.J.; Vogel, W.; Alonso-Vante, N.

2010-01-01

The oxygen reduction reaction (ORR) was investigated on carbon (XC-72) supported platinum nanoparticles, generated via the carbonyl chemical route and on oxide composites supported platinum generated via the UV-photo-deposition technique in sulfuric acid medium. The behavior of Pt/C was examined using a careful dosing of the catalyst loading spanning the range from 4.3 to 131 μg cm -2 . The ORR electrochemical response of Pt/C (in line with recent literature data) is put into contrast with the Pt/oxide-composite systems. Our results point out that it is possible to use smaller amounts of catalyst for the ORR when platinum atoms interact with the oxide (anatase) surface of the substrate composite. Evidence of the incipient metal-substrate interaction is discussed in the light of the results of XRD experiments.

The role of metals in production and scavenging of reactive oxygen species in photosystem II.

Science.gov (United States)

Pospíšil, Pavel

2014-07-01

Metal ions play a crucial role in enzymatic reactions in all photosynthetic organisms such as cyanobacteria, algae and plants. It well known that metal ions maintain the binding of substrate in the active site of the metalloenzymes and control the redox activity of the metalloenzyme in the enzymatic reaction. A large pigment-protein complex, PSII, known to serve as a water-plastoquinone oxidoreductase, contains three metal centers comprising non-heme iron, heme iron of Cyt b559 and the water-splitting manganese complex. Metal ions bound to PSII proteins maintain the electron transport from water to plastoquinone and regulate the pro-oxidant and antioxidant activity in PSII. In this review, attention is focused on the role of PSII metal centers in (i) the formation of superoxide anion and hydroxyl radicals by sequential one-electron reduction of molecular oxygen and the formation of hydrogen peroxide by incomplete two-electron oxidation of water; and (ii) the elimination of superoxide anion radical by one-electron oxidation and reduction (superoxide dismutase activity) and of hydrogen peroxide by two-electron oxidation and reduction (catalase activity). The balance between the formation and elimination of reactive oxygen species by PSII metal centers is discussed as an important aspect in the prevention of photo-oxidative damage of PSII proteins and lipids. © The Author 2014. Published by Oxford University Press on behalf of Japanese Society of Plant Physiologists. All rights reserved. For permissions, please email: journals.permissions@oup.com.

Electroenzymatic Reactions With Oxygen on Laccase-Modified Electrodes in Anhydrous (Pure) Organic Solvent

DEFF Research Database (Denmark)

Yarapolov, A.; Shleev, S.; Zaitseva, E.

2007-01-01

in two different ways: (i) by studying the electroreduction of oxygen in anhydrous DMSO via a direct electron transfer mechanism without proton donors and (ii) by doing the same experiments in the presence of laccase substrates, which display in pure organic solvents both the properties of electron......The electroenzymatic reactions of Trametes hirsuta laccase in the pure organic solvent dimethyl sulfoxide (DMSO) have been investigated within the framework for potential use as a catalytic reaction scheme for oxygen reduction. The bioelectrochemical characteristics of laccase were investigated...... donors as well as the properties of weak acids. The results obtained with laccase in anhydrous DMSO were compared with those obtained previously in aqueous buffer. It was shown that in the absence of proton donors under oxygenated conditions, formation of superoxide anion radicals is prevented at bare...

Kinetics of sodium borohydride direct oxidation and oxygen reduction in sodium hydroxide electrolyte - Part II. O-2 reduction

Czech Academy of Sciences Publication Activity Database

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

2006-01-01

Roč. 51, č. 25 (2006), s. 5452-5458 ISSN 0013-4686 Institutional research plan: CEZ:AV0Z40320502 Keywords : oxygen reduction reaction selectivity * platinum * silver Subject RIV: CA - Inorganic Chemistry Impact factor: 2.955, year: 2006

The development of efficient two-photon singlet oxygen sensitizers

DEFF Research Database (Denmark)

Nielsen, Christian Benedikt

The development of efficient two-photon singlet oxygen sensitizers is addressed focusing on organic synthesis. Photophysical measurements were carried out on new lipophilic molecules, where two-photon absorption cross sections and singlet oxygen quantumyields were measured. Design principles...... for making efficient two-photon singlet oxygen sensitizers were then constructed from these results. Charge-transfer in the excited state of the prepared molecules was shown to play a pivotal role in the generationof singlet oxygen. This was established through studies of substituent effects on both...... the singlet oxygen yield and the two-photon absorption cross section, where it was revealed that a careful balancing of the amount of charge transfer present in theexcited state of the sensitizer is necessary to obtain both a high singlet oxygen quantum yield and a high two-photon cross section. An increasing...

Heavy-ion induced secondary electron emission from Mg, Al, and Si partially covered with oxygen

International Nuclear Information System (INIS)

Weng, J; Veje, E.

1984-01-01

We have bombarded Mg, Al, and Si with 80 keV Ar + ions and measured the secondary electron emission yields at projectile incidence angles from 0 0 to 85 0 , with oxygen present at the target as well as under UHV conditions. The total secondary electron emission yields are found to depend fairly much on the amount of oxygen present. The three elements studied show relatively large individual variations. For all three elements, and with as well as without oxygen present, the relative secondary electron emission yield is observed to vary as 1/cos v, where v is the angle of incidence of the projectiles. This seems to indicate that the secondary electron production is initiated uniformly along the projectile path in the solid, in a region close to the surface. The results are discussed, and it is tentatively suggested, that the increase in secondary electron emission, caused by the presence of oxygen, originates from neutralization of sputtered oxygen, which initially is sitting as O 2- ions. (orig.)

Effects of grain boundaries at the electrolyte/cathode interfaces on oxygen reduction reaction kinetics of solid oxide fuel cells

Energy Technology Data Exchange (ETDEWEB)

Choi, Min Gi; Koo, Ja Yang; Ahn, Min Woo; Lee, Won Young [Dept. of Mechanical Engineering, Sungkyunkwan University, Suwon (Korea, Republic of)

2017-04-15

We systematically investigated the effects of grain boundaries (GBs) at the electrolyte/cathode interface of two conventional electrolyte materials, i.e., yttria-stabilized zirconia (YSZ) and gadolinia-doped ceria (GDC). We deposited additional layers by pulsed laser deposition to control the GB density on top of the polycrystalline substrates, obtaining significant improvements in peak power density (two-fold for YSZ and three-fold for GDC). The enhanced performance at high GB density in the additional layer could be ascribed to the accumulation of oxygen vacancies, which are known to be more active sites for oxygen reduction reactions (ORR) than grain cores. GDC exhibited a higher enhancement than YSZ, due to the easier formation, and thus higher concentration, of oxygen vacancies for ORR. The strong relation between the concentration of oxygen vacancies and the surface exchange characteristics substantiated the role of GBs at electrolyte/cathode interfaces on ORR kinetics, providing new design parameters for highly performing solid oxide fuel cells.

Aligned carbon nanotube with electro-catalytic activity for oxygen reduction reaction

Science.gov (United States)

Liu, Di-Jia; Yang, Junbing; Wang, Xiaoping

2010-08-03

A catalyst for an electro-chemical oxygen reduction reaction (ORR) of a bundle of longitudinally aligned carbon nanotubes having a catalytically active transition metal incorporated longitudinally in said nanotubes. A method of making an electro-chemical catalyst for an oxygen reduction reaction (ORR) having a bundle of longitudinally aligned carbon nanotubes with a catalytically active transition metal incorporated throughout the nanotubes, where a substrate is in a first reaction zone, and a combination selected from one or more of a hydrocarbon and an organometallic compound containing an catalytically active transition metal and a nitrogen containing compound and an inert gas and a reducing gas is introduced into the first reaction zone which is maintained at a first reaction temperature for a time sufficient to vaporize material therein. The vaporized material is then introduced to a second reaction zone maintained at a second reaction temperature for a time sufficient to grow longitudinally aligned carbon nanotubes over the substrate with a catalytically active transition metal incorporated throughout the nanotubes.

Role of apical oxygen in 2-1-4 electron-doped superconductors

Energy Technology Data Exchange (ETDEWEB)

Richard, P.; Riou, G.; Jandl, S.; Poirier, M.; Fournier, P.; Nekvasil, V.; Divis, M

2004-08-01

We report a crystal-field infrared transmission and Raman study of oxygenated and reduced Nd{sub 2-x}Ce{sub x}CuO{sub 4} single crystals. Some Nd{sup 3+} crystal-field absorption bands corresponding to rare-earth ions in non-regular sites are attributed to Nd{sup 3+} ions in the vicinity of apical oxygens. This is correlated with a study of the A{sup *} ({approx}580 cm{sup -1}) Raman local mode and with the transport properties of undoped materials. We show that the apical oxygen is not removed by the reduction.

Dissimilatory nitrate reduction by Aspergillus terreus isolated from the seasonal oxygen minimum zone in the Arabian Sea.

Science.gov (United States)

Stief, Peter; Fuchs-Ocklenburg, Silvia; Kamp, Anja; Manohar, Cathrine-Sumathi; Houbraken, Jos; Boekhout, Teun; de Beer, Dirk; Stoeck, Thorsten

2014-02-11

A wealth of microbial eukaryotes is adapted to life in oxygen-deficient marine environments. Evidence is accumulating that some of these eukaryotes survive anoxia by employing dissimilatory nitrate reduction, a strategy that otherwise is widespread in prokaryotes. Here, we report on the anaerobic nitrate metabolism of the fungus Aspergillus terreus (isolate An-4) that was obtained from sediment in the seasonal oxygen minimum zone in the Arabian Sea, a globally important site of oceanic nitrogen loss and nitrous oxide emission. Axenic incubations of An-4 in the presence and absence of oxygen and nitrate revealed that this fungal isolate is capable of dissimilatory nitrate reduction to ammonium under anoxic conditions. A ¹⁵N-labeling experiment proved that An-4 produced and excreted ammonium through nitrate reduction at a rate of up to 175 nmol ¹⁵NH₄⁺ g⁻¹ protein h⁻¹. The products of dissimilatory nitrate reduction were ammonium (83%), nitrous oxide (15.5%), and nitrite (1.5%), while dinitrogen production was not observed. The process led to substantial cellular ATP production and biomass growth and also occurred when ammonium was added to suppress nitrate assimilation, stressing the dissimilatory nature of nitrate reduction. Interestingly, An-4 used intracellular nitrate stores (up to 6-8 μmol NO₃⁻ g⁻¹ protein) for dissimilatory nitrate reduction. Our findings expand the short list of microbial eukaryotes that store nitrate intracellularly and carry out dissimilatory nitrate reduction when oxygen is absent. In the currently spreading oxygen-deficient zones in the ocean, an as yet unexplored diversity of fungi may recycle nitrate to ammonium and nitrite, the substrates of the major nitrogen loss process anaerobic ammonium oxidation, and the potent greenhouse gas nitrous oxide.

Correlating Structure and Oxygen Reduction Activity on Y/Pt(111) and Gd/Pt(111) Single Crystals

DEFF Research Database (Denmark)

Ulrikkeholm, Elisabeth Therese; Pedersen, Anders Filsøe; Johansson, Tobias Peter

2015-01-01

Polymer Electrolyte Membrane Fuel Cells (PEMFC) hold promise as a zero-emission source of power, particularly suitable for automotive vehicles. However, the high loading of Pt required to catalyse the Oxygen Reduction Reaction (ORR) at the PEMFC cathode prevents the commercialisation of this tech......Polymer Electrolyte Membrane Fuel Cells (PEMFC) hold promise as a zero-emission source of power, particularly suitable for automotive vehicles. However, the high loading of Pt required to catalyse the Oxygen Reduction Reaction (ORR) at the PEMFC cathode prevents the commercialisation...... of this technology. Improving the activity of Pt by alloying it with other metals could decrease the loading of Pt at the cathode to a level comparable to Pt-group metal loading in internal combustion engines. PtxY and PtxGd exhibit exceptionally high activity for oxygen reduction, both in the polycrystalline form...

Two-dimensional boron: Lightest catalyst for hydrogen and oxygen evolution reaction

Energy Technology Data Exchange (ETDEWEB)

Mir, Showkat H. [Centre for Nano Science, Central University of Gujarat, Gandhinagar 382030 (India); Chakraborty, Sudip, E-mail: sudiphys@gmail.com, E-mail: prakash.jha@cug.ac.in; Wärnå, John [Condensed Matter Theory Group, Department of Physics and Astronomy, Uppsala University, Uppsala 75120 (Sweden); Jha, Prakash C., E-mail: sudiphys@gmail.com, E-mail: prakash.jha@cug.ac.in [School of Applied Material Sciences, Central University of Gujarat, Gandhinagar 382030 (India); Soni, Himadri [Lehrstuhl für Theoretische Chemie, Friedrich-Alexander Universität Erlangen-Nürnberg, Egerlandstraße 3, 91058 Erlangen (Germany); Jha, Prafulla K. [Department of Physics, Faculty of Science, The Maharaja Sayajirao University of Baroda, Vadodara 390 002 (India); Ahuja, Rajeev [Condensed Matter Theory Group, Department of Physics and Astronomy, Uppsala University, Uppsala 75120 (Sweden); Department of Materials and Engineering, Royal Institute of Technology (KTH), 10044 Stockholm (Sweden)

2016-08-01

The hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) have been envisaged on a two-dimensional (2D) boron sheet through electronic structure calculations based on a density functional theory framework. To date, boron sheets are the lightest 2D material and, therefore, exploring the catalytic activity of such a monolayer system would be quite intuitive both from fundamental and application perspectives. We have functionalized the boron sheet (BS) with different elemental dopants like carbon, nitrogen, phosphorous, sulphur, and lithium and determined the adsorption energy for each case while hydrogen and oxygen are on top of the doping site of the boron sheet. The free energy calculated from the individual adsorption energy for each functionalized BS subsequently guides us to predict which case of functionalization serves better for the HER or the OER.

Methanol resistant ruthenium electrocatalysts for oxygen reduction synthesized by pyrolysis of Ru{sub 3}(CO){sub 12} in different atmospheres

Energy Technology Data Exchange (ETDEWEB)

Altamirano-Gutierrez, A.; Jimenez-Sandoval, O.; Uribe-Godinez, J.; Borja-Arco, E. [Centro de Investigacion y de Estudios Avanzados del Instituto Politecnico Nacional (Cinvestav), Unidad Queretaro, Apartado Postal 1-798, Queretaro, Qro. 76001 (Mexico); Castellanos, R.H. [Universidad del Papaloapan, Campus Tuxtepec, Circuito Central No. 200, Col. Parque Industrial, Tuxtepec, Oax. 68301 (Mexico); Olivares-Ramirez, J.M. [Universidad Tecnologica de San Juan del Rio, Av. La Palma No. 125, Col. Vista Hermosa, San Juan del Rio, Qro. 76800 (Mexico)

2009-10-15

Novel ruthenium electrocatalysts for the oxygen reduction reaction (ORR) were prepared by pyrolysis of Ru{sub 3}(CO){sub 12} in three atmospheres: neutral (N{sub 2}), partially oxidative (air) and partially reductive (70:30 N{sub 2}/H{sub 2}), at temperatures in the 80-700 C range. The materials were characterized by FT-IR spectroscopy, X-ray diffraction and scanning electron microscopy. A thermogravimetric analysis of the Ru{sub 3}(CO){sub 12} precursor in the three atmospheres was also performed. The electrocatalytic properties of the materials were evaluated by rotating disk electrode measurements in 0.5 mol L{sup -1} H{sub 2}SO{sub 4}. The kinetic parameters, such as the Tafel slope, exchange current density and charge transfer coefficient, are reported. The catalysts prepared in N{sub 2} and N{sub 2}/H{sub 2}, in general, show a higher performance than those synthesized in air. In the two nitrogen containing atmospheres, a pyrolysis temperature of 360 C seems to lead to better electrocatalytic properties for the ORR. The new electrocatalysts are also tolerant to methanol concentrations as high as 2.0 mol L{sup -1}. (author)

A metal-free electrocatalyst for carbon dioxide reduction to multi-carbon hydrocarbons and oxygenates

Science.gov (United States)

Wu, Jingjie; Ma, Sichao; Sun, Jing; Gold, Jake I.; Tiwary, Chandrasekhar; Kim, Byoungsu; Zhu, Lingyang; Chopra, Nitin; Odeh, Ihab N.; Vajtai, Robert; Yu, Aaron Z.; Luo, Raymond; Lou, Jun; Ding, Guqiao; Kenis, Paul J. A.; Ajayan, Pulickel M.

2016-12-01

Electroreduction of carbon dioxide into higher-energy liquid fuels and chemicals is a promising but challenging renewable energy conversion technology. Among the electrocatalysts screened so far for carbon dioxide reduction, which includes metals, alloys, organometallics, layered materials and carbon nanostructures, only copper exhibits selectivity towards formation of hydrocarbons and multi-carbon oxygenates at fairly high efficiencies, whereas most others favour production of carbon monoxide or formate. Here we report that nanometre-size N-doped graphene quantum dots (NGQDs) catalyse the electrochemical reduction of carbon dioxide into multi-carbon hydrocarbons and oxygenates at high Faradaic efficiencies, high current densities and low overpotentials. The NGQDs show a high total Faradaic efficiency of carbon dioxide reduction of up to 90%, with selectivity for ethylene and ethanol conversions reaching 45%. The C2 and C3 product distribution and production rate for NGQD-catalysed carbon dioxide reduction is comparable to those obtained with copper nanoparticle-based electrocatalysts.

A metal-free electrocatalyst for carbon dioxide reduction to multi-carbon hydrocarbons and oxygenates

Science.gov (United States)

Wu, Jingjie; Ma, Sichao; Sun, Jing; Gold, Jake I.; Tiwary, ChandraSekhar; Kim, Byoungsu; Zhu, Lingyang; Chopra, Nitin; Odeh, Ihab N.; Vajtai, Robert; Yu, Aaron Z.; Luo, Raymond; Lou, Jun; Ding, Guqiao; Kenis, Paul J. A.; Ajayan, Pulickel M.

2016-01-01

Electroreduction of carbon dioxide into higher-energy liquid fuels and chemicals is a promising but challenging renewable energy conversion technology. Among the electrocatalysts screened so far for carbon dioxide reduction, which includes metals, alloys, organometallics, layered materials and carbon nanostructures, only copper exhibits selectivity towards formation of hydrocarbons and multi-carbon oxygenates at fairly high efficiencies, whereas most others favour production of carbon monoxide or formate. Here we report that nanometre-size N-doped graphene quantum dots (NGQDs) catalyse the electrochemical reduction of carbon dioxide into multi-carbon hydrocarbons and oxygenates at high Faradaic efficiencies, high current densities and low overpotentials. The NGQDs show a high total Faradaic efficiency of carbon dioxide reduction of up to 90%, with selectivity for ethylene and ethanol conversions reaching 45%. The C2 and C3 product distribution and production rate for NGQD-catalysed carbon dioxide reduction is comparable to those obtained with copper nanoparticle-based electrocatalysts. PMID:27958290

Phosphine-functionalized graphene oxide, a high-performance electrocatalyst for oxygen reduction reaction

Science.gov (United States)

Ensafi, Ali A.; Golbon Haghighi, Mohsen; Jafari-Asl, Mehdi

2018-01-01

Here, a new approach for the synthesis of phosphine-functionalized graphene oxide (GO-PPh2) was developed. Using a simple method, diphenylphosphine group was linked to the hydroxyl group of OH-functionalized graphene that existing at the graphene surface. The electrochemical activity of GO-PPh2 for electrochemical oxygen reduction was checked. The results demonstrated that the new carbon hybrid material has a powerful potential for electrochemical oxygen reduction reaction (ORR). Moreover, GO-PPh2 as an electrocatalyst for ORR exhibited tolerance for methanol or ethanol as a result of crossover effect. In comparison with commercial Pt/C and Pt/rGO electrocatalysts, results showed that GO-PPh2 has a much higher selectivity, better durability, and much better electrochemical stability towards the ORR. The proposed method based on GO-PPh2 introduce an efficient electrocatalyst for further application in fuel cells.

Using an energized oxygen micro-jet for improved graphene etching by focused electron beam

Energy Technology Data Exchange (ETDEWEB)

Kim, Songkil; Henry, Mathias [George W. Woodruff School of Mechanical Engineering, Georgia Institute of Technology, Atlanta, Georgia 30332 (United States); Fedorov, Andrei G., E-mail: agf@gatech.edu [George W. Woodruff School of Mechanical Engineering, Georgia Institute of Technology, Atlanta, Georgia 30332 (United States); Parker H. Petit Institute for Bioengineering and Bioscience, Georgia Institute of Technology, Atlanta, Georgia 30332 (United States)

2015-12-07

We report on an improved Focused Electron Beam Induced Etching (FEBIE) process, which exploits heated oxygen delivery via a continuous supersonic micro-jet resulting in faster graphene patterning and better etch feature definition. Positioning a micro-jet in close proximity to a graphene surface with minimal jet spreading due to a continuous regime of gas flow at the exit of the 10 μm inner diameter capillary allows for focused exposure of the surface to reactive oxygen at high mass flux and impingement energy of a supersonic gas stream localized to a small etching area exposed to electron beam. These unique benefits of focused supersonic oxygen delivery to the surface enable a dramatic increase in the etch rate of graphene with no parasitic carbon “halo” deposition due to secondary electrons from backscattered electrons (BSE) in the area surrounding the etched regions. Increase of jet temperature via local nozzle heating provides means for enhancing kinetic energy of impinging oxygen molecules, which further speed up the etch, thus minimizing the beam exposure time and required electron dose, before parasitic carbon film deposition due to BSE mediated decomposition of adsorbed hydrocarbon contaminants has a measurable impact on quality of graphene etched features. Interplay of different physical mechanisms underlying an oxygen micro-jet assisted FEBIE process is discussed with support from experimental observations.

Using an energized oxygen micro-jet for improved graphene etching by focused electron beam

International Nuclear Information System (INIS)

Kim, Songkil; Henry, Mathias; Fedorov, Andrei G.

2015-01-01

We report on an improved Focused Electron Beam Induced Etching (FEBIE) process, which exploits heated oxygen delivery via a continuous supersonic micro-jet resulting in faster graphene patterning and better etch feature definition. Positioning a micro-jet in close proximity to a graphene surface with minimal jet spreading due to a continuous regime of gas flow at the exit of the 10 μm inner diameter capillary allows for focused exposure of the surface to reactive oxygen at high mass flux and impingement energy of a supersonic gas stream localized to a small etching area exposed to electron beam. These unique benefits of focused supersonic oxygen delivery to the surface enable a dramatic increase in the etch rate of graphene with no parasitic carbon “halo” deposition due to secondary electrons from backscattered electrons (BSE) in the area surrounding the etched regions. Increase of jet temperature via local nozzle heating provides means for enhancing kinetic energy of impinging oxygen molecules, which further speed up the etch, thus minimizing the beam exposure time and required electron dose, before parasitic carbon film deposition due to BSE mediated decomposition of adsorbed hydrocarbon contaminants has a measurable impact on quality of graphene etched features. Interplay of different physical mechanisms underlying an oxygen micro-jet assisted FEBIE process is discussed with support from experimental observations

Using an energized oxygen micro-jet for improved graphene etching by focused electron beam

Science.gov (United States)

Kim, Songkil; Henry, Mathias; Fedorov, Andrei G.

2015-12-01

We report on an improved Focused Electron Beam Induced Etching (FEBIE) process, which exploits heated oxygen delivery via a continuous supersonic micro-jet resulting in faster graphene patterning and better etch feature definition. Positioning a micro-jet in close proximity to a graphene surface with minimal jet spreading due to a continuous regime of gas flow at the exit of the 10 μm inner diameter capillary allows for focused exposure of the surface to reactive oxygen at high mass flux and impingement energy of a supersonic gas stream localized to a small etching area exposed to electron beam. These unique benefits of focused supersonic oxygen delivery to the surface enable a dramatic increase in the etch rate of graphene with no parasitic carbon "halo" deposition due to secondary electrons from backscattered electrons (BSE) in the area surrounding the etched regions. Increase of jet temperature via local nozzle heating provides means for enhancing kinetic energy of impinging oxygen molecules, which further speed up the etch, thus minimizing the beam exposure time and required electron dose, before parasitic carbon film deposition due to BSE mediated decomposition of adsorbed hydrocarbon contaminants has a measurable impact on quality of graphene etched features. Interplay of different physical mechanisms underlying an oxygen micro-jet assisted FEBIE process is discussed with support from experimental observations.

Decreasing the Hydroxylation Affinity of La _1–x Sr _x MnO ₃ Perovskites To Promote Oxygen Reduction Electrocatalysis

Energy Technology Data Exchange (ETDEWEB)

Stoerzinger, Kelsey A.; Hong, Wesley T.; Wang, Xiao Renshaw; Rao, Reshma R.; Bengaluru Subramanyam, Srinivas; Li, Changjian; Ariando,; Venkatesan, T.; Liu, Qiang [Advanced; Crumlin, Ethan J. [Advanced; Varanasi, Kripa K.; Shao-Horn, Yang

2017-11-17

Understanding the interaction between oxides and water is critical to design many of their functionalities, including the electrocatalysis of molecular oxygen reduction. In this study, we probed the hydroxylation of model (001)-oriented La(1-x)SrxMnO3 (LSMO) perovskite surfaces, where the electronic structure and manganese valence was controlled by five substitution levels of lanthanum with strontium, using ambient pressure X-ray photoelectron spectroscopy in a humid environment. The degree of hydroxyl formation on the oxide surface correlated with the proximity of the valence band center relative to the Fermi level. LSMO perovskites with a valence band center closer to the Fermi level were more reactive toward water, forming more hydroxyl species at a given relative humidity. More hydroxyl species correlate with greater electron-donating character to the surface free energy in wetting, and reduce the activity to catalyze oxygen reduction reaction (ORR) kinetics in basic solution. New strategies to design more active catalysts should include design of electronically conducting oxides with lower valence band centers relative to the Fermi level at ORR-relevant potentials.

Electron loss and capture from low-charge-state oxygen projectiles in methane

International Nuclear Information System (INIS)

Santos, A C F; Wolff, W; Sant’Anna, M M; Sigaud, G M; DuBois, R D

2013-01-01

Absolute cross sections for single- and double-electron loss and single- and multiple-electron capture of 15–1000 keV oxygen projectiles (q = −1, 0, 1, 2) colliding with the methane molecule are presented. The experimental data are used to examine cross-section scaling characteristics for the electron loss of various projectiles. In addition, a modified version of the free-collision model was employed for the calculation of the single- and total-electron-loss cross sections of oxygen projectiles presented in this work. The comparison of the calculated cross sections with the present experimental data shows very good agreement for projectile velocities above 1.0 au. The comparison of the present single-electron-capture cross sections with other projectiles having the same charge shows good agreement, and a common curve can be drawn through the different data sets. (paper)

Comparison of 250 MHz electron spin echo and continuous wave oxygen EPR imaging methods for in vivo applications

Science.gov (United States)

Epel, Boris; Sundramoorthy, Subramanian V.; Barth, Eugene D.; Mailer, Colin; Halpern, Howard J.

2011-01-01

Purpose: The authors compare two electron paramagnetic resonance imaging modalities at 250 MHz to determine advantages and disadvantages of those modalities for in vivo oxygen imaging. Methods: Electron spin echo (ESE) and continuous wave (CW) methodologies were used to obtain three-dimensional images of a narrow linewidth, water soluble, nontoxic oxygen-sensitive trityl molecule OX063 in vitro and in vivo. The authors also examined sequential images obtained from the same animal injected intravenously with trityl spin probe to determine temporal stability of methodologies. Results: A study of phantoms with different oxygen concentrations revealed a threefold advantage of the ESE methodology in terms of reduced imaging time and more precise oxygen resolution for samples with less than 70 torr oxygen partial pressure. Above∼100 torr, CW performed better. The images produced by both methodologies showed pO2 distributions with similar mean values. However, ESE images demonstrated superior performance in low pO2 regions while missing voxels in high pO2 regions. Conclusions: ESE and CW have different areas of applicability. ESE is superior for hypoxia studies in tumors. PMID:21626937

Cross-Linked CoMoO4/rGO Nanosheets as Oxygen Reduction Catalyst

Directory of Open Access Journals (Sweden)

Jiaqi Fu

2017-12-01

Full Text Available Development of inexpensive and robust electrocatalysts towards oxygen reduction reaction (ORR is crucial for the cost-affordable manufacturing of metal-air batteries and fuel cells. Here we show that cross-linked CoMoO4 nanosheets and reduced graphene oxide (CoMoO4/rGO can be integrated in a hybrid material under one-pot hydrothermal conditions, yielding a composite material with promising catalytic activity for oxygen reduction reaction (ORR. Cyclic voltammetry (CV and linear sweep voltammetry (LSV were used to investigate the efficiency of the fabricated CoMoO4/rGO catalyst towards ORR in alkaline conditions. The CoMoO4/rGO composite revealed the main reduction peak and onset potential centered at 0.78 and 0.89 V (vs. RHE, respectively. This study shows that the CoMoO4/rGO composite is a highly promising catalyst for the ORR under alkaline conditions, and potential noble metal replacement cathode in fuel cells and metal-air batteries.

Electron Transfer Pathways Facilitating U(VI) Reduction by Fe(II) on Al- vs Fe-Oxides

Energy Technology Data Exchange (ETDEWEB)

Taylor, S. D. [Pacific Northwest National Laboratory, Physical Sciences Division, P.O. Box; Becker, U. [The University of Michigan, Department of Earth; Rosso, K. M. [Pacific Northwest National Laboratory, Physical Sciences Division, P.O. Box

2017-09-06

This study continues mechanistic development of heterogeneous electron transfer (ET) pathways at mineral surfaces in aquatic environments that enable the reduction U(VI) by surface-associated Fe(II). Using computational molecular simulation within the framework of Marcus Theory, our findings highlight the importance of the configurations and interaction of the electron donor and acceptor species with the substrate, with respect to influencing its electronic structure and thereby the ability of semiconducting minerals to facilitate ET. U(VI) reduction by surface-associated Fe(II) (adsorbed or structurally incorporated into the lattice) on an insulating, corundum (001) surface (α-Al2O3) occurs when proximal inner-sphere (IS) surface complexes are formed, such that ET occurs through a combination of direct exchange (i.e., Fe d- and U f-orbitals overlap through space) and superexchange via intervening surface oxygen atoms. U(VI) reduction by coadsorbed Fe(II) on the isostructural semiconducting hematite (α-Fe2O3) basal surface requires either their direct electronic interaction (e.g., IS complexation) or mediation of this interaction indirectly through the surface via an intrasurface pathway. Conceptually possible longer-range ET by charge-hopping through surface Fe atoms was investigated to determine whether this indirect pathway is competitive with direct ET. The calculations show that energy barriers are large for this conduction-based pathway; interfacial ET into the hematite surface is endothermic (+80.1 kJ/mol) and comprises the rate-limiting step (10–6 s–1). The presence of the IS adsorbates appears to weaken the electronic coupling between underlying Fe ions within the surface, resulting in slower intra-surface ET (10–5 s–1) than expected in the bulk basal plane. Our findings lay out first insights into donor-acceptor communication via a charge-hopping pathway through the surface for heterogeneous reduction of U(VI) by Fe(II) and help provide a basis

Method for oxygen reduction in a uranium-recovery process. [US DOE patent application

Science.gov (United States)

Hurst, F.J.; Brown, G.M.; Posey, F.A.

1981-11-04

An improvement in effecting uranium recovery from phosphoric acid solutions is provided by sparging dissolved oxygen contained in solutions and solvents used in a reductive stripping stage with an effective volume of a nonoxidizing gas before the introduction of the solutions and solvents into the stage. Effective volumes of nonoxidizing gases, selected from the group consisting of argon, carbon dioxide, carbon monoxide, helium, hydrogen, nitrogen, sulfur dioxide, and mixtures thereof, displace oxygen from the solutions and solvents thereby reduce deleterious effects of oxygen such as excessive consumption of elemental or ferrous iron and accumulation of complex iron phosphates or cruds.

Giant onsite electronic entropy enhances the performance of ceria for water splitting.

Science.gov (United States)

Naghavi, S Shahab; Emery, Antoine A; Hansen, Heine A; Zhou, Fei; Ozolins, Vidvuds; Wolverton, Chris

2017-08-18

Previous studies have shown that a large solid-state entropy of reduction increases the thermodynamic efficiency of metal oxides, such as ceria, for two-step thermochemical water splitting cycles. In this context, the configurational entropy arising from oxygen off-stoichiometry in the oxide, has been the focus of most previous work. Here we report a different source of entropy, the onsite electronic configurational entropy, arising from coupling between orbital and spin angular momenta in lanthanide f orbitals. We find that onsite electronic configurational entropy is sizable in all lanthanides, and reaches a maximum value of ≈4.7 k B per oxygen vacancy for Ce 4+ /Ce 3+ reduction. This unique and large positive entropy source in ceria explains its excellent performance for high-temperature catalytic redox reactions such as water splitting. Our calculations also show that terbium dioxide has a high electronic entropy and thus could also be a potential candidate for solar thermochemical reactions.Solid-state entropy of reduction increases the thermodynamic efficiency of ceria for two-step thermochemical water splitting. Here, the authors report a large and different source of entropy, the onsite electronic configurational entropy arising from coupling between orbital and spin angular momenta in f orbitals.

Targeted design of α-MnO2 based catalysts for oxygen reduction

Czech Academy of Sciences Publication Activity Database

Lehtimäki, M.; Hoffmannová, Hana; Boytsová, O.; Bastl, Zdeněk; Bush, M.; Halck, N. B.; Rossmeisl, J.; Krtil, Petr

2016-01-01

Roč. 191, FEB 2016 (2016), s. 452-461 ISSN 0013-4686 EU Projects: European Commission(XE) 214936 - ELCAT Institutional support: RVO:61388955 Keywords : electrocatalysis * oxygen reduction * MnO2 Subject RIV: CG - Electrochemistry Impact factor: 4.798, year: 2016

Nitrogen-doped graphene-wrapped iron nanofragments for high-performance oxygen reduction electrocatalysts

Energy Technology Data Exchange (ETDEWEB)

Lee, Jang Yeol [Korea Institute of Science and Technology, Photo-Electronic Hybrid Research Center (Korea, Republic of); Kim, Na Young [Korea Institute of Science and Technology, Fuel Cell Research Center (Korea, Republic of); Shin, Dong Yun [Chungbuk National University, Department of Environmental Engineering (Korea, Republic of); Park, Hee-Young [Korea Institute of Science and Technology, Fuel Cell Research Center (Korea, Republic of); Lee, Sang-Soo [Korea Institute of Science and Technology, Photo-Electronic Hybrid Research Center (Korea, Republic of); Joon Kwon, S. [Korea Institute of Science and Technology, Nanophotonics Research Center (Korea, Republic of); Lim, Dong-Hee [Chungbuk National University, Department of Environmental Engineering (Korea, Republic of); Bong, Ki Wan [Korea University, Department of Chemical and Biological Engineering (Korea, Republic of); Son, Jeong Gon, E-mail: jgson@kist.re.kr [Korea Institute of Science and Technology, Photo-Electronic Hybrid Research Center (Korea, Republic of); Kim, Jin Young, E-mail: jinykim@kist.re.kr [Korea Institute of Science and Technology, Fuel Cell Research Center (Korea, Republic of)

2017-03-15

Transition metals, such as iron (Fe)- or cobalt (Co)-based nanomaterials, are promising electrocatalysts for oxygen reduction reactions (ORR) in fuel cells due to their high theoretical activity and low cost. However, a major challenge to using these metals in place of precious metal catalysts for ORR is their low efficiency and poor stability, thus new concepts and strategies should be needed to address this issue. Here, we report a hybrid aciniform nanostructures of Fe nanofragments embedded in thin nitrogen (N)-doped graphene (Fe@N-G) layers via a heat treatment of graphene oxide-wrapped iron oxide (Fe{sub 2}O{sub 3}) microparticles with melamine. The heat treatment leads to transformation of Fe{sub 2}O{sub 3} microparticles to nanosized zero-valent Fe fragments and formation of core-shell structures of Fe nanofragments and N-doped graphene layers. Thin N-doped graphene layers massively promote electron transfer from the encapsulated metals to the graphene surface, which efficiently optimizes the electronic structure of the graphene surface and thereby triggers ORR activity at the graphene surface. With the synergistic effect arising from the N-doped graphene and Fe nanoparticles with porous aciniform nanostructures, the Fe@N-G hybrid catalyst exhibits high catalytic activity, which was evidenced by high E{sub 1/2} of 0.82 V, onset potential of 0.93 V, and limiting current density of 4.8 mA cm{sup −2} indicating 4-electron ORR, and even exceeds the catalytic stability of the commercial Pt catalyst.

Importance of the support and the grade of Pt in the oxygen reduction reaction

International Nuclear Information System (INIS)

Enriquez M, O.; Fernandez V, S.M.

2004-01-01

The technology of the fuel cells type Proton Exchange Membrane (PEM), needs to define clearly the influence of the different involved parameters, this is made in general using methods of electrochemical impedance, in which the involved reactions can be presupposed. Another form of making is identifying experimentally the influence of the different parameters. In this work the obtained results are reported with for the oxygen reduction reaction using as electro catalyst platinum analytical grade and fuel cell grade and like support graphite and vulcan. It was found that as much the support as the particle size modify the over potential for the oxygen reduction reaction (Orr). (Author)

The Range of 1-3 keV Electrons in Solid Oxygen and Carbon Monoxide

DEFF Research Database (Denmark)

Oehlenschlæger, M.; Andersen, H.H.; Schou, Jørgen

1985-01-01

The range of 1-3 keV electrons in films of solid oxygen and carbon monoxide has been measured by a mirror substrate method. The technique used here is identical to the one previously used for range measurements in solid hydrogen and nitrogen. The range in oxygen is slightly shorter than that in n......The range of 1-3 keV electrons in films of solid oxygen and carbon monoxide has been measured by a mirror substrate method. The technique used here is identical to the one previously used for range measurements in solid hydrogen and nitrogen. The range in oxygen is slightly shorter than...

Pt Monolayer Shell on Nitrided Alloy Core—A Path to Highly Stable Oxygen Reduction Catalyst

Directory of Open Access Journals (Sweden)

Jue Hu

2015-07-01

Full Text Available The inadequate activity and stability of Pt as a cathode catalyst under the severe operation conditions are the critical problems facing the application of the proton exchange membrane fuel cell (PEMFC. Here we report on a novel route to synthesize highly active and stable oxygen reduction catalysts by depositing Pt monolayer on a nitrided alloy core. The prepared PtMLPdNiN/C catalyst retains 89% of the initial electrochemical surface area after 50,000 cycles between potentials 0.6 and 1.0 V. By correlating electron energy-loss spectroscopy and X-ray absorption spectroscopy analyses with electrochemical measurements, we found that the significant improvement of stability of the PtMLPdNiN/C catalyst is caused by nitrogen doping while reducing the total precious metal loading.

Obtaining of platinum-titanium alloys by sol-gel and their performance for the detachment reactions and oxygen reduction

International Nuclear Information System (INIS)

Regueira R, B. I.

2011-01-01

In the present work, platinum-titanium (Pt-Ti) alloys were prepared, characterized and evaluated in acid media as bifunctional electrocatalysts for the oxygen evolution reaction (Oer) and oxygen reduction reactions (Orr) in acid media. The alloys were synthesized by sol-gel method, heating the gel at temperatures of 400 and 600 C. The alloys characterization was realized by X-ray diffraction, scanning electron microscopy and EDS. Both alloys were formed by agglomerates of nanometer particles. The particle sizes were lower for the alloy obtained at 400 C (120 nm to 257 nm) compared to the alloy prepared at 600 C (555 nm to 833 nm). Cyclic and linear voltammetry techniques were used for the electrochemical evaluation of the alloy obtained at both temperatures for the Oer and Orr, in a 0.5 M sulfuric acid solution. The materials have response for both electrochemical reactions, therefore the best performance was for the Pt-Ti alloy, obtained at 400 C and it was stable for the oxygen evolution reaction. The alloy obtained at 400 C presents satisfactory electrocatalytic characteristics to be used as bifunctional material in a unified regenerative fuel cell. (Author)

Oxygen reduction kinetics on mixed conducting SOFC model cathodes

Energy Technology Data Exchange (ETDEWEB)

Baumann, F.S.

2006-07-01

The kinetics of the oxygen reduction reaction at the surface of mixed conducting solid oxide fuel cell (SOFC) cathodes is one of the main limiting factors to the performance of these promising systems. For ''realistic'' porous electrodes, however, it is usually very difficult to separate the influence of different resistive processes. Therefore, a suitable, geometrically well-defined model system was used in this work to enable an unambiguous distinction of individual electrochemical processes by means of impedance spectroscopy. The electrochemical measurements were performed on dense thin film microelectrodes, prepared by PLD and photolithography, of mixed conducting perovskite-type materials. The first part of the thesis consists of an extensive impedance spectroscopic investigation of La0.6Sr0.4Co0.8Fe0.2O3 (LSCF) microelectrodes. An equivalent circuit was identified that describes the electrochemical properties of the model electrodes appropriately and enables an unambiguous interpretation of the measured impedance spectra. Hence, the dependencies of individual electrochemical processes such as the surface exchange reaction on a wide range of experimental parameters including temperature, dc bias and oxygen partial pressure could be studied. As a result, a comprehensive set of experimental data has been obtained, which was previously not available for a mixed conducting model system. In the course of the experiments on the dc bias dependence of the electrochemical processes a new and surprising effect was discovered: It could be shown that a short but strong dc polarisation of a LSCF microelectrode at high temperature improves its electrochemical performance with respect to the oxygen reduction reaction drastically. The electrochemical resistance associated with the oxygen surface exchange reaction, initially the dominant contribution to the total electrode resistance, can be reduced by two orders of magnitude. This &apos

Oxygen Reduction Kinetics Enhancement on a Heterostructured Oxide Surface for Solid Oxide Fuel Cells

KAUST Repository

Crumlin, Ethan J.

2010-11-04

Heterostructured interfaces of oxides, which can exhibit transport and reactivity characteristics remarkably different from those of bulk oxides, are interesting systems to explore in search of highly active cathodes for the oxygen reduction reaction (ORR). Here, we show that the ORR of ∼85 nm thick La0.8Sr0.2CoO3-δ (LSC113) films prepared by pulsed laser deposition on (001)-oriented yttria-stabilized zirconia (YSZ) substrates is dramatically enhanced (∼3-4 orders of magnitude above bulk LSC113) by surface decorations of (La 0.5Sr0.5)2CoO4±δ (LSC214) with coverage in the range from ∼0.1 to ∼15 nm. Their surface and atomic structures were characterized by atomic force, scanning electron, and scanning transmission electron microscopy, and the ORR kinetics were determined by electrochemical impedance spectroscopy. Although the mechanism for ORR enhancement is not yet fully understood, our results to date show that the observed ORR enhancement can be attributed to highly active interfacial LSC113/LSC214 regions, which were shown to be atomically sharp. © 2010 American Chemical Society.

Oxygen Reduction Kinetics Enhancement on a Heterostructured Oxide Surface for Solid Oxide Fuel Cells

KAUST Repository

Crumlin, Ethan J.; Mutoro, Eva; Ahn, Sung-Jin; la O’ , Gerardo Jose; Leonard, Donovan N.; Borisevich, Albina; Biegalski, Michael D.; Christen, Hans M.; Shao-Horn, Yang

2010-01-01

Heterostructured interfaces of oxides, which can exhibit transport and reactivity characteristics remarkably different from those of bulk oxides, are interesting systems to explore in search of highly active cathodes for the oxygen reduction reaction (ORR). Here, we show that the ORR of ∼85 nm thick La0.8Sr0.2CoO3-δ (LSC113) films prepared by pulsed laser deposition on (001)-oriented yttria-stabilized zirconia (YSZ) substrates is dramatically enhanced (∼3-4 orders of magnitude above bulk LSC113) by surface decorations of (La 0.5Sr0.5)2CoO4±δ (LSC214) with coverage in the range from ∼0.1 to ∼15 nm. Their surface and atomic structures were characterized by atomic force, scanning electron, and scanning transmission electron microscopy, and the ORR kinetics were determined by electrochemical impedance spectroscopy. Although the mechanism for ORR enhancement is not yet fully understood, our results to date show that the observed ORR enhancement can be attributed to highly active interfacial LSC113/LSC214 regions, which were shown to be atomically sharp. © 2010 American Chemical Society.

Oxygen adsorption on Cu-9 at. %Al(111) studied by low energy electron diffraction and Auger electron spectroscopy

Science.gov (United States)

Yoshitake, Michiko; Bera, Santanu; Yamauchi, Yasuhiro; Song, Weijie

2003-07-01

Cu-based alloys have been used for electric cables for long time. In the field of microelectronics, Al had been used for electrical wiring. However, it became clear that electromigration occurs in Al that causes breaking of wires in minute wirings. Due to this problem, Cu wiring is used in most advanced microprocessors. Cu metal is more corrosive than Al and Cu-based alloys with a small amount of Al is expected to solve problems both on electromigration and corrosion. The initial stage of corrosion is oxygen adsorption. We studied surface segregation of Al on Cu-9% Al(111) and oxygen adsorption on the surface with/without Al segregation in ultrahigh vacuum by low energy electron diffraction (LEED) and Auger electron spectroscopy. It was found that Al segregates on the surface to form (√3×√3)R30° structure and the structure vanishes above 595 K to give (1×1) structure while Al still segregates. The specimen was exposed to oxygen at different temperatures. The amount of oxygen uptake was not structure dependent but temperature dependent. Below 595 K, only a small amount of oxygen adsorbed. Between 595 and 870 K, oxygen adsorbed surface showed amorphous LEED pattern. The specimen was annealed at 1070 K after oxygen exposure. When the specimen was exposed oxygen below 870 K, the oxygen Auger intensity decreased significantly by annealing and the annealed surface showed (√3×√3)R30° structure at room temperature. When the specimen was exposed to oxygen at 870 K, diffused spots developed newly in LEED pattern but the pattern disappeared after 1070 K annealing while oxygen Auger intensity remained almost constant. Exposing the specimen to oxygen at 995 K resulted in clear spots in the LEED pattern, which were attributed to the (7/√3×7√3)R30° structure.

Selective reduction of nitric oxide over Cu/ZSM-5: The role of oxygen in suppressing catalyst deactivation by carbonaceous deposits

Energy Technology Data Exchange (ETDEWEB)

d' Itri, Julie L; Sachtler, Wolfgang M.H. [V.N. Ipatieff Laboratory, Center for Catalysis and Surface Science, Departments of Chemical Engineering and Chemistry, Northwestern University, Evanston, IL (United States)

1993-06-15

The role of oxygen in the selective reduction of nitrogen monoxide by either propane or propene over 'excessively' ion-exchanged Cu/ZSM-5 has been studied. In a wide temperature region and in the absence of additives such as steam, propane is a more effective reductant than propene; with propane and in the presence of oxygen reduction of nitric oxide to nitrogen approaches 100% above 600 K. The difference in effectiveness is due to the different degree of catalyst deactivation by carbonaceous deposits: more carbonaceous material is deposited from propene than from propane. Temperature-programmed oxidation shows that above 600 K the rate of oxidation of carbonaceous deposits by oxygen is significant. The amount of such carbonaceous deposits is, therefore, lower when catalytic tests above 600 K are done in the presence of oxygen. At very high temperatures, the in situ volatilization of the deposits by reaction with oxygen keeps the catalyst surface clean in the steady state of nitric oxide reduction.

The effect of temperature and pressure on the oxygen reduction reactions in polyelectrolyte membranes

Energy Technology Data Exchange (ETDEWEB)

Holdcroft, S.; Abdou, M.S.; Beattie, P.; Basura, V. [Simon Fraser Univ., Burnaby, BC (Canada). Dept. of Chemistry

1997-12-31

The effect of temperature and pressure on the oxygen reduction reaction in polyelectrolyte membranes was described. Polyelectrolytes chosen for the experiment differed in composition, weight and flexibility of the polymer chains. The study was conducted in a solid state electrochemical cell at temperatures between 30 and 95 degrees C and in the pressure range of 1 to 5 atm. The solubility of oxygen in these membranes was found to follow Henry`s Law, while the diffusion coefficient decreased with pressure. The effect of temperature on the solubility of oxygen and the diffusion coefficient of oxygen in the membranes was similar to that observed in solution electrolytes. 2 refs., 3 figs.

Pulse radiolysis investigation of the reaction of the electronic adduct of bovine serum albumin with oxygen. Polychromatic kinetics of the reaction with adsorbed oxygen

International Nuclear Information System (INIS)

Pribush, A.G.

1986-01-01

The method of pulse radiolysis was used to investigate the reaction of the electronic adduct of bovine serum albumin with oxygen. It was suggested that the disappearance of the electronic adduct of the protein occurs in the course of its interaction with oxygen adsorbed on the globular protein molecule

Autotrophic antimonate bio-reduction using hydrogen as the electron donor.

Science.gov (United States)

Lai, Chun-Yu; Wen, Li-Lian; Zhang, Yin; Luo, Shan-Shan; Wang, Qing-Ying; Luo, Yi-Hao; Chen, Ran; Yang, Xiaoe; Rittmann, Bruce E; Zhao, He-Ping

2016-01-01

Antimony (Sb), a toxic metalloid, is soluble as antimonate (Sb(V)). While bio-reduction of Sb(V) is an effective Sb-removal approach, its bio-reduction has been coupled to oxidation of only organic electron donors. In this study, we demonstrate, for the first time, the feasibility of autotrophic microbial Sb(V) reduction using hydrogen gas (H2) as the electron donor without extra organic carbon source. SEM and EDS analysis confirmed the production of the mineral precipitate Sb2O3. When H2 was utilized as the electron donor, the consortium was able to fully reduce 650 μM of Sb(V) to Sb(III) in 10 days, a rate comparable to the culture using lactate as the electron donor. The H2-fed culture directed a much larger fraction of it donor electrons to Sb(V) reduction than did the lactate-fed culture. While 98% of the electrons from H2 were used to reduce Sb(V) by the H2-fed culture, only 12% of the electrons from lactate was used to reduce Sb(V) by the lactate-fed culture. The rest of the electrons from lactate went to acetate and propionate through fermentation, to methane through methanogenesis, and to biomass synthesis. High-throughput sequencing confirmed that the microbial community for the lactate-fed culture was much more diverse than that for the H2-fed culture, which was dominated by a short rod-shaped phylotype of Rhizobium (α-Protobacteria) that may have been active in Sb(V) reduction. Copyright © 2015 Elsevier Ltd. All rights reserved.

Electron loss from multiply protonated lysozyme ions in high energy collisions with molecular oxygen

DEFF Research Database (Denmark)

Hvelplund, P; Nielsen, SB; Sørensen, M

2001-01-01

We report on the electron loss from multiply protonated lysozyme ions Lys-Hn(n)+ (n = 7 - 17) and the concomitant formation of Lys-Hn(n+1)+. in high-energy collisions with molecular oxygen (laboratory kinetic energy = 50 x n keV). The cross section for electron loss increases with the charge state...... of the precursor from n = 7 to n = 11 and then remains constant when n increases further. The absolute size of the cross section ranges from 100 to 200 A2. The electron loss is modeled as an electron transfer process between lysozyme cations and molecular oxygen....

Monolayer group-III monochalcogenides by oxygen functionalization: a promising class of two-dimensional topological insulators

Science.gov (United States)

Zhou, Si; Liu, Cheng-Cheng; Zhao, Jijun; Yao, Yugui

2018-03-01

Monolayer group-III monochalcogenides (MX, M = Ga, In; X = S, Se, Te), an emerging category of two-dimensional (2D) semiconductors, hold great promise for electronics, optoelectronics and catalysts. By first-principles calculations, we show that the phonon dispersion and Raman spectra, as well as the electronic and topological properties of monolayer MX can be tuned by oxygen functionalization. Chemisorption of oxygen atoms on one side or both sides of the MX sheet narrows or even closes the band gap, enlarges work function, and significantly reduces the carrier effective mass. More excitingly, InS, InSe, and InTe monolayers with double-side oxygen functionalization are 2D topological insulators with sizeable bulk gap up to 0.21 eV. Their low-energy bands near the Fermi level are dominated by the px and py orbitals of atoms, allowing band engineering via in-plane strains. Our studies provide viable strategy for realizing quantum spin Hall effect in monolayer group-III monochalcogenides at room temperature, and utilizing these novel 2D materials for high-speed and dissipationless transport devices.

Nitrogen-doped graphene aerogel-supported spinel CoMn2O4 nanoparticles as an efficient catalyst for oxygen reduction reaction

Science.gov (United States)

Liu, Yisi; Li, Jie; Li, Wenzhang; Li, Yaomin; Chen, Qiyuan; Zhan, Faqi

2015-12-01

Spinel CoMn2O4 (CMO) nanoparticles grown on three-dimensional (3D) nitrogen-doped graphene areogel (NGA) is prepared by a facile two-step hydrothermal method. The NGA not only possesses the intrinsic property of graphene, but also has abundant pore conformations for supporting spinel metal oxide nanoparticles, thus would be suitable as a good electrocatalysts' support for oxygen reduction reaction (ORR). The structure, morphology, porous properties, and chemical composition of CMO/NGA are investigated by X-ray diffraction (XRD) spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectroscopy, nitrogen adsorption-desorption measurements, and X-ray photoelectron spectroscopy (XPS). The electrocatalytic activity of catalysts is discussed by cyclic voltammograms (CV), electrochemical impedance spectroscopy (EIS), and rotating disk electrode (RDE) measurements in O2-saturated 0.1 M KOH electrolyte. The CMO/NGA hybrid exhibits more positive onset potential and half-wave potential, faster charge transfer than that of CMO and NGA, and its electrocatalytic performance is comparable with the commercial 20 wt.% Pt/C. Furthermore, it mainly favors a direct 4e- reaction pathway, and has excellent ethanol tolerance and high durability, which is attributed to the unique 3D crumpled porous nanostructure of NGA with large specific area and fast electron transport, and the synergic covalent coupling between the CoMn2O4 nanoparticles and NGA.

Tailored Combination of Low Dimensional Catalysts for Efficient Oxygen Reduction and Evolution in Li-O2 Batteries.

Science.gov (United States)

Yoon, Ki Ro; Kim, Dae Sik; Ryu, Won-Hee; Song, Sung Ho; Youn, Doo-Young; Jung, Ji-Won; Jeon, Seokwoo; Park, Yong Joon; Kim, Il-Doo

2016-08-23

The development of efficient bifunctional catalysts for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is a key issue pertaining high performance Li-O2 batteries. Here, we propose a heterogeneous electrocatalyst consisting of LaMnO3 nanofibers (NFs) functionalized with RuO2 nanoparticles (NPs) and non-oxidized graphene nanoflakes (GNFs). The Li-O2 cell employing the tailored catalysts delivers an excellent electrochemical performance, affording significantly reduced discharge/charge voltage gaps (1.0 V at 400 mA g(-1) ), and superior cyclability for over 320 cycles. The outstanding performance arises from (1) the networked LaMnO3 NFs providing ORR/OER sites without severe aggregation, (2) the synergistic coupling of RuO2 NPs for further improving the OER activity and the electrical conductivity on the surface of the LaMnO3 NFs, and (3) the use of GNFs providing a fast electronic pathway as well as improved ORR kinetics. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Oxygen diffusion kinetics and reactive lifetimes in bacterial and mammalian cells irradiated with nanosecond pulses of high intensity electrons

International Nuclear Information System (INIS)

Epp, E.R.; Weiss, H.; Ling, C.C.; Djordjevic, B.; Kessaris, N.D.

1975-01-01

Experiaments have been designed to gain information on the lifetime of oxygen-sensitive species suspected to be produced in critical molecules in irradiated cells and on the time-diffusion of oxygen in cells. An approach developed in this laboratory involves the delivery of two high intensity electron pulses each of 3 ns duration to a thin layer of cells equilibrated with a known concentration of oxygen. The first pulse serves to render the cells totally anoxic by the radiochemical depletion of oxygen; the second is delivered at a time electronically delayed after the first allowing for diffusion of oxygen during this time. Under these conditions the radiosensitivity of E coli B/r has been measured over six decades of interpulse time. Cellular time-diffusion curves constructed from the measurements show that oxygen establishes its sensitizing effect within 10 -4 s after the creation of intracellular anoxia establishing this time as an upper limit to the lifetime of the species. Unusual behaviour of the diffusion curve observed for longer delay times can be explained by a model wherein it is postulated that a radiation-induced inhibiting agent slows down diffusion. Application of this model to the experimental data yields a value of 0.4x10 -5 cm 2 s -1 for the cellular oxygen diffusion coefficient. Similar experiments recently carried out for Serratia marcescens will also be described. The oxygen effect in cultured HeLa cells exposed to single short electron pulses has been examined over a range of oxygen concentrations. A family of breaking survival curves was obtained similar to those previously measured for E coli B/r by this laboratory. The data appear to be reasonably consistent with a physicochemical mechanism involving the radiochemical depletion of oxygen previously invoked for bacteria. (author)

Predicting the Oxygen-Binding Properties of Platinum Nanoparticle Ensembles by Combining High-Precision Electron Microscopy and Density Functional Theory.

Science.gov (United States)

Aarons, Jolyon; Jones, Lewys; Varambhia, Aakash; MacArthur, Katherine E; Ozkaya, Dogan; Sarwar, Misbah; Skylaris, Chris-Kriton; Nellist, Peter D

2017-07-12

Many studies of heterogeneous catalysis, both experimental and computational, make use of idealized structures such as extended surfaces or regular polyhedral nanoparticles. This simplification neglects the morphological diversity in real commercial oxygen reduction reaction (ORR) catalysts used in fuel-cell cathodes. Here we introduce an approach that combines 3D nanoparticle structures obtained from high-throughput high-precision electron microscopy with density functional theory. Discrepancies between experimental observations and cuboctahedral/truncated-octahedral particles are revealed and discussed using a range of widely used descriptors, such as electron-density, d-band centers, and generalized coordination numbers. We use this new approach to determine the optimum particle size for which both detrimental surface roughness and particle shape effects are minimized.

Three-dimensional iron, nitrogen-doped carbon foams as efficient electrocatalysts for oxygen reduction reaction in alkaline solution

International Nuclear Information System (INIS)

Ma, Yanjiao; Wang, Hui; Feng, Hanqing; Ji, Shan; Mao, Xuefeng; Wang, Rongfang

2014-01-01

Graphical abstract: Three-dimentional Fe, N-doped carbon foams prepared by two steps exhibited comparable catalytic activity for oxygen reduction reaction to commercial Pt/C due to the unique structure and the synergistic effect of Fe and N atoms. - Highlights: • Three-dimensional Fe, N-doped carbon foam (3D-CF) were prepared. • 3D-CF exhibits comparable catalytic activity to Pt/C for oxygen reduction reaction. • The enhanced activity of 3D-CF results of its unique structure. - Abstract: Three-dimensional (3D) Fe, N-doped carbon foams (3D-CF) as efficient cathode catalysts for the oxygen reduction reaction (ORR) in alkaline solution are reported. The 3D-CF exhibit interconnected hierarchical pore structure. In addition, Fe, N-doped carbon without porous strucuture (Fe-N-C) and 3D N-doped carbon without Fe (3D-CF’) are prepared to verify the electrocatalytic activity of 3D-CF. The electrocatalytic performance of as-prepared 3D-CF for ORR shows that the onset potential on 3D-CF electrode positively shifts about 41 mV than those of 3D-CF’ and Fe-N-C respectively. In addition, the onset potential on 3D-CF electrode for ORR is about 27 mV more negative than that on commercial Pt/C electrode. 3D-CF also show better methanol tolerance and durability than commercial Pt/C catalyst. These results show that to synthesize 3D hierarchical pores with high specific surface area is an efficient way to improve the ORR performance

Metal-free and Oxygen-free Graphene as Oxygen Reduction Catalysts for Highly Efficient Fuel Cells

Science.gov (United States)

2013-06-30

analysis was carried out by a TA instrument with a heating rate of 10 °C in N2. The Raman spectra were collected on a Raman spectrometer (Renishaw...kinematics viscosity for KOH (v = 0.01 cm 2 s -1 ) and CO2 is concentration of O2 in the solution (CO2 = 1.2 × 10 -6 mol cm -3 ). The constant 0.2 is...functionalizing graphene to impart electrocatalytic activity for oxygen reduction reaction (ORR) in fuel cells. Raman and X-ray photoelectron spectroscopic

Investigations of oxygen reduction reactions in non-aqueous electrolytes and the lithium-air battery

Science.gov (United States)

O'Laoire, Cormac Micheal

Unlocking the true energy capabilities of the lithium metal negative electrode in a lithium battery has until now been limited by the low capacity intercalation and conversion reactions at the positive electrodes. This is overcome by removing these electrodes and allowing lithium to react directly with oxygen in the atmosphere forming the Li-air battery. Chapter 2 discusses the intimate role of electrolyte, in particular the role of ion conducting salts on the mechanism and kinetics of oxygen reduction in non-aqueous electrolytes designed for such applications and in determining the reversibility of the electrode reactions. Such fundamental understanding of this high energy density battery is crucial to harnessing its full energy potential. The kinetics and mechanisms of O2 reduction in solutions of hexafluorophosphate salts of the general formula X+ PF6-, where, X = tetra butyl ammonium (TBA), K, Na and Li, in acetonitrile have been studied on glassy carbon electrodes using cyclic voltammetry (CV) and rotating disk electrode (RDE) techniques. Our results show that cation choice strongly influences the reduction mechanism of O2. Electrochemical data supports the view that alkali metal oxides formed via electrochemical and chemical reactions passivate the electrode surface inhibiting the kinetics and reversibility of the processes. The O2 reduction mechanisms in the presence of the different cations have been supplemented by kinetic parameters determined from detailed analyses of the CV and RDE data. The organic solvent present in the Li+-conducting electrolyte has a major role on the reversibility of each of the O2 reduction products as found from the work discussed in the next chapter. A fundamental study of the influence of solvents on the oxygen reduction reaction (ORR) in a variety of non-aqueous electrolytes was conducted in chapter 4. In this work special attention was paid to elucidate the mechanism of the oxygen electrode processes in the rechargeable Li

High Oxygen Reduction Reaction Performances of Cathode Materials Combining Polyoxometalates, Coordination Complexes, and Carboneous Supports.

Science.gov (United States)

Zhang, Shuangshuang; Oms, Olivier; Hao, Long; Liu, Rongji; Wang, Meng; Zhang, Yaqin; He, Hong-Yan; Dolbecq, Anne; Marrot, Jérôme; Keita, Bineta; Zhi, Linjie; Mialane, Pierre; Li, Bin; Zhang, Guangjin

2017-11-08

A series of carbonaceous-supported precious-metal-free polyoxometalate (POM)-based composites which can be easily synthesized on a large scale was shown to act as efficient cathode materials for the oxygen reduction reaction (ORR) in neutral or basic media via a four-electron mechanism with high durability. Moreover, exploiting the versatility of the considered system, its activity was optimized by the judicious choice of the 3d metals incorporated in the {(PW 9 ) 2 M 7 } (M = Co, Ni) POM core, the POM counterions and the support (thermalized triazine-based frameworks (TTFs), fluorine-doped TTF (TTF-F), reduced graphene oxide, or carbon Vulcan XC-72. In particular, for {(PW 9 ) 2 Ni 7 }/{Cu(ethylenediamine) 2 }/TTF-F, the overpotential required to drive the ORR compared well with those of Pt/C. This outstanding ORR electrocatalytic activity is linked with two synergistic effects due to the binary combination of the Cu and Ni centers and the strong interaction between the POM molecules and the porous and highly conducting TTF-F framework. To our knowledge, {(PW 9 ) 2 Ni 7 }/{Cu(ethylenediamine) 2 }/TTF-F represents the first example of POM-based noble-metal-free ORR electrocatalyst possessing both comparable ORR electrocatalytic activity and much higher stability than that of Pt/C in neutral medium.

Long distance electron transport in marine sediments: Microbial and geochemical implications

DEFF Research Database (Denmark)

Risgaard-Petersen, Nils; Larsen, Steffen; Pfeffer, Christian

and promotes the formation of Mg-calcite and iron oxides in the oxic zone. Oxygen seems to be the major electron acceptor, and more than 40% of the oxygen consumption in sediments can be driven by long distance electron transfer from distant electron donors. The major e-donor is sulfide, which is oxidized......Anaerobic oxidation of organic matter in marine sediment is traditionally considered to be coupled to oxygen reduction via a cascade of redox processes and transport of intermittent electron donors and acceptors. Electric currents have been found to shortcut this cascade and directly couple...... oxidation of sulphide centimeters down in marine sediment to the reduction of oxygen at the very surface1 . This electric coupling of spatially separated redox half-reactions seems to be mediated by centimeter long filamentous Desulfubulbus affiliated bacteria with morphological and ultra...

Spin transport in oxygen adsorbed graphene nanoribbon

Science.gov (United States)

Kumar, Vipin

2018-04-01

The spin transport properties of pristine graphene nanoribbons (GNRs) have been most widely studied using theoretical and experimental tools. The possibilities of oxidation of fabricated graphene based nano electronic devices may change the device characteristics, which motivates to further explore the properties of graphene oxide nanoribbons (GONRs). Therefore, we present a systematic computational study on the spin polarized transport in surface oxidized GNR in antiferromagnetic (AFM) spin configuration using density functional theory combined with non-equilibrium Green's function (NEGF) method. It is found that the conductance in oxidized GNRs is significantly suppressed in the valance band and the conduction band. A further reduction in the conductance profile is seen in presence of two oxygen atoms on the ribbon plane. This change in the conductance may be attributed to change in the surface topology of the ribbon basal plane due to presence of the oxygen adatoms, where the charge transfer take place between the ribbon basal plane and the oxygen atoms.

Reduction of oxygen concentration by heater design during Czochralski Si growth

Science.gov (United States)

Zhou, Bing; Chen, Wenliang; Li, Zhihui; Yue, Ruicun; Liu, Guowei; Huang, Xinming

2018-02-01

Oxygen is one of the highest-concentration impurities in single crystals grown by the Czochralski (CZ) process, and seriously impairs the quality of the Si wafer. In this study, computer simulations were applied to design a new CZ system. A more appropriate thermal field was acquired by optimization of the heater structure. The simulation results showed that, compared with the conventional system, the oxygen concentration in the newly designed CZ system was reduced significantly throughout the entire CZ process because of the lower crucible wall temperature and optimized convection. To verify the simulation results, experiments were conducted on an industrial single-crystal furnace. The experimental results showed that the oxygen concentration was reduced significantly, especially at the top of the CZ-Si ingot. Specifically, the oxygen concentration was 6.19 × 1017 atom/cm3 at the top of the CZ-Si ingot with the newly designed CZ system, compared with 9.22 × 1017 atom/cm3 with the conventional system. Corresponding light-induced degradation of solar cells based on the top of crystals from the newly designed CZ system was 1.62%, a reduction of 0.64% compared with crystals from the conventional system (2.26%).

Secondary electron emission influenced by oxidation on the aluminum surface: the roles of the chemisorbed oxygen and the oxide layer

Science.gov (United States)

Li, Jiangtao; Hoekstra, Bart; Wang, Zhen-Bin; Qiu, Jie; Pu, Yi-Kang

2018-04-01

A relationship between the apparent secondary electron yield ({γ }{{se}}) and the oxygen coverage/oxide layer thickness on an aluminum cathode is obtained in an experiment under a controlled environment. The apparent secondary electron yield ({γ }{{se}}) is deduced from the breakdown voltage between two parallel plate electrodes in a 360 mTorr argon environment using a simple Townsend breakdown model with the assumption that the variation of the apparent secondary electron yield is dominated by the variation of the argon ion induced processes. The oxygen coverage/oxide layer thickness on the aluminum cathode is measured by a semi in situ x-ray photoemission spectroscopy equipment which is directly attached to the discharge chamber. It is found that three phases exist: (1) in the monomonolayer regime, as the oxygen coverage increases from 0 to 0.3, {γ }{{se}} decreases by nearly 40 % , (2) as the oxygen coverage increases from 0.3 to 1, {γ }{{se}} keeps nearly constant, (3) as the oxide layer thickness increases from about 0.3 nm to about 1.1 nm, {γ }{{se}} increases by 150 % . We propose that, in the submonolayer regime, the chemisorbed oxygen on the aluminum surface causes the decrease of {γ }{{se}} by creating a local potential barrier, which reduces the Auger neutralization rate and the energy gained by the Auger electrons. In the multilayer regime, as the oxide layer grows in thickness, there are three proposed mechanisms which cause the increase of {γ }{{se}}: (1) the work function decreases; (2) resonance neutralization and Auger de-excitation may exist. This is served as another channel for secondary electron production; (3) the kinetic energy of Auger electrons is increased on average, leading to a higher probability for electrons to overcome the surface potential barrier.

Reductant-dependent electron distribution among redox sites of laccase

DEFF Research Database (Denmark)

Farver, O; Goldberg, M; Wherland, S

1978-01-01

Rhus laccase (monophenol monooxygenase, monophenol,dihydroxyphenylalanine:oxygen oxidoreductase, EC 1.14.18.1) an O2/H2O oxidoreductase containing four copper ions bound to three redox sites (type 1, type 2, and type 3 Cu pair), was titrated anaerobically with several reductants having various ch...

Thermoelectric properties of Sr0.61Ba0.39Nb2O6-δ ceramics in different oxygen-reduction conditions

Science.gov (United States)

Li, Yi; Liu, Jian; Wang, Chun-Lei; Su, Wen-Bin; Zhu, Yuan-Hu; Li, Ji-Chao; Mei, Liang-Mo

2015-04-01

The thermoelectric properties of Sr0.61Ba0.39Nb2O6-δ ceramics, reduced in different conditions, are investigated in the temperature range from 323 K to 1073 K. The electrical transport behaviors of the samples are dominated by the thermal-activated polaron hopping in the low temperature range, the Fermi glass behavior in the middle temperature range, and the Anderson localized behavior in the high temperature range. The thermal conductivity presents a plateau at high-temperatures, indicating a glass-like thermal conduction behavior. Both the thermoelectric power factor and the thermal conductivity increase with the increase of the degree of oxygen-reduction. Taking these two factors into account, the oxygen-reduction can still contribute to promoting the thermoelectric figure of merit. The highest ZT value is obtained to be ˜0.19 at 1073 K in the heaviest oxygen reduced sample. Project supported by the National Basic Research Program of China (Grant No. 2013CB632506) and the National Natural Science Foundation of China (Grant Nos. 51202132 and 51002087).

Co- and defect-rich carbon nanofiber films as a highly efficient electrocatalyst for oxygen reduction

Science.gov (United States)

Kim, Il To; Song, Myeong Jun; Shin, Seoyoon; Shin, Moo Whan

2018-03-01

Many efforts are continuously devoted to developing high-efficiency, low-cost, and highly scalable oxygen reduction reaction (ORR) electrocatalysts to replace precious metal catalysts. Herein, we successfully synthesize Co- and defect-rich carbon nanofibers (CNFs) using an efficient heat treatment approach involving the pyrolysis of electrospun fibers at 370 °C under air. The heat treatment process produces Co-decorated CNFs with a high Co mass ratio, enriched pyridinic N, Co-pyridinic Nx clusters, and defect-rich carbon structures. The synergistic effects from composition and structural changes in the designed material increase the number of catalytically active sites for the ORR in an alkaline solution. The prepared Co- and defect-rich CNFs exhibit excellent ORR activities with a high ORR onset potential (0.954 V vs. RHE), a large reduction current density (4.426 mA cm-2 at 0.40 V), and a nearly four-electron pathway. The catalyst also exhibits a better long-term durability than commercial Pt/C catalysts. This study provides a novel hybrid material as an efficient ORR catalyst and important insight into the design strategy for CNF-based hybrid materials as electrochemical electrodes.

Oxygen: the two-faced elixir of life.

Science.gov (United States)

Biddle, Chuck

2008-02-01

Take a moment and consider our planet without oxygen. Imagine the earth some 2.5 billion years ago when oxygen first appeared as a waste product of early anaerobes. Oxygen, as we know it today, is essential for life. Abundant and relatively inexpensive to manufacture, oxygen has widespread use in industry and healthcare. Anesthesia providers routinely administer oxygen in concentrations exceeding that in ambient air to ensure clinical safety and to offset the predictable sequelae associated with patient, drug-related, and procedural factors. Understanding the history of this unique element is critical in evaluating the often contentious body of contemporary research that has illuminated its efficacy (as elixir) and its attendant complications (its "two-faced" nature). Of particular interest is its role in free radical formation as etiogenic in developing complications. Oxygen is a mainstay in the perioperative management of patients, but its administration should be guided by thoughtful and rational goal-directed outcomes to maximize efficacy and minimize complications associated with its use.

Synthesis of 2D Nitrogen-Doped Mesoporous Carbon Catalyst for Oxygen Reduction Reaction

Directory of Open Access Journals (Sweden)

Zhipeng Yu

2017-02-01

Full Text Available 2D nitrogen-doped mesoporous carbon (NMC is synthesized by using a mesoporous silica film as hard template, which is then investigated as a non-precious metal catalyst for the oxygen reduction reaction (ORR. The effect of the synthesis conditions on the silica template and carbon is extensively investigated. In this work, we employ dual templates—viz. graphene oxide and triblock copolymer F127—to control the textural features of a 2D silica film. The silica is then used as a template to direct the synthesis of a 2D nitrogen-doped mesoporous carbon. The resultant nitrogen-doped mesoporous carbon is characterized by transmission electron microscopy (TEM, nitrogen ad/desorption isotherms, X-ray photoelectron spectroscopy (XPS, cyclic voltammetry (CV, and rotating disk electrode measurements (RDE. The electrochemical test reveals that the obtained 2D-film carbon catalyst yields a highly electrochemically active surface area and superior electrocatalytic activity for the ORR compared to the 3D-particle. The superior activity can be firstly attributed to the difference in the specific surface area of the two catalysts. More importantly, the 2D-film morphology makes more active sites accessible to the reactive species, resulting in a much higher utilization efficiency and consequently better activity. Finally, it is noted that all the carbon catalysts exhibit a higher ORR activity than a commercial Pt catalyst, and are promising for use in fuel cells.

Single-Step versus Stepwise Two-Electron Reduction of Polyarylpyridiniums: Insights from the Steric Switching of Redox Potential Compression

Czech Academy of Sciences Publication Activity Database

Fortage, J.; Peltier, C.; Perruchot, Ch.; Takemoto, Y.; Teki, Y.; Bedioui, F.; Marvand, V.; Dupeyre, G.; Pospíšil, Lubomír; Adamo, C.; Hromadová, Magdaléna; Ciofini, I.; Lainé, P. P.

2012-01-01

Roč. 134, č. 5 (2012), s. 2691-2705 ISSN 0002-7863 Institutional research plan: CEZ:AV0Z40400503 Keywords : FUNCTIONALIZED TERPYRIDYL LIGANDS * GATED PHOTOINDUCED PROCESSES * ONE-ELECTRON REDUCTION Subject RIV: CG - Electrochemistry Impact factor: 10.677, year: 2012

Sheath and heat flow of a two-electron-temperature plasma in the presence of electron emission

International Nuclear Information System (INIS)

Sato, Kunihiro; Miyawaki, Fujio

1992-01-01

The electrostatic sheath and the heat flow of a two-electron-temperature plasma in the presence of electron emission are investigated analytically. It is shown that the energy flux is markedly enhanced to a value near the electron free-flow energy flux as a result of considerable reduction of the sheath potential due to electron emission if the fraction of hot electrons at the sheath edge is much smaller than one. If the hot- to cold-electron temperature ratio is of the order of ten and the hot electron density is comparable to the cold electron density, the action of the sheath as a thermal insulator is improved as a result of suppression of electron emission due to the space-charge effect of hot electrons. (author)

Hollow hemisphere-shaped macroporous graphene/tungsten carbide/platinum nanocomposite as an efficient electrocatalyst for the oxygen reduction reaction

International Nuclear Information System (INIS)

Li, Zesheng; Liu, Zhisen; Li, Bolin; Liu, Zhenghui; Li, Dehao; Wang, Hongqiang; Li, Qingyu

2016-01-01

Graphical abstract: Newfashioned hollow hemisphere-shaped macroporous graphene/tungsten carbide/platinum (HMG/WC/Pt) nanocomposite with interesting three-dimensional architecture bas been successfully fabricated as an efficient electrocatalyst for the oxygen reduction reaction. - Highlights: • Hollow hemisphere-shaped macroporous graphene is proposed as ORR catalyst support. • Honeycomb-like macroporous graphene/WC/Pt electrocatalyst is firsy prepared for ORR. • The present electrocatalyst exhibited greatly enhanced ORR catalytic activity and stability. - Abstract: Hollow hemisphere-shaped macroporous graphene/tungsten carbide/platinum (HMG/WC/Pt) nanocomposite has been synthesized as an efficient electrocatalyst for the oxygen reduction reaction (ORR). The HMG/WC/Pt sample has been systematically characterized by the X-ray diffraction (XRD), Scanning electron microscope (SEM) and Transmission electron microscopy (TEM). The analysis results indicate that the sample has an interesting three-dimensional hollow hemisphere-shaped macroporous architecture. The results also demonstrate the successful integration of WC and Pt nanoparticles on the HMG, in which the WC nanoparticles are in size of about 10 nm and the Pt nanoparticles are in size of about 3 nm. The as-prepared HMG/WC/Pt electrode displays excellent electrocatalytic performances for the ORR in 0.1 mol L −1 HClO 4 electrolyte. The mass activity (i m at 0.9 V) of HMG/WC/Pt is 206 mA mg −1 Pt, which is about 85% higher than that of Pt/C (112 mA mg −1 Pt). It also displayed a very high activity retention of 84.5% after 2000 cyclic voltammetry cycles for the HMG/WC/Pt, while that of the Pt/C is only 70.5%. The HMG/WC/Pt nanocomposite would be a promising electrocatalytic material for the ORR in Fuel cell applications.

Uranium- and Thorium-Doped Graphene for Efficient Oxygen and Hydrogen Peroxide Reduction

Czech Academy of Sciences Publication Activity Database

Sofer, Z.; Jankovský, O.; Šimek, P.; Klimová, K.; Macková, Anna; Pumera, M.

2014-01-01

Roč. 8, č. 7 (2014), s. 7106-7114 ISSN 1936-0851 R&D Projects: GA ČR(CZ) GBP108/12/G108 Institutional support: RVO:61389005 Keywords : graphene * actinides * electrochemistry * oxygen reduction * uranium Subject RIV: BG - Nuclear, Atomic and Molecular Physics, Colliders Impact factor: 12.881, year: 2014

Enhancing oxygen transport through Mixed-Ionic-and-Electronic-Conducting ceramic membranes

Science.gov (United States)

Yu, Anthony S.

Ceramic membranes based on Mixed-Ionic-and-Electronic-Conducting (MIEC) oxides are capable of separating oxygen from air in the presence of an oxygen partial-pressure gradient. These MIEC membranes show great promise for oxygen consuming industrial processes, such as the production of syngas from steam reforming of natural gas (SRM), as well as for electricity generation in Solid Oxide Fuel Cells (SOFC). For both applications, the overall performance is dictated by the rate of oxygen transport across the membrane. Oxygen transport across MIEC membranes is composed of a bulk oxygen-ion diffusion process and surface processes, such as surface reactions and adsorption/desorption of gaseous reactants/products. The main goal of this thesis was to determine which process is rate-limiting in order to significantly enhance the overall rate of oxygen transport in MIEC membrane systems. The rate-limiting step was determined by evaluating the total resistance to oxygen transfer, Rtot. Rtot is the sum of a bulk diffusion resistance in the membrane itself, Rb, and interfacial loss components, Rs. Rb is a function of the membrane's ionic conductivity and thickness, while Rs arises primarily from slow surface-exchange kinetics that cause the P(O2) at the surfaces of the membrane to differ from the P(O 2) in the adjacent gas phases. Rtot can be calculated from the Nernst potential across the membrane and the measured oxygen flux. The rate-limiting process can be determined by evaluating the relative contributions of the various losses, Rs and Rb, to Rtot. Using this method, this thesis demonstrates that for most membrane systems, Rs is the dominating factor. In the development of membrane systems with high oxygen transport rates, thin membranes with high ionic conductivities are required to achieve fast bulk oxygen-ion diffusion. However, as membrane thickness is decreased, surface reaction kinetics become more important in determining the overall transport rate. The two

Formation of Hydrogen Peroxide by Electrochemical Reduction of Molecular Oxygen using Luminol Chemiluminescence

International Nuclear Information System (INIS)

Rana, Sohail

2005-01-01

Formation of hydrogen peroxide by electrochemical reduction of molecular oxygen was examined by measuring luminol chemiluminescence and absorption spectrum using flow-injection method. Ferryl porphyrin is widely accepted as responsible species to stimulate the emission in hydrogen peroxide/ iron porphyrin/ luminol system. Emission was observed under cathodic potentials (0.05V at pH2.0 and -0.3V at pH11.0) by the electrochemical reduction of aerated electrolytes solution but emission was observed at anodic potentials. Iron porphyrin solution was added at down stream of the working electrode and was essential for the emission. Removal of the dissolved molecular oxygen resulted in the decrease of emission intensity by more than 70%. In order to examine the life time of reduced active species, delay tubes were introduced between working electrode Fe TMPyP inlet. Experimental results suggested the active species were stable for quite a long period. The emission was quenched considerably (>90%) when hydroperoxy was added at the down stream of working electrode whereas the Superoxide dismutase (SOD) had little effect and mannitol had no effect. The spectra at reduction potential under aerated condition were shifted to the longer wavelength (>430nm) compared to the original spectrum of Fe TMPyP (422nm), indicating that the ferryl species were mixed to some extent. These observations lead to the conclusion that hydrogen peroxide was produced first by electrochemical reduction of molecular oxygen which then converted Fe TMPyP into O=FeTMPyP to activate luminol. Comparing emission intensities with the reference experiments, the current efficiencies for the formation of hydrogen peroxide were estimated as about 30-65% in all over the pH range used. (author)

An investigation on the electrocatalytic properties of polypyrrole films on the kinetics of oxygen reduction reaction in PEMFC

Energy Technology Data Exchange (ETDEWEB)

Saremi, M.; Sharifi Asl, S.; Kazemi, Sh. [Tehran Univ., Tehran (Iran, Islamic Republic of). School of Metallurgy and Material Science Engineering

2008-07-01

A proton exchange membrane (PEM) fuel cell has high power density, low weight, very short start-up time and no leakage of electrolytes. However, there are some disadvantages when operating the PEM fuel cell at room temperature. Many studies involving the widespread commercial use of Pt-based electrocatalysts search for low-cost electrocatalysts for the oxygen reduction reaction. In recent years, much attention has been placed on the use of electrocatalysis for the conducting polymer electrode. Polypyrrole has attracted much attention as an advanced conducting material because of its good environmental stability, easy synthesis and high conductivity. This study examined the effect of the polypyrrole catalyst in a PEMFC cathode. The electropolymerization of pyrrole was carried out in a 3-electrode cell using pure hydrogen and oxygen as the reactants. Tests were carried out at room temperature and cell impedance was measured. The polymer was formed galvanostatically in a 0.1 M pyrrole with a 0.15 KCl aqueous solution with a 20 mA/cm{sup 2} current density. The effect of operating voltage and oxygen mass transport was examined by EIS method, which separates these two phenomena. The study showed that polypyrrole has a catalytic effect for oxygen reduction reaction in PEMFC comparable to a Pt catalyzed electrode. Although the cell potential with polypyrrole was slightly lower than a Pt coated cell, it was found to be more economical. 8 refs., 2 figs.

Structure of the Zymomonas mobilis respiratory chain: oxygen affinity of electron transport and the role of cytochrome c peroxidase.

Science.gov (United States)

Balodite, Elina; Strazdina, Inese; Galinina, Nina; McLean, Samantha; Rutkis, Reinis; Poole, Robert K; Kalnenieks, Uldis

2014-09-01

The genome of the ethanol-producing bacterium Zymomonas mobilis encodes a bd-type terminal oxidase, cytochrome bc1 complex and several c-type cytochromes, yet lacks sequences homologous to any of the known bacterial cytochrome c oxidase genes. Recently, it was suggested that a putative respiratory cytochrome c peroxidase, receiving electrons from the cytochrome bc1 complex via cytochrome c552, might function as a peroxidase and/or an alternative oxidase. The present study was designed to test this hypothesis, by construction of a cytochrome c peroxidase mutant (Zm6-perC), and comparison of its properties with those of a mutant defective in the cytochrome b subunit of the bc1 complex (Zm6-cytB). Disruption of the cytochrome c peroxidase gene (ZZ60192) caused a decrease of the membrane NADH peroxidase activity, impaired the resistance of growing culture to exogenous hydrogen peroxide and hampered aerobic growth. However, this mutation did not affect the activity or oxygen affinity of the respiratory chain, or the kinetics of cytochrome d reduction. Furthermore, the peroxide resistance and membrane NADH peroxidase activity of strain Zm6-cytB had not decreased, but both the oxygen affinity of electron transport and the kinetics of cytochrome d reduction were affected. It is therefore concluded that the cytochrome c peroxidase does not terminate the cytochrome bc1 branch of Z. mobilis, and that it is functioning as a quinol peroxidase. © 2014 The Authors.

The electrochemical behavior of cobalt phthalocyanine/platinum as methanol-resistant oxygen-reduction electrocatalysts for DMFC

Energy Technology Data Exchange (ETDEWEB)

Lu, Yuhao; Reddy, Ramana G. [Department of Metallurgical and Materials Engineering, The University of Alabama, P.O. Box 870202, Tuscaloosa, AL 35487 (United States)

2007-02-01

The electrochemical behavior of cobalt phthalocyanine/platinum as methanol-resistant oxygen-reduction electrocatalyst for DMFC was investigated. Platinum was chemically deposited on the carbon-supported cobalt phthalocyanine (CoPc), and then it was heat-treated in high purity nitrogen at 300 C, 635 C and 980 C. In order to evaluate the electrocatalytic behavior of CoPc-Pt/C, the PtCo/C and Pt/C as reference catalysts were employed. TGA, XRD, EDAX, XPS and electrochemical experiments were used to study the thermal stability, crystal structure, physical characterization and electrochemical behavior of these catalysts. These catalysts exhibited similar electrocatalytic activity for oxygen reaction in 0.5 M H{sub 2}SO{sub 4} solution. In methanol tolerance experiments, Pt/C, PtCo/C and CoPc-Pt/C heated at 980 C were active for the methanol oxidation reaction (MOR). The presence of Co did not improve resistance to methanol poisoning. However, the CoPc-Pt/C after 300 C or 635 C heat-treatment demonstrated significant inactivity for MOR, hence they have a good ability to resist methanol poisoning. The current study indicated that the macrocyclic structure of phthalocyanine is the most important factor to improve the methanol tolerance of CoPc-Pt/C as the oxygen-reduction reaction (ORR) electrocatalyst. The CoPc-Pt based catalyst should be a good alternation for oxygen electro-reduction reaction in DMFC. (author)

Reduced-graphene-oxide supported tantalum-based electrocatalysts: Controlled nitrogen doping and oxygen reduction reaction

Science.gov (United States)

Yang, Xiaoyun; Mo, Qijie; Guo, Yulin; Chen, Nana; Gao, Qingsheng

2018-03-01

Controlled N-doping is feasible to engineer the surface stoichiometry and the electronic configuration of metal-oxide electrocatalysts toward efficient oxygen reduction reactions (ORR). Taking reduced graphene oxide supported tantalum-oxides (TaOx/RGO) for example, this work illustrated the controlled N-doping in both metal-oxides and carbon supports, and the contribution to the improved ORR activity. The active N-doped TaOx/RGO electrocatalysts were fabricated via SiO2-assisted pyrolysis, in which the amount and kind of N-doping were tailored toward efficient electrocatalysis. The optimal nanocomposites showed a quite positive half-wave potential (0.80 V vs. RHE), the excellent long-term stability, and the outstanding tolerance to methanol crossing. The improvement in ORR was reasonably attributed to the synergy between N-doped TaOx and N-doped RGO. Elucidating the importance of controlled N-doping for electrocatalysis, this work will open up new opportunities to explore noble-metal-free materials for renewable energy applications.

Recent advances in the kinetics of oxygen reduction

Energy Technology Data Exchange (ETDEWEB)

Adzic, R.

1996-07-01

Oxygen reduction is considered an important electrocatalytic reaction; the most notable need remains improvement of the catalytic activity of existing metal electrocatalysts and development of new ones. A review is given of new advances in the understanding of reaction kinetics and improvements of the electrocatalytic properties of some surfaces, with focus on recent studies of relationship of the surface properties to its activity and reaction kinetics. The urgent need is to improve catalytic activity of Pt and synthesize new, possibly non- noble metal catalysts. New experimental techniques for obtaining new level of information include various {ital in situ} spectroscopies and scanning probes, some involving synchrotron radiation. 138 refs, 18 figs, 2 tabs.

Improvement of electron emission characteristics of porous silicon emitter by using cathode reduction and electrochemical oxidation

Energy Technology Data Exchange (ETDEWEB)

Li, He; Wenjiang, Wang, E-mail: wwj@mail.xjtu.edu.cn; Xiaoning, Zhang

2017-03-31

Highlights: • An electron emitter based on porous silicon having the strong application potential was prepared in the studying. • A new simple and convenient post-treat technique was proposed to improve the electron emission properties of the PS emitter. • It demonstrated that the improving of the PS morphology and the oxygen distribution is very important to the PS emitter. - Abstract: A new simple and convenient post-treat technique combined the cathode reduction (CR) and electrochemical oxidation (ECO) was proposed to improve the electron emission properties of the surface-emitting cold cathodes based on the porous silicon (PS). It is demonstrated here that by introducing this new technique combined CR and ECO, the emission properties of the diode have been significantly improved than those as-prepared samples. The experimental results showed that the emission current densities and efficiencies of sample treated by CR were 62 μA/cm{sup 2} and 12.10‰, respectively, nearly 2 orders of magnitude higher than those of as-prepared sample. Furthermore, the CR-treated PS emitter shows higher repeatability and stability compared with the as-prepared PS emitter. The scanning electron microscope (SEM), atomic force microscope (AFM), energy dispersive spectrometer (EDS), furier transformed infrared (FTIR) spectroscopy results indicated that the improved mechanism is mainly due to the passivation of the PS, which not only improve the PS morphology by the passivation of the H{sup +} but also improve the uniformity of the oxygen content distribution in the whole PS layer. Therefore, the method combined the CR treatment and ECO is expected to be a valuable technique to enhance the electron emission characteristics of the PS emitter.

Improvement of electron emission characteristics of porous silicon emitter by using cathode reduction and electrochemical oxidation

International Nuclear Information System (INIS)

Li, He; Wenjiang, Wang; Xiaoning, Zhang

2017-01-01

Highlights: • An electron emitter based on porous silicon having the strong application potential was prepared in the studying. • A new simple and convenient post-treat technique was proposed to improve the electron emission properties of the PS emitter. • It demonstrated that the improving of the PS morphology and the oxygen distribution is very important to the PS emitter. - Abstract: A new simple and convenient post-treat technique combined the cathode reduction (CR) and electrochemical oxidation (ECO) was proposed to improve the electron emission properties of the surface-emitting cold cathodes based on the porous silicon (PS). It is demonstrated here that by introducing this new technique combined CR and ECO, the emission properties of the diode have been significantly improved than those as-prepared samples. The experimental results showed that the emission current densities and efficiencies of sample treated by CR were 62 μA/cm"2 and 12.10‰, respectively, nearly 2 orders of magnitude higher than those of as-prepared sample. Furthermore, the CR-treated PS emitter shows higher repeatability and stability compared with the as-prepared PS emitter. The scanning electron microscope (SEM), atomic force microscope (AFM), energy dispersive spectrometer (EDS), furier transformed infrared (FTIR) spectroscopy results indicated that the improved mechanism is mainly due to the passivation of the PS, which not only improve the PS morphology by the passivation of the H"+ but also improve the uniformity of the oxygen content distribution in the whole PS layer. Therefore, the method combined the CR treatment and ECO is expected to be a valuable technique to enhance the electron emission characteristics of the PS emitter.

Using rates of oxygen and nitrate reduction to map the subsurface distribution of groundwater denitrification

Science.gov (United States)

Kolbe, T.; De Dreuzy, J. R.; Abbott, B. W.; Aquilina, L.; Babey, T.; Green, C. T.; Fleckenstein, J. H.; Labasque, T.; Laverman, A.; Marçais, J.; Peiffer, S.; Thomas, Z.; Pinay, G.

2017-12-01

Widespread fertilizer application over the last 70 years has caused serious ecological and socioeconomic problems in aquatic and estuarine ecosystems. When surplus nitrogen leaches as nitrate (a major groundwater pollutant) to the aquifer, complex flow dynamics and naturally occurring degradation processes control its transport. Under the conditions of depleted oxygen and abundant electron donors, microorganisms reduce NO3- to N2 (denitrification). Denitrification rates vary over orders of magnitude among sites within the same aquifer, complicating estimation of denitrification capacity at the catchment scale. Because it is impractical or impossible to access the subsurface to directly quantify denitrification rates, reactivity is often assumed to occur continuous along flowlines, potentially resulting in substantial over- or underestimation of denitrification. Here we investigated denitrification in an unconfined crystalline aquifer in western France using a combination of common tracers (chlorofluorocarbons, O2, NO3-, and N2) measured in 16 wells to inform a time-based modeling approach. We found that spatially variable denitrification rates arise from the intersection of nitrate rich water with reactive zones defined by the abundance of electron donors (primarily pyrite). Furthermore, based on observed reaction rates of the sequential reduction of oxygen and nitrate, we present a general framework to estimate the location and intensity of the reactive zone in aquifers. Accounting for the vertical distribution of reaction rates results in large differences in estimations of net denitrification rates that assume homogeneous reactivity. This new framework provides a tractable approach for quantifying catchment and regional groundwater denitrification rates that could be used to improve estimation of groundwater resilience to nitrate pollution and develop more realistic management strategies.

Electron Paramagnetic Resonance pO2 Image Tumor Oxygen-Guided Radiation Therapy Optimization.

Science.gov (United States)

Epel, Boris; Maggio, Matt; Pelizzari, Charles; Halpern, Howard J

2017-01-01

Modern standards for radiation treatment do not take into account tumor oxygenation for radiation treatment planning. Strong correlation between tumor oxygenation and radiation treatment success suggests that oxygen-guided radiation therapy (OGRT) may be a promising enhancement of cancer radiation treatment. We have developed an OGRT protocol for rodents. Electron paramagnetic resonance (EPR) imaging is used for recording oxygen maps with high spatial resolution and excellent accuracy better than 1 torr. Radiation is delivered with an animal intensity modulated radiation therapy (IMRT) XRAD225Cx micro-CT/ therapy system. The radiation plan is delivered in two steps. First, a uniform 15% tumor control dose (TCD 15 ) is delivered to the whole tumor. In the second step, an additional booster dose amounting to the difference between TCD 98 and TCD 15 is delivered to radio-resistant, hypoxic tumor regions. Delivery of the booster dose is performed using a multiport conformal beam protocol. For radiation beam shaping we used individual radiation blocks 3D-printed from tungsten infused ABS polymer. Calculation of beam geometry and the production of blocks is performed next to the EPR imager, immediately after oxygen imaging. Preliminary results demonstrate the sub-millimeter precision of the radiation delivery and high dose accuracy. The efficacy of the radiation treatment is currently being tested on syngeneic FSa fibrosarcoma tumors grown in the legs of C3H mice.

S- and N-Doped Graphene Nanomaterials for the Oxygen Reduction Reaction

Directory of Open Access Journals (Sweden)

Luis Miguel Rivera

2017-09-01

Full Text Available In the current work, heteroatom-doped graphene materials containing different atomic ratios of nitrogen and sulphur were employed as electrocatalysts for the oxygen reduction reaction (ORR in acidic and alkaline media. To this end, the hydrothermal route and different chemical reducing agents were employed to synthesize the catalytic materials. The physicochemical characterization of the catalysts was performed by several techniques, such as X-ray diffraction, Raman spectroscopy and elemental analysis; meanwhile, the electrochemical performance of the materials toward the ORR was analyzed by linear sweep voltammetry (LSV, rotating disk electrode (RDE and rotating ring-disk electrode (RRDE techniques. The main results indicate that the ORR using heteroatom-doped graphene is a direct four-electron pathway, for which the catalytic activity is higher in alkaline than in acidic media. Indeed, a change of the reaction mechanism was observed with the insertion of N into the graphenic network, by the rate determining step changes from the first electrochemical step (formation of adsorbed OOH on glassy carbon to the removal of adsorbed O (Oad from the N-graphene surface. Moreover, the addition of sulphur atoms into the N-graphene structure increases the catalytic activity toward the ORR, as the desorption of Oad is accelerated.

Heteroatom-doped porous carbon from methyl orange dye wastewater for oxygen reduction

Directory of Open Access Journals (Sweden)

Yiqing Wang

2018-04-01

Full Text Available Banana peel-derived porous carbon (BPPC was prepared from banana peel and used as an adsorbent for methyl orange (MO wastewater removal. BPPC-MO50 is a N,S-doped BPPC obtained via secondary carbonization. The BPPC-MO50 exhibited a high specific surface area of 1774.3 m2/g. Heteroatom-doped porous carbon (PC was successfully synthesized from the BPPC absorbed MO at high temperature and used for oxygen reduction. The BPPC-MO50 displayed the highest ORR onset potential among all carbon-based electrocatalysts, i.e., 0.93 V vs. reversible hydrogen electrode (RHE. This is the first report to describe porous carbon-activated materials from agriculture and forestry waste that is used for adsorption of dyes from wastewater via an enhanced heteroatom (N,S content. These results may contribute to the sustainable development of dye wastewater treatment by transforming saturated PC into an effective material and has potential applications in fuel cells or as energy sources. Keywords: Banana peel, Dye wastewater, Porous carbon, Heteroatom doping, Oxygen reduction reaction

Communication: Enhanced oxygen reduction reaction and its underlying mechanism in Pd-Ir-Co trimetallic alloys

Energy Technology Data Exchange (ETDEWEB)

Ham, Hyung Chul; Hwang, Gyeong S., E-mail: gshwang@che.utexas.edu [Department of Chemical Engineering, The University of Texas at Austin, Austin, Texas 78712 (United States); Manogaran, Dhivya [Department of Chemistry and Biochemistry, The University of Texas at Austin, Austin, Texas 78712 (United States); Lee, Kang Hee; Jin, Seon-ah; You, Dae Jong; Pak, Chanho [Energy Lab, Samsung Advanced Institute of Technology, Samsung Electronics Co., Ltd., Suwon (Korea, Republic of); Kwon, Kyungjung [Department of Energy and Mineral Resources Engineering, Sejong University, Seoul 143-747 (Korea, Republic of)

2013-11-28

Based on a combined density functional theory and experimental study, we present that the electrochemical activity of Pd{sub 3}Co alloy catalysts toward oxygen reduction reaction (ORR) can be enhanced by adding a small amount of Ir. While Ir tends to favorably exist in the subsurface layers, the underlying Ir atoms are found to cause a substantial modification in the surface electronic structure. As a consequence, we find that the activation barriers of O/OH hydrogenation reactions are noticeably lowered, which would be mainly responsible for the enhanced ORR activity. Furthermore, our study suggests that the presence of Ir in the near-surface region can suppress Co out-diffusion from the Pd{sub 3}Co substrate, thereby improving the durability of Pd-Ir-Co catalysts. We also discuss the relative roles played by Ir and Co in enhancing the ORR activity relative to monometallic Pd catalysts.

Communication: Enhanced oxygen reduction reaction and its underlying mechanism in Pd-Ir-Co trimetallic alloys

International Nuclear Information System (INIS)

Ham, Hyung Chul; Hwang, Gyeong S.; Manogaran, Dhivya; Lee, Kang Hee; Jin, Seon-ah; You, Dae Jong; Pak, Chanho; Kwon, Kyungjung

2013-01-01

Based on a combined density functional theory and experimental study, we present that the electrochemical activity of Pd 3 Co alloy catalysts toward oxygen reduction reaction (ORR) can be enhanced by adding a small amount of Ir. While Ir tends to favorably exist in the subsurface layers, the underlying Ir atoms are found to cause a substantial modification in the surface electronic structure. As a consequence, we find that the activation barriers of O/OH hydrogenation reactions are noticeably lowered, which would be mainly responsible for the enhanced ORR activity. Furthermore, our study suggests that the presence of Ir in the near-surface region can suppress Co out-diffusion from the Pd 3 Co substrate, thereby improving the durability of Pd-Ir-Co catalysts. We also discuss the relative roles played by Ir and Co in enhancing the ORR activity relative to monometallic Pd catalysts

Preparation of Bimetallic Pd-Co Nanoparticles on Graphene Support for Use as Methanol Tolerant Oxygen Reduction Electrocatalysts

Directory of Open Access Journals (Sweden)

R. N. Singh

2012-12-01

Full Text Available Graphene-supported (40-x wt% Pd x wt% Co (0≤x≤13.33 alloys/composites have been prepared by a microwave-assisted polyol reduction method and been investigated for their structural and electrocatalytic properties for the oxygen reduction reaction (ORR in 0.5 M H2SO4 at 298 K. The study demonstrated that the bimetallic Pd-Co composite nanoparticles are, in fact, alloy nanoparticles with fcc crystalline structure. Partial substitution of Pd by Co (from 3.64 to 13.33 wt% in 40 wt% Pd/graphene decreases the lattice parameter as well as the crystallite size and increases the apparent catalytic activity, the latter, however, being the greatest with 8 wt% Co. The ORR activity of the active 32 wt% Pd 8wt% Co is found to be considerably low when it was deposited on the support multiwall carbon nanotubes under similar conditions. The rotating disk electrode study indicated that the ORR on 32 wt% Pd 8 wt% Co/GNS in 0.5 M H2SO4 follows approximately the four-electron pathway.

Silver nanowires as catalytic cathodes for stabilizing lithium-oxygen batteries

Science.gov (United States)

Kwak, Won-Jin; Jung, Hun-Gi; Lee, Seon-Hwa; Park, Jin-Bum; Aurbach, Doron; Sun, Yang-Kook

2016-04-01

Silver nanowires have been investigated as a catalytic cathode material for lithium-oxygen batteries. Their high aspect ratio contributes to the formation of a corn-shaped layer structure of the poorly crystalline lithium peroxide (Li2O2) nanoparticles produced by oxygen reduction in poly-ether based electrolyte solutions. The nanowire morphology seems to provide the necessary large contact area and facile electron supply for a very effective oxygen reduction reaction. The unique morphology and structure of the Li2O2 deposits and the catalytic nature of the silver nano-wires promote decomposition of Li2O2 at low potentials (below 3.4 V) upon the oxygen evolution. This situation avoids decomposition of the solution species and oxidation of the electrodes during the anodic (charge) reactions, leading to high electrical efficiently of lithium-oxygen batteries.

Heterogeneous electron transfer of a two-centered heme protein: redox and electrocatalytic properties of surface-immobilized cytochrome C(4).

Science.gov (United States)

Monari, Stefano; Battistuzzi, Gianantonio; Borsari, Marco; Di Rocco, Giulia; Martini, Laura; Ranieri, Antonio; Sola, Marco

2009-10-15

The recombinant diheme cytochrome c(4) from the psycrophilic bacterium Pseudoalteromonas haloplanktis TAC 125 and its Met64Ala and Met164Ala variants, which feature a hydroxide ion axially bound to the heme iron at the N- and C-terminal domains, respectively, were found to exchange electrons efficiently with a gold electrode coated with a SAM of 11-mercapto-1-undecanoic acid. The mutation-induced removal of the redox equivalence of the two heme groups and changes in the net charge of the protein lobes yield two-centered protein systems with unprecedented properties in the electrode-immobilized state. The heterogeneous and intraheme electron transfer processes were characterized for these species in which the high- and low-potential heme groups are swapped over in the bilobal protein framework and experience a constrained (M64A) and unconstrained (M164A) orientation toward the electrode. The reduction thermodynamics for the native and mutated hemes were measured for the first time for a diheme cytochrome c. In the diffusing regime, they reproduce closely those for the corresponding centers in single-heme class-I cytochromes c, despite the low sequence identity. Larger differences are observed in the thermodynamics of the immobilized species and in the heterogeneous electron transfer rate constants. T-dependent kinetic measurements show that the proteins are positioned approximately 7 A from the HOOC-terminated SAM-coated electrode. Protein-electrode orientation and efficient intraheme ET enable the His,OH(-)-ligated heme A of the immobilized Met64Ala variant to carry out the reductive electrocatalysis of molecular oxygen. This system therefore constitutes a novel two-centered heme-based biocatalytic interface to be exploited for "third-generation" amperometric biosensing.

Humin as an electron donor for enhancement of multiple microbial reduction reactions with different redox potentials in a consortium.

Science.gov (United States)

Zhang, Dongdong; Zhang, Chunfang; Xiao, Zhixing; Suzuki, Daisuke; Katayama, Arata

2015-02-01

A solid-phase humin, acting as an electron donor, was able to enhance multiple reductive biotransformations, including dechlorination of pentachlorophenol (PCP), dissimilatory reduction of amorphous Fe (III) oxide (FeOOH), and reduction of nitrate, in a consortium. Humin that was chemically reduced by NaBH4 served as an electron donor for these microbial reducing reactions, with electron donating capacities of 0.013 mmol e(-)/g for PCP dechlorination, 0.15 mmol e(-)/g for iron reduction, and 0.30 mmol e(-)/g for nitrate reduction. Two pairs of oxidation and reduction peaks within the humin were detected by cyclic voltammetry analysis. 16S rRNA gene sequencing-based microbial community analysis of the consortium incubated with different terminal electron acceptors, suggested that Dehalobacter sp., Bacteroides sp., and Sulfurospirillum sp. were involved in the PCP dechlorination, dissimilatory iron reduction, and nitrate reduction, respectively. These findings suggested that humin functioned as a versatile redox mediator, donating electrons for multiple respiration reactions with different redox potentials. Copyright © 2014 The Society for Biotechnology, Japan. Published by Elsevier B.V. All rights reserved.

Novel VN/C nanocomposites as methanol-tolerant oxygen reduction electrocatalyst in alkaline electrolyte

OpenAIRE

K. Huang; K. Bi; C. Liang; S. Lin; R. Zhang; W. J. Wang; H. L. Tang; M. Lei

2015-01-01

A novel VN/C nanostructure consisting of VN nanoparticles and graphite-dominant carbon layers is synthesized by nitridation of V2O5 using melamine as reductant under inert atmosphere. High crystalline VN nanoparticles are observed to be uniformly distributed in carbon layers with an average size of ca13.45?nm. Moreover, the electrocatalytic performance of VN/C towards oxygen reduction reaction (ORR) in alkaline electrolyte is fascinating. The results show that VN/C has a considerable ORR acti...

The Nernst equation applied to oxidation-reduction reactions in myoglobin and hemoglobin. Evaluation of the parameters.

Science.gov (United States)

Saroff, Harry A

Analyses of the binding of oxygen to monomers such as myoglobin employ the Mass Action equation. The Mass Action equation, as such, is not directly applicable for the analysis of the binding of oxygen to oligomers such as hemoglobin. When the binding of oxygen to hemoglobin is analyzed, models incorporating extensions of mass action are employed. Oxidation-reduction reactions of the heme group in myoglobin and hemoglobin involve the binding and dissociation of electrons. This reaction is described with the Nernst equation. The Nernst equation is applicable only to a monomeric species even if the number of electrons involved is greater than unity. To analyze the oxidation-reduction reaction in a molecule such as hemoglobin a model is required which incorporates extensions of the Nernst equation. This communication develops models employing the Nernst equation for oxidation-reduction reactions analogous to those employed for hemoglobin in the analysis of the oxygenation (binding of oxygen) reaction.

Effect of hypolimnetic oxygenation on oxygen depletion rates in two water-supply reservoirs.

Science.gov (United States)

Gantzer, Paul A; Bryant, Lee D; Little, John C

2009-04-01

Oxygenation systems, such as bubble-plume diffusers, are used to improve water quality by replenishing dissolved oxygen (DO) in the hypolimnia of water-supply reservoirs. The diffusers induce circulation and mixing, which helps distribute DO throughout the hypolimnion. Mixing, however, has also been observed to increase hypolimnetic oxygen demand (HOD) during system operation, thus accelerating oxygen depletion. Two water-supply reservoirs (Spring Hollow Reservoir (SHR) and Carvins Cove Reservoir (CCR)) that employ linear bubble-plume diffusers were studied to quantify diffuser effects on HOD. A recently validated plume model was used to predict oxygen addition rates. The results were used together with observed oxygen accumulation rates to evaluate HOD over a wide range of applied gas flow rates. Plume-induced mixing correlated well with applied gas flow rate and was observed to increase HOD. Linear relationships between applied gas flow rate and HOD were found for both SHR and CCR. HOD was also observed to be independent of bulk hypolimnion oxygen concentration, indicating that HOD is controlled by induced mixing. Despite transient increases in HOD, oxygenation caused an overall decrease in background HOD, as well as a decrease in induced HOD during diffuser operation, over several years. This suggests that the residual or background oxygen demand decreases from one year to the next. Despite diffuser-induced increases in HOD, hypolimnetic oxygenation remains a viable method for replenishing DO in thermally-stratified water-supply reservoirs such as SHR and CCR.

Oxygen Reduction on Gas-Diffusion Electrodes for Phosphoric Acid Fuel Cells by a Potential Decay Method

DEFF Research Database (Denmark)

Li, Qingfeng; Gang, Xiao; Hjuler, Hans Aage

1995-01-01

The reduction of gaseous oxygen on carbon supported platinum electrodes has been studied at 150 degrees C with polarization and potential decay measurements. The electrolyte was either 100 weight percent phosphoric acid or that acid with a fluorinated additive, potassium perfluorohexanesulfonate ......6F13SO3K). The pseudo-Tafel curves of the overpotential vs. log (ii(L)/(i(L) - i)) show a two-slope behavior, probably due to different adsorption mechanisms. The potential relaxations as functions of log (t + tau) and log (-d eta/dt) have been plotted. The variations of these slopes...

Electrocatalytic Performance of Carbon Supported WO3-Containing Pd–W Nanoalloys for Oxygen Reduction Reaction in Alkaline Media

Directory of Open Access Journals (Sweden)

Nan Cui

2018-05-01

Full Text Available In this paper, we report that WOx containing nanoalloys exhibit stable electrocatalytic performance in alkaline media, though bulk WO3 is easy to dissolve in NaOH solution. Carbon supported oxide-rich Pd–W alloy nanoparticles (PdW/C with different Pd:W atom ratios were prepared by the reduction–oxidation method. Among the catalysts, the oxide-rich Pd0.8W0.2/C (Pd/W = 8:2, atom ratio exhibits the highest catalytic activity for the oxygen reduction reaction. The X-ray photoelectron spectroscopy data shows that ~40% of Pd atoms and ~60% of the W atoms are in their oxide form. The Pd 3d5/2 binding energy of the oxide-rich Pd–W nanoalloys is higher than that of Pd/C, indicating the electronic structure of Pd is affected by the strong interaction between Pd and W/WO3. Compare to Pd/C, the onset potential of the oxygen reduction reaction at the oxide-rich Pd0.8W0.2/C shifts to a higher potential. The current density (mA·mg Pd−1 at the oxide-rich Pd0.8W0.2/C is ~1.6 times of that at Pd/C. The oxide-rich Pd0.8W0.2/C also exhibits higher catalytic stability than Pd/C, which demonstrates that it is a prospective candidate for the cathode of fuel cells operating with alkaline electrolyte.

The oxygen reduction reaction mechanism on Pt(111) from density functional theory calculations

DEFF Research Database (Denmark)

Tripkovic, Vladimir; Skulason, Egill; Siahrostami, Samira

2010-01-01

We study the oxygen reduction reaction (ORR) mechanism on a Pt(1 1 1) surface using density functional theory calculations We find that at low overpotentials the surface is covered with a half dissociated water layer We estimate the barrier for proton transfer to this surface and the barrier...

Defect-induced Catalysis toward the Oxygen Reduction Reaction in Single-walled Carbon Nanotube: Nitrogen doped and Non-nitrogen doped

International Nuclear Information System (INIS)

Lu, Di; Wu, Dan; Jin, Jian; Chen, Liwei

2016-01-01

Single-walled carbon nanotubes (SWNTs) are post-treated by argon (Ar) or ammonia (NH 3 ) plasma irradiation to introduce defects that are potentially related to catalysis towards the oxygen reduction reaction (ORR). Electrochemical characterization in alkali medium suggests that the plasma irradiated SWNTs demonstrate enhanced catalytic activity toward the ORR with a positively shifted threshold potential. Moreover the enhanced desired four-electron pathway catalytic activity, which exhibited as the positive shifted threshold potential, is independent of the nitrogen dopant. The nature of the defects is probed with Raman and X-ray photoelectron spectroscopy. The results indicate that the non-nitrogen doped defects of SWNTs contribute to the actual active site for the ORR.

Electrocatalytic behavior of thin Co-Te-O films in oxygen evolution and reduction reactions

International Nuclear Information System (INIS)

Rashkova, V.; Kitova, S.; Vitanov, T.

2007-01-01

Co-Te-O catalytic films, obtain by vacuum co-evaporation of Co and TeO 2 are investigated as electrocatalysts for oxygen reactions in alkaline media. Bifunctional gas-diffusion oxygen electrodes (gde) are prepared by direct deposition of catalyst films on gas-diffusion membranes (gdm) consisting of hydrophobized carbon blacks or hydrophobized 'Ebonex' (suboxides of titanium dioxide). Thus obtained electrodes with different atomic ratio R Co/Te of the catalyst, treated at different temperatures were electrochemically tested by means of cyclic voltammetry and steady-state voltammetry. It is shown that the electrodes exhibit high catalytic activity toward oxygen evolution and reduction reaction despite very low catalyst loading of about 0.05-0.5 mg cm -2

Electron transfer number control of the oxygen reduction reaction on nitrogen-doped reduced graphene oxides for the air electrodes of zinc-air batteries and organic degradation

International Nuclear Information System (INIS)

Wu, Sheng-Hui; Li, Po-Chieh; Hu, Chi-Chang

2016-01-01

The mean electron transfer number (n) of the oxygen reduction reaction (ORR) on reduced graphene oxide (rGO) is controlled by nitrogen doping for the air electrodes of Zn-air batteries and electrochemical organic degradation. Melamine and pyrrole are employed as the nitrogen sources for fabricating N-doped rGO (N-rGO) by microwave-assisted hydrothermal synthesis (MAHS). The n value of the ORR is determined by the rotating ring-disk electrode (RRDE) voltammetry and is successfully controlled from 2.34 to 3.93 by preparation variables. The N-doped structures are examined by the x-ray photoelectron spectroscopic (XPS) analysis. The morphology and the defect degree of N-rGOs are characterized by high resolution transmission electron microscopy (HR-TEM) and Raman spectroscopy. N-rGOs with high and low n values are employed as the air electrode catalysts of zinc-air batteries and in-situ hydrogen peroxide (H_2O_2) generation, respectively. The highest discharge cell voltage of 1.235 V for a Zn-air battery is obtained at 2 mA cm"−"2 meanwhile the current efficiency of H_2O_2 generation in 1-h electrolysis at 0 V (vs. RHE) reaches 43%. The electrocatalytic degradation of orange G (OG), analyzed by UV-VIS absorption spectra, reveals a high decoloration degree from the relative absorbance of 0.38 for the azo π-conjugation structure of OG. - Highlights: • The mean electron transfer number (n) is controlled by nitrogen doping. • Melamine and pyrrole are used as the nitrogen sources for fabricating N-rGO. • The n value is successfully controlled from 2.34 to 3.93 by preparation variables. • The highest discharge cell voltage of 1.235 V for a Zn-air battery. • The current efficiency of H_2O_2 generation 1-h electrolysis reaches 43%.

Singlet oxygen in the low-temperature plasma of an electron-beam-sustained discharge

International Nuclear Information System (INIS)

Vagin, N. P.; Ionin, A. A.; Klimachev, Yu. M.; Kotkov, A. A.; Kochetov, I. V.; Napartovich, A. P.; Podmar'kov, Yu. P.; Rulev, O. A.; Seleznev, L. V.; Sinitsyn, D. V.; Frolov, M. P.; Yuryshev, N. N.

2006-01-01

Results are presented from experimental and theoretical studies of the production of singlet delta oxygen in a pulsed electron-beam-sustained discharge ignited in a large (∼18-1) volume at a total gas mixture pressure of up to 210 Torr. The measured yield of singlet oxygen reaches 10.5%. It is found that varying the reduced electric field from ∼2 to ∼11 kV/(cm atm) slightly affects singlet oxygen production. It is shown experimentally that an increase in the gas mixture pressure or the specific input energy reduces the duration of singlet oxygen luminescence. The calculated time evolution of the singlet oxygen concentration is compared with experimental results

Efficient oxygen reduction reaction using ruthenium tetrakis(diaquaplatinum)octacarboxyphthalocyanine catalyst supported on MWCNT platform

CSIR Research Space (South Africa)

Maxakato, NW

2011-02-01

Full Text Available -1 Electroanalysis 2011, 23, No. 2, 325 ? 329 Efficient Oxygen Reduction Reaction Using Ruthenium Tetrakis(diaquaplatinum)Octacarboxyphthalocyanine Catalyst Supported on MWCNT Platform Nobanathi W. Maxakato,a Solomon A. Mamuru,a Kenneth I. Ozoemena*a, b a...

Growth and chemosensory behavior of sulfate-reducing bacteria in oxygen-sulfide gradients

DEFF Research Database (Denmark)

Sass, Andrea M.; Wieland, Andrea Eschemann; Kühl, Michael

2002-01-01

Growth and chemotactic behavior in oxic–anoxic gradients were studied with two freshwater and four marine strains of sulfate-reducing bacteria related to the genera Desulfovibrio, Desulfomicrobium or Desulfobulbus. Cells were grown in oxygen–sulfide counter-gradients within tubes filled with agar...... chemotactically to lactate, nitrate, sulfate and thiosulfate, and even sulfide functioned as an attractant. In oxic–anoxic gradients the bacteria moved away from high oxygen concentrations and formed bands at the outer edge of the oxic zone at low oxygen concentration (... to actively change the extension and slope of the gradients by oxygen reduction with lactate or even sulfide as electron donor. Generally, the chemotactic behavior was in agreement with a defense strategy that re-establishes anoxic conditions, thus promoting anaerobic growth and, in a natural community...

Electron Bifurcation: Thermodynamics and Kinetics of Two-Electron Brokering in Biological Redox Chemistry.

Science.gov (United States)

Zhang, Peng; Yuly, Jonathon L; Lubner, Carolyn E; Mulder, David W; King, Paul W; Peters, John W; Beratan, David N

2017-09-19

processes of their own. We dissect the thermodynamics and kinetics of electron bifurcation in Nfn and find that the key features of electron bifurcation are (1) spatially separated transfer pathways that diverge from a two-electron donor, (2) one thermodynamically uphill and one downhill redox pathway, with a large negative shift in the donor's reduction potential after departure of the first electron, and (3) electron tunneling and activation factors that enable bifurcation, producing a 1:1 partitioning of electrons onto the two pathways. Electron bifurcation is found in the CO 2 reducing pathways of methanogenic archaea, in the hydrogen pathways of hydrogenases, in the nitrogen fixing pathway of Fix, and in the mitochondrial charge transfer chain of complex III, cytochrome bc 1 . While crossed potentials may offer the biological advantage of producing tightly regulated high energy reactive species, neither kinetic nor thermodynamic considerations mandate crossed potentials to generate successful electron bifurcation. Taken together, the theoretical framework established here, focusing on the underpinning electron tunneling barriers and activation free energies, explains the logic of electron bifurcation that enables energy conversion and conservation in Nfn, points toward bioinspired schemes to execute multielectron redox chemistry, and establishes a roadmap for examining novel electron bifurcation networks in nature.

Charge transfer mediator based systems for electrocatalytic oxygen reduction

Science.gov (United States)

Stahl, Shannon S.; Gerken, James B.; Anson, Colin W.

2017-07-18

Disclosed are systems for the electrocatalytic reduction of oxygen, having redox mediator/redox catalyst pairs and an electrolyte solution in contact with an electrode. The redox mediator is included in the electrolyte solution, and the redox catalyst may be included in the electrolyte solution, or alternatively, may be in contact with the electrolyte solution. In one form a cobalt redox catalyst is used with a quinone redox mediator. In another form a nitrogen oxide redox catalyst is used with a nitroxyl type redox mediator. The systems can be used in electrochemical cells wherein neither the anode nor the cathode comprise an expensive metal such as platinum.

Charge transfer mediator based systems for electrocatalytic oxygen reduction

Energy Technology Data Exchange (ETDEWEB)

Stahl, Shannon S.; Gerken, James B.; Anson, Colin W.

2017-11-07

Disclosed are systems for the electrocatalytic reduction of oxygen, having redox mediator/redox catalyst pairs and an electrolyte solution in contact with an electrode. The redox mediator is included in the electrolyte solution, and the redox catalyst may be included in the electrolyte solution, or alternatively, may be in contact with the electrolyte solution. In one form a cobalt redox catalyst is used with a quinone redox mediator. In another form a nitrogen oxide redox catalyst is used with a nitroxyl type redox mediator. The systems can be used in electrochemical cells wherein neither the anode nor the cathode comprise an expensive metal such as platinum.

Targeted design of α-MnO₂ based catalysts for oxygen reduction

DEFF Research Database (Denmark)

Lehtimaeki, Matti; Hoffmannova, Hana; Boytsova, Olga

2016-01-01

The paper focuses on theoretical and experimental aspects of an oxide surface optimization for oxygen reduction reaction (ORR). Various doped α-MnO2 based electrocatalysts were prepared by microwave-assisted hydrothermal synthesis and electrochemically characterized to validate density functional...

Investigation of the electrocatalytic activity for oxygen reduction of sputter deposited mixed metal films

International Nuclear Information System (INIS)

Schumacher, L.C.; Holzheuter, I.B.; Nucara, M.C.; Dignam, M.J.

1989-01-01

Sputter-deposited films of silver with lead, manganese and nickel have been studied as possible oxygen reduction electrocatalysts using cyclic voltammetry, rotating disc studies, steady-state polarization and Auger analysis. In general, the Ag-Pb and Ag-Mn films display superior electrocatalytic activity for O 2 reduction, while the Ag-Ni films' performance is inferior to that of pure Ag. For the Ag-Pb films, which show the highest electrocatalytic activity, the mixed metal films display oxidation-reduction behavior which is not simply a superposition of that of the separate metals, and suggests a mechanism for the improved behavior

One step synthesis of chlorine-free Pt/Nitrogen-doped graphene composite for oxygen reduction reaction

KAUST Repository

Varga, Tamá s; Varga, Á gnes Tí mea; Ballai, Gergő; Haspel, Henrik; Kukovecz, Á kos; Kó nya, Z.

2018-01-01

Chlorine-free Platinum/nitrogen-doped graphene oxygen reduction reaction catalysts were synthesized by a one step method of annealing a mixture of platinum acetylacetonate and graphene oxide under ammonia atmosphere. Nanoparticles with close

Kinetics of oxygen reduction in perovskite cathodes for solid oxide fuel cells: A combined modeling and experimental approach

Science.gov (United States)

Miara, Lincoln James

Solid oxide fuel cells (SOFCs) have the potential to replace conventional stationary power generation technologies; however, there are major obstacles to commercialization, the most problematic of which is poor cathode performance. Commercialization of SOFCs will follow when the mechanisms occurring at the cathode are more thoroughly understood and adapted for market use. The catalytic reduction of oxygen occurring in SOFC cathodes consists of many elementary steps such as gas phase diffusion, chemical and/or electrochemical reactions which lead to the adsorption and dissociation of molecular oxygen onto the cathode surface, mass transport of oxygen species along the surface and/or through the bulk of the cathode, and full reduction and incorporation of the oxygen at the cathode/electrolyte two or three phase boundary. Electrochemical impedance spectroscopy (EIS) is the main technique used to identify the occurrence of these different processes, but when this technique is used without an explicit model describing the kinetics it is difficult to unravel the interdependence of each of these processes. The purpose of this dissertation is to identify the heterogeneous reactions occurring at the cathode of an SOFC by combining experimental EIS results with mathematical models describing the time dependent behavior of the system. This analysis is performed on two different systems. In the first case, experimental EIS results from patterned half cells composed of Ca-doped lanthanum manganite (LCM)| yttria-doped ZrO2 (YSZ) are modeled to investigate the temperature and partial pressure of oxygen, pO2, dependence of oxygen adsorption/dissociation onto the LCM surface, surface diffusion of atomic oxygen, and electrochemical reduction and incorporation of the oxygen into the electrolyte in the vicinity of the triple phase boundary (TPB). This model determines the time-independent state-space equations from which the Faradaic admittance transfer function is obtained. The

Hollow Spheres of Iron Carbide Nanoparticles Encased in Graphitic Layers as Oxygen Reduction Catalysts

DEFF Research Database (Denmark)

Hu, Yang; Jensen, Jens Oluf; Zhang, Wei

2014-01-01

Nonprecious metal catalysts for the oxygen reduction reaction are the ultimate materials and the foremost subject for low‐temperature fuel cells. A novel type of catalysts prepared by high‐pressure pyrolysis is reported. The catalyst is featured by hollow spherical morphologies consisting...

Ruthenium supported on nitrogen-doped carbon nanotubes for the oxygen reduction reaction in alkaline

CSIR Research Space (South Africa)

Mabena, LF

2012-10-01

Full Text Available between 0 and 10 wt.%. The activity of the prepared nanocatalysts toward the oxygen reduction reaction (ORR) was characterized using the rotating disk electrode and voltammetry techniques. The ORR activity was higher at lower concentrations of Ru on N...

The competing impacts of climate change and nutrient reductions on dissolved oxygen in Chesapeake Bay

Science.gov (United States)

Irby, Isaac D.; Friedrichs, Marjorie A. M.; Da, Fei; Hinson, Kyle E.

2018-05-01

The Chesapeake Bay region is projected to experience changes in temperature, sea level, and precipitation as a result of climate change. This research uses an estuarine-watershed hydrodynamic-biogeochemical modeling system along with projected mid-21st-century changes in temperature, freshwater flow, and sea level rise to explore the impact climate change may have on future Chesapeake Bay dissolved-oxygen (DO) concentrations and the potential success of nutrient reductions in attaining mandated estuarine water quality improvements. Results indicate that warming bay waters will decrease oxygen solubility year-round, while also increasing oxygen utilization via respiration and remineralization, primarily impacting bottom oxygen in the spring. Rising sea level will increase estuarine circulation, reducing residence time in bottom waters and increasing stratification. As a result, oxygen concentrations in bottom waters are projected to increase, while oxygen concentrations at mid-depths (3 < DO < 5 mg L-1) will typically decrease. Changes in precipitation are projected to deliver higher winter and spring freshwater flow and nutrient loads, fueling increased primary production. Together, these multiple climate impacts will lower DO throughout the Chesapeake Bay and negatively impact progress towards meeting water quality standards associated with the Chesapeake Bay Total Maximum Daily Load. However, this research also shows that the potential impacts of climate change will be significantly smaller than improvements in DO expected in response to the required nutrient reductions, especially at the anoxic and hypoxic levels. Overall, increased temperature exhibits the strongest control on the change in future DO concentrations, primarily due to decreased solubility, while sea level rise is expected to exert a small positive impact and increased winter river flow is anticipated to exert a small negative impact.

Oxygen Reduction Reaction Activity of Platinum Thin Films with Different Densities

Energy Technology Data Exchange (ETDEWEB)

Ergul, Busra; Begum, Mahbuba; Kariuki, Nancy; Myers, Deborah J.; Karabacak, Tansel

2017-08-24

Platinum thin films with different densities were grown on glassy carbon electrodes by high pressure sputtering deposition and evaluated as oxygen reduction reaction catalysts for polymer electrolyte fuel cells using cyclic voltammetry and rotating disk electrode techniques in aqueous perchloric acid electrolyte. The electrochemically active surface area, ORR mass activity (MA) and specific activity (SA) of the thin film electrodes were obtained. MA and SA were found to be higher for low-density films than for high-density film.

Two-Electron Transfer Pathways.

Science.gov (United States)

Lin, Jiaxing; Balamurugan, D; Zhang, Peng; Skourtis, Spiros S; Beratan, David N

2015-06-18

The frontiers of electron-transfer chemistry demand that we develop theoretical frameworks to describe the delivery of multiple electrons, atoms, and ions in molecular systems. When electrons move over long distances through high barriers, where the probability for thermal population of oxidized or reduced bridge-localized states is very small, the electrons will tunnel from the donor (D) to acceptor (A), facilitated by bridge-mediated superexchange interactions. If the stable donor and acceptor redox states on D and A differ by two electrons, it is possible that the electrons will propagate coherently from D to A. While structure-function relations for single-electron superexchange in molecules are well established, strategies to manipulate the coherent flow of multiple electrons are largely unknown. In contrast to one-electron superexchange, two-electron superexchange involves both one- and two-electron virtual intermediate states, the number of virtual intermediates increases very rapidly with system size, and multiple classes of pathways interfere with one another. In the study described here, we developed simple superexchange models for two-electron transfer. We explored how the bridge structure and energetics influence multielectron superexchange, and we compared two-electron superexchange interactions to single-electron superexchange. Multielectron superexchange introduces interference between singly and doubly oxidized (or reduced) bridge virtual states, so that even simple linear donor-bridge-acceptor systems have pathway topologies that resemble those seen for one-electron superexchange through bridges with multiple parallel pathways. The simple model systems studied here exhibit a richness that is amenable to experimental exploration by manipulating the multiple pathways, pathway crosstalk, and changes in the number of donor and acceptor species. The features that emerge from these studies may assist in developing new strategies to deliver multiple

Role of the adsorbed oxygen species in the selective electrochemical reduction of CO_2 to alcohols and carbonyls on copper electrodes

International Nuclear Information System (INIS)

Le Duff, Cecile S.; Lawrence, Matthew J.; Rodriguez, Paramaconi

2017-01-01

The electrochemical reduction of CO_2 into fuels has gained significant attention recently as source of renewable carbon-based fuels. The unique high selectivity of copper in the electrochemical reduction of CO_2 to hydrocarbons has called much interest in discovering its mechanism. In order to provide significant information about the role of oxygen in the electrochemical reduction of CO_2 on Cu electrodes, the conditions of the surface structure and the composition of the Cu single crystal electrodes were controlled over time. This was achieved using pulsed voltammetry, since the pulse sequence can be programmed to guarantee reproducible initial conditions for the reaction at every fraction of time and at a given frequency. In contrast to the selectivity of CO_2 reduction using cyclic voltammetry and chronoamperometric methods, a large selection of oxygenated hydrocarbons was found under alternating voltage conditions. Product selectivity towards the formation of oxygenated hydrocarbon was associated to the coverage of oxygen species, which is surface-structure- and potential-dependent. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

Oxygen reduction reaction on carbon-supported CoSe2 nanoparticles in an acidic medium

International Nuclear Information System (INIS)

Feng Yongjun; He Ting; Alonso-Vante, Nicolas

2009-01-01

We investigated the effect of CoSe 2 /C nanoparticle loading rate on oxygen reduction reaction (ORR) activity and H 2 O 2 production using the rotating disk electrode and the rotating ring-disk electrode techniques. We prepared carbon-supported CoSe 2 nanoparticles with different nominal loading rates and evaluated these samples by means of powder X-ray diffraction. All the catalysts had an OCP value of 0.81 V vs. RHE. H 2 O 2 production during the ORR process decreased with an increase in catalytic layer thickness. This decrease was related to the CoSe 2 loading on the disk electrode. H 2 O 2 production also decreased with increasing catalytic site density, a phenomenon related to the CoSe 2 loading rate on the carbon substrate. The cathodic current density significantly increased with increasing catalytic layer thickness, but decreased with increasing catalytic site density. In the case of 20 wt% CoSe 2 /C nanoparticles at 22 μg cm -2 , we determined that the transfer process involves about 3.5 electrons.

Reentrant resistance and giant Andreev back scattering in a two-dimensional electron gas coupled to superconductors

NARCIS (Netherlands)

den Hartog, Sander; Wees, B.J. van; Nazarov, Yu.V.; Klapwijk, T.M.; Borghs, G.

1998-01-01

We first present the bias-voltage dependence of the superconducting phase-dependent reduction in the differential resistance of a disordered T-shaped two-dimensional electron gas (2DEG) coupled to two superconductors. This reduction exhibits a reentrant behavior, since it first increases upon

Reductive dehalogenation of 5-bromouracil by aliphatic organic radicals in aqueous solutions; electron transfer and proton-coupled electron transfer mechanisms

Science.gov (United States)

Matasović, Brunislav; Bonifačić, Marija

2011-06-01

Reductive dehalogenation of 5-bromouracil by aliphatic organic radicals CO2-rad , rad CH 2OH, rad CH(CH 3)OH, and rad CH(CH 3)O - have been studied in oxygen free aqueous solutions in the presence of organic additives: formate, methanol or ethanol. For radicals production 60Co γ-radiolysis was employed and the yield of bromide was measured by means of ion chromatography. Both radical anions have reducing potential negative enough to transfer an electron to BrU producing bromide ion and U rad radical. High yields of bromide have been measured increasing proportional to the concentration of the corresponding organic additives at a constant dose rate. This is characteristic for a chain process where regeneration of radical ions occurs by H-atom abstraction by U rad radical from formate or ethanol. Results with the neutral radicals conformed earlier proposition that the reduction reaction of α-hydroxyalkyl radicals proceeds by the proton-coupled electron transfer mechanism ( Matasović and Bonifačić, 2007). Thus, while both rad CH 2OH and rad CH(CH 3)OH did not react with BrU in water/alcohol solutions, addition of bicarbonate and acetate in mmol dm -3 concentrations, pH 7, brought about chain debromination to occur in the case of rad CH(CH 3)OH radical as reactant. Under the same conditions phosphate buffer, a base with higher bulk proton affinity, failed to have any influence. The results are taken as additional proofs for the specific complex formation of α-hydroxyalkyl radicals with suitable bases which enhances radicals' reduction potential in comparison with only water molecules as proton acceptors. Rate constants for the H-atom abstraction from ethanol and formate by U rad radicals have been estimated to amount to about ≥85 and 1200 dm 3 mol -1 s -1, respectively.

Spectrum analysis of the reduction degree of two-step reduced graphene oxide (GO) and the polymer/r-GO composites

Energy Technology Data Exchange (ETDEWEB)

She, Xilin, E-mail: xlshe@qdu.edu.cn [College of Chemical and Environmental Engineering, Qingdao University, Qingdao 266071 (China); Liu, Tongchao; Wu, Nan [College of Chemical and Environmental Engineering, Qingdao University, Qingdao 266071 (China); Xu, Xijin [School of Physics and Technology, University of Jinan, Jinan 250022 (China); Li, Jianjiang [College of Chemical and Environmental Engineering, Qingdao University, Qingdao 266071 (China); Yang, Dongjiang, E-mail: d.yang@qdu.edu.cn [College of Chemical and Environmental Engineering, Qingdao University, Qingdao 266071 (China); School of Chemistry, Physics and Mechanical Engineering, Science and Engineering Faculty, Queensland University of Technology, GPO Box 2434, Brisbane, Queensland 4001 (Australia); Frost, Ray [School of Chemistry, Physics and Mechanical Engineering, Science and Engineering Faculty, Queensland University of Technology, GPO Box 2434, Brisbane, Queensland 4001 (Australia)

2013-12-16

In this paper, the reduction degree of graphene oxide (GO) reduced using chemical reduction and thermal reduction methods was characterized by spectrum analysis. The optimized conditions of reducing GO were determined that the hydrazine hydrate is the best reducing agent and the appropriate thermal reduction temperature is at 240 °C. The obtained GO solution was mixed with polystyrene (PS) solution to prepare PS/r-GO composites by using two-step reduction technique under the optimized conditions. The structure and micro-morphology of GO, r-GO and PS/r-GO composites were characterized by Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), Scanning electron microscopy (SEM), Transmission electron microscopy (TEM) respectively. It is also observed that the two-step reduction pathway is more effective than one-step reduction for improving the reduction degree of GO. Accordingly, the electric conductivity of PS/r-GO composites prepared by two-step reduction technique is as high as 21.45 S m{sup −1}, which is much higher than that of composites fabricated by one-step reduction method. The spectrum techniques will highlight new opportunities for investigating the reduction degree of GO in polymer composites. - Highlights: • Spectrum analysis on the reduction degree of GO reduced by different methods. • Determine the optimized reduction conditions of GO and polymer/r-GO composites. • The two-step reduction is more effective than one-step reduction.

Spectrum analysis of the reduction degree of two-step reduced graphene oxide (GO) and the polymer/r-GO composites

International Nuclear Information System (INIS)

She, Xilin; Liu, Tongchao; Wu, Nan; Xu, Xijin; Li, Jianjiang; Yang, Dongjiang; Frost, Ray

2013-01-01

In this paper, the reduction degree of graphene oxide (GO) reduced using chemical reduction and thermal reduction methods was characterized by spectrum analysis. The optimized conditions of reducing GO were determined that the hydrazine hydrate is the best reducing agent and the appropriate thermal reduction temperature is at 240 °C. The obtained GO solution was mixed with polystyrene (PS) solution to prepare PS/r-GO composites by using two-step reduction technique under the optimized conditions. The structure and micro-morphology of GO, r-GO and PS/r-GO composites were characterized by Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), Scanning electron microscopy (SEM), Transmission electron microscopy (TEM) respectively. It is also observed that the two-step reduction pathway is more effective than one-step reduction for improving the reduction degree of GO. Accordingly, the electric conductivity of PS/r-GO composites prepared by two-step reduction technique is as high as 21.45 S m −1 , which is much higher than that of composites fabricated by one-step reduction method. The spectrum techniques will highlight new opportunities for investigating the reduction degree of GO in polymer composites. - Highlights: • Spectrum analysis on the reduction degree of GO reduced by different methods. • Determine the optimized reduction conditions of GO and polymer/r-GO composites. • The two-step reduction is more effective than one-step reduction

Localized versus itinerant states created by multiple oxygen vacancies in SrTiO3

Science.gov (United States)

Jeschke, Harald O.; Shen, Juan; Valentí, Roser

2015-02-01

Oxygen vacancies in strontium titanate surfaces (SrTiO3) have been linked to the presence of a two-dimensional electron gas with unique behavior. We perform a detailed density functional theory study of the lattice and electronic structure of SrTiO3 slabs with multiple oxygen vacancies, with a main focus on two vacancies near a titanium dioxide terminated SrTiO3 surface. We conclude based on total energies that the two vacancies preferably inhabit the first two layers, i.e. they cluster vertically, while in the direction parallel to the surface, the vacancies show a weak tendency towards equal spacing. Analysis of the nonmagnetic electronic structure indicates that oxygen defects in the surface TiO2 layer lead to population of Ti {{t}2g} states and thus itinerancy of the electrons donated by the oxygen vacancy. In contrast, electrons from subsurface oxygen vacancies populate Ti eg states and remain localized on the two Ti ions neighboring the vacancy. We find that both the formation of a bound oxygen-vacancy state composed of hybridized Ti 3eg and 4p states neighboring the oxygen vacancy as well as the elastic deformation after extracting oxygen contribute to the stabilization of the in-gap state.

Evidence of enzymatic catalysis of oxygen reduction on stainless steels under marine biofilm.

Science.gov (United States)

Faimali, Marco; Benedetti, Alessandro; Pavanello, Giovanni; Chelossi, Elisabetta; Wrubl, Federico; Mollica, Alfonso

2011-04-01

Cathodic current trends on stainless steel samples with different surface percentages covered by biofilm and potentiostatically polarized in natural seawater were studied under oxygen concentration changes, temperature increases, and additions of enzymic inhibitors to the solution. The results showed that on each surface fraction covered by biofilm the oxygen reduction kinetics resembled a reaction catalyzed by an immobilised enzyme with high oxygen affinity (apparent Michaelis-Menten dissociation constant close to K(O(2))(M)  ≈ 10 μM) and low activation energy (W ≈ 20 KJ mole(-1)). The proposed enzyme rapidly degraded when the temperature was increased above the ambient (half-life time of ∼1 day at 25°C, and of a few minutes at 50°C). Furthermore, when reversible enzymic inhibitors (eg sodium azide and cyanide) were added, the cathodic current induced by biofilm growth was inhibited.

Supramolecular tetracluster-cobalt porphyrin: a four-electron transfer catalyst for dioxygen reduction

International Nuclear Information System (INIS)

Winnischofer, Herbert; Otake, Vesper Yoshiyuki; Dovidauskas, Sergio; Nakamura, Marcelo; Toma, Henrique Eisi; Araki, Koiti

2004-01-01

Electrocatalysis by CoTCP {CoTCP meso-tetrakis(4-pyridyl)porphynatocobalt(III)} coordinated to four [Ru 3 (μ 3 -O)(μ 2 -CH 3 CO 2 ) 6 (py) 2 ] + complexes in the four-electron reduction of dioxygen, has been unequivocally demonstrated in this work by using two types of electrostatically assembled films of CoTCP and anionic zinc or free-base meso-tetrakis(4-sulfonatophenyl)porphyrins (ZnTPPS or H 2 TPPS), as well as, by employing different electrode materials. An enhanced electrocatalytic activity has been observed, in spite of the fact that the typical bis-coordination of dioxygen to two cobalt porphyrin sites is precluded in such CoTCP/ZnTPPS or CoTCP/H 2 TPPS bilayered films. In addition, negligible ring currents have been observed in ring-disk voltammetry measurements, yielding straight Levich and Koutecky-Levich plots, whose slopes approached the theoretical 4e - curve in air, or in O 2 saturated solutions (pH 3-5). The use of gold instead of glassy carbon (GC) electrodes has not also significantly perturbed the mechanism. By ruling out any influence from the electrode materials, a well known critical point in the catalysis by cobalt porphyrins, the results have shown that CoTCP is acting as a four-electron transfer catalyst for dioxygen reduction. Also, by excluding the possibility of bis-coordination of dioxygen, it was shown that the electronic and supramolecular effects exerted by the peripheral ruthenium cluster complexes should be triggering the four-electron catalytic activity of the cobalt porphyrin center

Redox functionality mediated by adsorbed oxygen on a Pd oxide film over a Pd(100) thin structure: a first-principles study

International Nuclear Information System (INIS)

Kusakabe, K; Ikuno, Y k; Nagara, H; Harada, K

2009-01-01

Stable oxygen sites on a PdO film over a Pd(100) thin structure with a (√5x√5)R27 o surface unit cell are determined using the first-principles electronic structure calculations with the generalized gradient approximation. The adsorbed monatomic oxygen goes to a site bridging two twofold-coordinated Pd atoms or to a site bridging a twofold-coordinated Pd atom and a fourfold-coordinated Pd atom. Estimated reaction energies of CO oxidation by reduction of the oxidized PdO film and N 2 O reduction mediated by oxidation of the PdO film are both exothermic. Motion of the adsorbed oxygen atom between the two stable sites is evaluated using the nudged elastic band method, where an energy barrier for a translational motion of the adsorbed oxygen may become ∼0.45 eV, which is low enough to allow fluxionality of the surface oxygen at high temperatures. The oxygen fluxionality is allowed by the existence of twofold-coordinated Pd atoms on the PdO film, whose local structure has a similarity to that of Pd catalysts for the Suzuki-Miyaura cross-coupling. Although NO x (including NO 2 and NO) reduction is not always catalyzed by the PdO film only, we conclude that continual redox reactions may happen mediated by oxygen-adsorbed PdO films over a Pd surface structure, when the influx of NO x and CO continues, and when the reaction cycle is kept on a well-designed oxygen surface.

Thermodynamic driving force effects in the oxygen reduction catalyzed by a metal-free porphyrin

Czech Academy of Sciences Publication Activity Database

Trojánek, Antonín; Langmaier, Jan; Samec, Zdeněk

2012-01-01

Roč. 82, SI (2012), s. 457-462 ISSN 0013-4686 R&D Projects: GA ČR GAP208/11/0697 Institutional research plan: CEZ:AV0Z40400503 Keywords : oxygen reduction * metal-free porphyrin * electrocatalysis Subject RIV: CG - Electrochemistry Impact factor: 3.777, year: 2012

Phosphorescent probes for two-photon microscopy of oxygen (Conference Presentation)

Science.gov (United States)

Vinogradov, Sergei A.; Esipova, Tatiana V.

2016-03-01

The ability to quantify oxygen in vivo in 3D with high spatial and temporal resolution is much needed in many areas of biological research. Our laboratory has been developing the phosphorescence quenching technique for biological oximetry - an optical method that possesses intrinsic microscopic capability. In the past we have developed dendritically protected oxygen probes for quantitative imaging of oxygen in tissue. More recently we expanded our design on special two-photon enhanced phosphorescent probes. These molecules brought about first demonstrations of the two-photon phosphorescence lifetime microscopy (2PLM) of oxygen in vivo, providing new information for neouroscience and stem cell biology. However, current two-photon oxygen probes suffer from a number of limitations, such as sub-optimal brightness and high cost of synthesis, which dramatically reduce imaging performance and limit usability of the method. In this paper we discuss principles of 2PLM and address the interplay between the probe chemistry, photophysics and spatial and temporal imaging resolution. We then present a new approach to brightly phosphorescent chromophores with internally enhanced two-photon absorption cross-sections, which pave a way to a new generation of 2PLM probes.

The competing impacts of climate change and nutrient reductions on dissolved oxygen in Chesapeake Bay

Directory of Open Access Journals (Sweden)

I. D. Irby

2018-05-01

Full Text Available The Chesapeake Bay region is projected to experience changes in temperature, sea level, and precipitation as a result of climate change. This research uses an estuarine-watershed hydrodynamic–biogeochemical modeling system along with projected mid-21st-century changes in temperature, freshwater flow, and sea level rise to explore the impact climate change may have on future Chesapeake Bay dissolved-oxygen (DO concentrations and the potential success of nutrient reductions in attaining mandated estuarine water quality improvements. Results indicate that warming bay waters will decrease oxygen solubility year-round, while also increasing oxygen utilization via respiration and remineralization, primarily impacting bottom oxygen in the spring. Rising sea level will increase estuarine circulation, reducing residence time in bottom waters and increasing stratification. As a result, oxygen concentrations in bottom waters are projected to increase, while oxygen concentrations at mid-depths (3 < DO < 5 mg L−1 will typically decrease. Changes in precipitation are projected to deliver higher winter and spring freshwater flow and nutrient loads, fueling increased primary production. Together, these multiple climate impacts will lower DO throughout the Chesapeake Bay and negatively impact progress towards meeting water quality standards associated with the Chesapeake Bay Total Maximum Daily Load. However, this research also shows that the potential impacts of climate change will be significantly smaller than improvements in DO expected in response to the required nutrient reductions, especially at the anoxic and hypoxic levels. Overall, increased temperature exhibits the strongest control on the change in future DO concentrations, primarily due to decreased solubility, while sea level rise is expected to exert a small positive impact and increased winter river flow is anticipated to exert a small negative impact.

Basic regulatory principles of Escherichia coli's electron transport chain for varying oxygen conditions.

Science.gov (United States)

Henkel, Sebastian G; Ter Beek, Alexander; Steinsiek, Sonja; Stagge, Stefan; Bettenbrock, Katja; de Mattos, M Joost Teixeira; Sauter, Thomas; Sawodny, Oliver; Ederer, Michael

2014-01-01

For adaptation between anaerobic, micro-aerobic and aerobic conditions Escherichia coli's metabolism and in particular its electron transport chain (ETC) is highly regulated. Although it is known that the global transcriptional regulators FNR and ArcA are involved in oxygen response it is unclear how they interplay in the regulation of ETC enzymes under micro-aerobic chemostat conditions. Also, there are diverse results which and how quinones (oxidised/reduced, ubiquinone/other quinones) are controlling the ArcBA two-component system. In the following a mathematical model of the E. coli ETC linked to basic modules for substrate uptake, fermentation product excretion and biomass formation is introduced. The kinetic modelling focusses on regulatory principles of the ETC for varying oxygen conditions in glucose-limited continuous cultures. The model is based on the balance of electron donation (glucose) and acceptance (oxygen or other acceptors). Also, it is able to account for different chemostat conditions due to changed substrate concentrations and dilution rates. The parameter identification process is divided into an estimation and a validation step based on previously published and new experimental data. The model shows that experimentally observed, qualitatively different behaviour of the ubiquinone redox state and the ArcA activity profile in the micro-aerobic range for different experimental conditions can emerge from a single network structure. The network structure features a strong feed-forward effect from the FNR regulatory system to the ArcBA regulatory system via a common control of the dehydrogenases of the ETC. The model supports the hypothesis that ubiquinone but not ubiquinol plays a key role in determining the activity of ArcBA in a glucose-limited chemostat at micro-aerobic conditions.

Noncovalently functionalized graphitic mesoporous carbon as a stable support of Pt nanoparticles for oxygen reduction

Energy Technology Data Exchange (ETDEWEB)

Shao, Yuyan; Zhang, Sheng; Kou, Rong; Wang, Chongmin; Viswanathan, Vilayanur; Liu, Jun; Wang, Yong; Lin, Yuehe [Pacific Northwest National Laboratory, Richland, WA 99352 (United States); Wang, Xiqing; Dai, Sheng [Oak Ridge National Laboratory, Oak Ridge, TN 37831 (United States)

2010-04-02

We report a durable electrocatalyst support, highly graphitized mesoporous carbon (GMPC), for oxygen reduction in polymer electrolyte membrane (PEM) fuel cells. GMPC is prepared through graphitizing the self-assembled soft-template mesoporous carbon (MPC) under high temperature. Heat-treatment at 2800 C greatly improves the degree of graphitization while most of the mesoporous structures and the specific surface area of MPC are retained. GMPC is then noncovalently functionalized with poly(diallyldimethylammonium chloride) (PDDA) and loaded with Pt nanoparticles by reducing Pt precursor (H{sub 2}PtCl{sub 6}) in ethylene glycol. Pt nanoparticles of {proportional_to}3.0 nm in diameter are uniformly dispersed on GMPC. Compared to Pt supported on Vulcan XC-72 carbon black (Pt/XC-72), Pt/GMPC exhibits a higher mass activity towards oxygen reduction reaction (ORR) and the mass activity retention (in percentage) is improved by a factor of {proportional_to}2 after 44 h accelerated degradation test under the potential step (1.4-0.85 V) electrochemical stressing condition which focuses on support corrosion. The enhanced activity and durability of Pt/GMPC are attributed to the graphitic structure of GMPC which is more resistant to corrosion. These findings demonstrate that GMPC is a promising oxygen reduction electrocatalyst support for PEM fuel cells. The approach reported in this work provides a facile, eco-friendly promising strategy for synthesizing stable metal nanoparticles on hydrophobic support materials. (author)

The mitochondrial outer membrane protein mitoNEET is a redox enzyme catalyzing electron transfer from FMNH2 to oxygen or ubiquinone.

Science.gov (United States)

Wang, Yiming; Landry, Aaron P; Ding, Huangen

2017-06-16

Increasing evidence suggests that mitoNEET, a target of the type II diabetes drug pioglitazone, is a key regulator of energy metabolism in mitochondria. MitoNEET is anchored to the mitochondrial outer membrane via its N-terminal α helix domain and hosts a redox-active [2Fe-2S] cluster in its C-terminal cytosolic region. The mechanism by which mitoNEET regulates energy metabolism in mitochondria, however, is not fully understood. Previous studies have shown that mitoNEET specifically interacts with the reduced flavin mononucleotide (FMNH 2 ) and that FMNH 2 can quickly reduce the mitoNEET [2Fe-2S] clusters. Here we report that the reduced mitoNEET [2Fe-2S] clusters can be readily oxidized by oxygen. In the presence of FMN, NADH, and flavin reductase, which reduces FMN to FMNH 2 using NADH as the electron donor, mitoNEET mediates oxidation of NADH with a concomitant reduction of oxygen. Ubiquinone-2, an analog of ubiquinone-10, can also oxidize the reduced mitoNEET [2Fe-2S] clusters under anaerobic or aerobic conditions. Compared with oxygen, ubiquinone-2 is more efficient in oxidizing the mitoNEET [2Fe-2S] clusters, suggesting that ubiquinone could be an intrinsic electron acceptor of the reduced mitoNEET [2Fe-2S] clusters in mitochondria. Pioglitazone or its analog NL-1 appears to inhibit the electron transfer activity of mitoNEET by forming a unique complex with mitoNEET and FMNH 2 The results suggest that mitoNEET is a redox enzyme that may promote oxidation of NADH to facilitate enhanced glycolysis in the cytosol and that pioglitazone may regulate energy metabolism in mitochondria by inhibiting the electron transfer activity of mitoNEET. © 2017 by The American Society for Biochemistry and Molecular Biology, Inc.

Nitrogen-doped graphene prepared by a transfer doping approach for the oxygen reduction reaction application

Science.gov (United States)

Mo, Zaiyong; Zheng, Ruiping; Peng, Hongliang; Liang, Huagen; Liao, Shijun

2014-01-01

Well defined nitrogen-doped graphene (NG) is prepared by a transfer doping approach, in which the graphene oxide (GO) is deoxidized and nitrogen doped by the vaporized polyaniline, and the GO is prepared by a thermal expansion method from graphite oxide. The content of doped nitrogen in the doped graphene is high up to 6.25 at% by the results of elements analysis, and oxygen content is lowered to 5.17 at%. As a non-precious metal cathode electrocatalyst, the NG catalyst exhibits excellent activity toward the oxygen reduction reaction, as well as excellent tolerance toward methanol. In 0.1 M KOH solution, its onset potential, half-wave potential and limiting current density for the oxygen reduction reaction reach 0.98 V (vs. RHE), 0.87 V (vs. RHE) and 5.38 mA cm-2, respectively, which are comparable to those of commercial 20 wt% Pt/C catalyst. The well defined graphene structure of the catalyst is revealed clearly by HRTEM and Raman spectra. It is suggested that the nitrogen-doping and large surface area of the NG sheets give the main contribution to the high ORR catalytic activity.

Numerical study on characteristics of radio-frequency discharge at atmospheric pressure in argon with small admixtures of oxygen

Science.gov (United States)

Wang, Yinan; Liu, Yue

2017-07-01

In this paper, a 1D fluid model is developed to study the characteristics of a discharge in argon with small admixtures of oxygen at atmospheric pressure. This model consists of a series of equations, including continuity equations for electrons, positive ions, negative ions and neutral particles, the energy equation, and the Poisson equation for electric potential. Special attention has been paid to the electron energy dissipation and the mechanisms of electron heating, while the admixture of oxygen is in the range of 0.1%-0.6%. It is found that when the oxygen-to-argon ratio grows, the discharge is obviously divided into three stages: electron growth, electron reduction and the electron remaining unchanged. Furthermore, the cycle-averaged electric field, electron temperature, electron Ohmic heating, electron collisionless heating, electron energy dissipation and the net electron production are also studied in detail, and when the oxygen-to-argon ratio is relatively larger (R = 0.6%), double value peaks of electron Ohmic heating appear in the sheath. According to the results of the numerical simulation, various oxygen-to-argon ratios result in different amounts of electron energy dissipation and electron heating.

Synthesis of AuPd alloyed nanoparticles via room-temperature electron reduction with argon glow discharge as electron source.

Science.gov (United States)

Yang, Manman; Wang, Zongyuan; Wang, Wei; Liu, Chang-Jun

2014-01-01

Argon glow discharge has been employed as a cheap, environmentally friendly, and convenient electron source for simultaneous reduction of HAuCl4 and PdCl2 on the anodic aluminum oxide (AAO) substrate. The thermal imaging confirms that the synthesis is operated at room temperature. The reduction is conducted with a short time (30 min) under the pressure of approximately 100 Pa. This room-temperature electron reduction operates in a dry way and requires neither hydrogen nor extra heating nor chemical reducing agent. The analyses using X-ray photoelectron spectroscopy (XPS) confirm all the metallic ions have been reduced. The characterization with X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM) shows that AuPd alloyed nanoparticles are formed. There also exist some highly dispersed Au and Pd monometallic particles that cannot be detected by XRD and transmission electron microscopy (TEM) because of their small particle sizes. The observed AuPd alloyed nanoparticles are spherical with an average size of 14 nm. No core-shell structure can be observed. The room-temperature electron reduction can be operated in a larger scale. It is an easy way for the synthesis of AuPd alloyed nanoparticles.

Two electron Rydberg states

International Nuclear Information System (INIS)

Cooke, W.E.

1981-01-01

This paper addresses the study of two-electron Rydberg atoms. With Multichannel Quantum Defect Theory (MQDT), there is a technique for characterizing a spectra in terms of a small number of parameters. A survey of some important effects specific to two-electon Rydberg states, using primarily the alkaline earth atoms for examples, is made. The remainder of the paper deals with a discussion of the electron-electron interaction, including some of the basic points of MQDT. Energy exchange between two electrons is also addressed

O-, N-Atoms-Coordinated Mn Cofactors within a Graphene Framework as Bioinspired Oxygen Reduction Reaction Electrocatalysts.

Science.gov (United States)

Yang, Yang; Mao, Kaitian; Gao, Shiqi; Huang, Hao; Xia, Guoliang; Lin, Zhiyu; Jiang, Peng; Wang, Changlai; Wang, Hui; Chen, Qianwang

2018-05-28

Manganese (Mn) is generally regarded as not being sufficiently active for the oxygen reduction reaction (ORR) compared to other transition metals such as Fe and Co. However, in biology, manganese-containing enzymes can catalyze oxygen-evolving reactions efficiently with a relative low onset potential. Here, atomically dispersed O and N atoms coordinated Mn active sites are incorporated within graphene frameworks to emulate both the structure and function of Mn cofactors in heme-copper oxidases superfamily. Unlike previous single-metal catalysts with general M-N-C structures, here, it is proved that a coordinated O atom can also play a significant role in tuning the intrinsic catalytic activities of transition metals. The biomimetic electrocatalyst exhibits superior performance for the ORR and zinc-air batteries under alkaline conditions, which is even better than that of commercial Pt/C. The excellent performance can be ascribed to the abundant atomically dispersed Mn cofactors in the graphene frameworks, confirmed by various characterization methods. Theoretical calculations reveal that the intrinsic catalytic activity of metal Mn can be significantly improved via changing local geometry of nearest coordinated O and N atoms. Especially, graphene frameworks containing the Mn-N 3 O 1 cofactor demonstrate the fastest ORR kinetics due to the tuning of the d electronic states to a reasonable state. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Cobamide-mediated enzymatic reductive dehalogenation via long-range electron transfer.

Science.gov (United States)

Kunze, Cindy; Bommer, Martin; Hagen, Wilfred R; Uksa, Marie; Dobbek, Holger; Schubert, Torsten; Diekert, Gabriele

2017-07-03

The capacity of metal-containing porphyrinoids to mediate reductive dehalogenation is implemented in cobamide-containing reductive dehalogenases (RDases), which serve as terminal reductases in organohalide-respiring microbes. RDases allow for the exploitation of halogenated compounds as electron acceptors. Their reaction mechanism is under debate. Here we report on substrate-enzyme interactions in a tetrachloroethene RDase (PceA) that also converts aryl halides. The shape of PceA's highly apolar active site directs binding of bromophenols at some distance from the cobalt and with the hydroxyl substituent towards the metal. A close cobalt-substrate interaction is not observed by electron paramagnetic resonance spectroscopy. Nonetheless, a halogen substituent para to the hydroxyl group is reductively eliminated and the path of the leaving halide is traced in the structure. Based on these findings, an enzymatic mechanism relying on a long-range electron transfer is concluded, which is without parallel in vitamin B 12 -dependent biochemistry and represents an effective mode of RDase catalysis.

One-step preparation of N-doped graphene/Co nanocomposite as an advanced oxygen reduction electrocatalyst

International Nuclear Information System (INIS)

Bai, Fo; Huang, Hao; Tan, Yanlei; Hou, Changmin; Zhang, Ping

2015-01-01

Graphical abstract: N-doped graphene/Co nanocomposites were synthesized through one-step pyrolysis process and the product exhibits high performance for ORR and excellent stability in alkaline medium. - Highlights: • N-doped graphene/Co nano-composite is directly synthesized by a one-step method from Co(NO3)2∙6H2O, glucose and dicyandiamide (DCDA). • The electrocatalytic performance of as-prepared NG/Co-0.5 shows the peak potential positively shifts about 10 mV than commercial Pt/C electrode. • The material shows an excellent stability and tolerance to methanol poisoning effects in alkaline medium. - Abstract: N-doped graphene/Co nanocomposites (NG/Co NPs) have been prepared by a simple one-step pyrolysis of Co(NO 3 ) 2 ∙6H 2 O, glucose and dicyandiamide (DCDA). The products with nitrogen doped and suitable graphitic degree perform high electrocatalytic activity (with the reduction peak at −0.099 V vs Ag/AgCl) and near four-electron selectivity for the oxygen reduction reaction (ORR), with excellent stability and durability in alkaline medium comparable to a commercial Pt/C catalyst. Owing to the superb ORR performance, low cost and facile preparation, the catalysts of NG/Co NPs have great potential applications in fuel cells, metal-air batteries and ORR-related electrochemical industries

Oxygen Extraction from Minerals

Science.gov (United States)

Muscatello, Tony

2017-01-01

Oxygen, whether used as part of rocket bipropellant or for astronaut life support, is a key consumable for space exploration and commercialization. In Situ Resource Utilization (ISRU) has been proposed many times as a method for making space exploration more cost effective and sustainable. On planetary and asteroid surfaces the presence of minerals in the regolith that contain oxygen is very common, making them a potential oxygen resource. The majority of research and development for oxygen extraction from minerals has been for lunar regolith although this work would generally be applicable to regolith at other locations in space. This presentation will briefly survey the major methods investigated for oxygen extraction from regolith with a focus on the current status of those methods and possible future development pathways. The major oxygen production methods are (1) extraction from lunar ilmenite (FeTiO3) with either hydrogen or carbon monoxide, (2) carbothermal reduction of iron oxides and silicates with methane, and (3) molten regolith electrolysis (MRE) of silicates. Methods (1) and (2) have also been investigated in a two-step process using CO reduction and carbon deposition followed by carbothermal reduction. All three processes have byproducts that could also be used as resources. Hydrogen or carbon monoxide reduction produce iron metal in small amounts that could potentially be used as construction material. Carbothermal reduction also makes iron metal along with silicon metal and a glass with possible applications. MRE produces iron, silicon, aluminum, titanium, and glass, with higher silicon yields than carbothermal reduction. On Mars and possibly on some moons and asteroids, water is present in the form of mineral hydrates, hydroxyl (-OH) groups on minerals, andor water adsorbed on mineral surfaces. Heating of the minerals can liberate the water which can be electrolyzed to provide a source of oxygen as well. The chemistry of these processes, some key

Oxygen reduction at platimun/ionomer interface: effects of phase separation of ionomer

Energy Technology Data Exchange (ETDEWEB)

Chlistunoff, Jerzy [Los Alamos National Laboratory

2008-01-01

Oxygen reduction reaction (ORR) at the interface between platinum and recast ionomers (Nafion EW 1100 and 950 and 6F-40) was studied at different temperatures (20--80{sup o}C) and humidities (10--100%) employing smooth Pt and Pt-black-covered ultramicroelectrodes. ORR was strongly inhibited on smooth electrodes. The inhibition increased with the reduction time, temperature and humidity, but was absent for Nafion EW 1100 in contact with liquid water. It was attributed to the hydrophobic component of ionomer blocking both active sites and oxygen transport. It was postulated that the dynamic changes in interfacial phase separation of ionomer are facilitated by the attractive interactions between the hydrophobic component of ionomer and bare platinum and between oxide-covered Pt and the hydrophilic component of ionomer. These interactions were also proposed to be responsible for the differences in ORR voltammetry for films prepared and equilibrated under different conditions. The decrease in ORR inhibition, Nafion EW 950> Nafion EW 1100> 6F-40, was correlated with physical and molecular properties of the ionomers. The lack of inhibition for Pt-black-covered electrodes was attributed to the more random distribution of ionomer chains and the high activation barriers for the ionomer restructuring at rough interfaces.

Stability and electronic properties of oxygen-doped ZnS polytypes: DFTB study

Science.gov (United States)

Popov, Ilya S.; Vorokh, Andrey S.; Enyashin, Andrey N.

2018-06-01

Synthesis from aqueous solutions is an affordable method for fabrication of II-VI semiconductors. However, application of this method often imposes a disorder of crystal lattice, manifesting as a rich variety of polytypes arising from wurtzite and zinc blende phases. The origin of this disordering still remains debatable. Here, the influence of the most likely impurity at water environment - substitutional oxygen - on the polytypic equilibrium of zinc sulphide is studied by means of density-functional tight-binding method. According to calculations, the inclusion of such oxygen does not affect the polytypic equilibrium. Apart of thermodynamic stability, the electronic and elastic properties of ZnS polytypes are studied as the function of oxygen distribution.

Spatially and Temporally Resolved Atomic Oxygen Measurements in Short Pulse Discharges by Two Photon Laser Induced Fluorescence

Science.gov (United States)

Lempert, Walter; Uddi, Mruthunjaya; Mintusov, Eugene; Jiang, Naibo; Adamovich, Igor

2007-10-01

Two Photon Laser Induced Fluorescence (TALIF) is used to measure time-dependent absolute oxygen atom concentrations in O2/He, O2/N2, and CH4/air plasmas produced with a 20 nanosecond duration, 20 kV pulsed discharge at 10 Hz repetition rate. Xenon calibrated spectra show that a single discharge pulse creates initial oxygen dissociation fraction of ˜0.0005 for air like mixtures at 40-60 torr total pressure. Peak O atom concentration is a factor of approximately two lower in fuel lean (φ=0.5) methane/air mixtures. In helium buffer, the initially formed atomic oxygen decays monotonically, with decay time consistent with formation of ozone. In all nitrogen containing mixtures, atomic oxygen concentrations are found to initially increase, for time scales on the order of 10-100 microseconds, due presumably to additional O2 dissociation caused by collisions with electronically excited nitrogen. Further evidence of the role of metastable N2 is demonstrated from time-dependent N2 2^nd Positive and NO Gamma band emission spectroscopy. Comparisons with modeling predictions show qualitative, but not quantitative, agreement with the experimental data.

Radiobiology of Bacillus megaterium spores: physicochemical events involving oxygen and caffeine

International Nuclear Information System (INIS)

Raghu, B.; Kesavan, P.C.

1986-01-01

Caffeine which is now known to react with the radiolytically produced electrons and hydroxyl radicals, is a radioprotector against the oxic, but a radiosensitizer of the anoxic component of the gamma-ray-induced damage to B. megaterium spores. A specific scavenger of hydroxyl radicals, t-butanol, also affords partial protection to spores irradiated in O 2 , thus revealing an 'OH-component' within the oxygen-dependent damage. Based on the data on inactivation constant (k) and H 2 O 2 yields of spores irradiated in O 2 or N 2 with a mixture of caffeine and t-butanol, it is suggested that radioprotection against oxic damage accrues from the competition of the former with oxygen for electrons. The simplest interpretation of radioprotection, therefore, is the substantial reduction in the formation of oxygen-electron adducts (HO 2 , O 2 , RO 2 ). The hypothesis of 'electron sequestration' satisfactorily accounts for the anoxic radiosensitization by caffeine. (author)

Hydrothermal synthesis of Fe_2O_3/polypyrrole/graphene oxide composites as highly efficient electrocatalysts for oxygen reduction reaction in alkaline electrolyte

International Nuclear Information System (INIS)

Ren, Suzhen; Ma, Shaobo; Yang, Ying; Mao, Qing; Hao, Ce

2015-01-01

Graphical abstract: Fe_2O_3/polypyrrole/graphene oxide electrocatalysts for oxygen reduction reaction (ORR) are successfully prepared through one simple polypyrrole-assisted hydrothermal method and possess very high ORR activity and are able to selectively reduce O_2 to water through the four-electron transfer reaction mechanism in alkaline electrolyte. - Abstract: Advantages in low cost, and excellent catalytic activity of Fe-based nanomaterials dispersed on nitrogen-doped graphene supports render them to be good electrocatalysts for the oxygen reduction reaction (ORR) in fuel cells. Here, Fe_2O_3/polypyrrole/graphene oxide (Fe_2O_3/Ppy/GO) composites with the Fe_2O_3 embedded in the Ppy modified GO are synthesized using hydrothermal method. With an optimal iron atom content ratio of 1.6% in graphene oxide and heat treatment at 800 °C, the Fe_2O_3/Ppy/GO exhibited enhanced catalytic performance for ORR with the onset potential of −0.1 V (vs SCE), cathodic potential of −0.24 V (vs SCE), an approximate 4e"− transfer process in O_2-saturated 0.1 M KOH, and superior stability that only reduced 5% catalytic activity after 5000 cycles. The decisive factors in improving the electrocatalytic and durable performance are the intimate and large contact interfaces between nanocrystallines of Fe_2O_3 and Ppy/GO, in addition to the high electron withdrawing/storing ability and the high conductivity of GO doped with nitrogen from Ppy during the hydrothermal reaction. The Fe_2O_3/Ppy/GO showed significantly improved ORR properties and confirmed that Fe-N-C-based electrocatalysts played a key role in fuel cells.

Catalytic Activity Enhancement for Oxygen Reduction on Epitaxial Perovskite Thin Films for Solid-Oxide Fuel Cells

KAUST Repository

la O', Gerardo Jose; Ahn, Sung-Jin; Crumlin, Ethan; Orikasa, Yuki; Biegalski, Michael D.; Christen, Hans M.; Shao-Horn, Yang

2010-01-01

Figure Presented The active ingredient: La0.8Sr 0.2CoO3-δ (LSC) epitaxial thin films are prepared on (001 )-oriented yttria-stabilized zirconia (YSZ) single crystals with a gadolinium-doped ceria (GDC) buffer layer (see picture). The LSC epitaxial films exhibit better oxygen reduction kinetics than bulk LSC. The enhanced activity is attributed in part to higher oxygen nonstoichiometry. © 2010 Wiley-VCH Verlag GmbH & Co. KCaA, Weinheim.

Catalytic Activity Enhancement for Oxygen Reduction on Epitaxial Perovskite Thin Films for Solid-Oxide Fuel Cells

KAUST Repository

la O', Gerardo Jose

2010-06-22

Figure Presented The active ingredient: La0.8Sr 0.2CoO3-δ (LSC) epitaxial thin films are prepared on (001 )-oriented yttria-stabilized zirconia (YSZ) single crystals with a gadolinium-doped ceria (GDC) buffer layer (see picture). The LSC epitaxial films exhibit better oxygen reduction kinetics than bulk LSC. The enhanced activity is attributed in part to higher oxygen nonstoichiometry. © 2010 Wiley-VCH Verlag GmbH & Co. KCaA, Weinheim.

Electronic states of carbon alloy catalysts and nitrogen substituent effects on catalytic activity

Science.gov (United States)

Hata, Tomoyuki; Ushiyama, Hiroshi; Yamashita, Koichi

2013-03-01

In recent years, Carbon Alloy Catalysts (CACs) are attracting attention as a candidate for non-platinum-based cathode catalysts in fuel cells. Oxygen reduction reactions at the cathode are divided into two elementary processes, electron transfer and oxygen adsorption. The electron transfer reaction is the rate-determining, and by comparison of energy levels, catalytic activity can be evaluated quantitatively. On the other hand, to begin with, adsorption mechanism is obscure. The purpose of this study is to understand the effect of nitrogen substitution and oxygen adsorption mechanism, by first-principle electronic structure calculations for nitrogen substituted models. To reproduce the elementary processes of oxygen adsorption, we assumed that the initial structures are formed based on the Pauling model, a CACs model and nitrogen substituted CACs models in which various points are replaced with nitrogen. When we try to focus only on the DOS peaks of oxygen, in some substituted model that has high adsorption activity, a characteristic partial occupancy state was found. We conclude that this state will affect the adsorption activity, and discuss on why partially occupied states appear with simplification by using an orbital correlation diagram.

A novel method for synthesis of phosphomolybdic acid-modified Pd/C catalysts for oxygen reduction reaction

Science.gov (United States)

Zhu, Mingyuan; Gao, Xiaoling; Luo, Guangqin; Dai, Bin

2013-03-01

This manuscript reports a convenient method for immobilizing phosphomolybdic acid (HPMo) on polyaniline (PAN-) functionalized carbon supports. The obtained HPMo-PAN-C sample is used as the support to prepare a Pd/HPMo-PAN-C catalyst. The samples are characterized by Fourier transform infrared spectroscopy, transmission electron microscopy and X-ray diffraction analysis. The results suggest that HPMo retains its Keggin structure and that the presence of HPMo reduces the average particle size of the Pd nano-particles in the obtained Pd/HPMo-PAN-C catalyst. Electro-chemical measurements in 0.5 M HClO4 solution reveal that the Pd/HPMo-PAN-C catalyst has higher catalytic activity for oxygen reduction reactions than does a Pd/C catalyst prepared using a similar procedure. The stability of the Pd/HPMo-PAN-C catalyst is evaluated by multiple-cycle voltammetry techniques; the mass catalytic activity decreases by only 10% after 100 scanning cycles.

First principles investigation of the activity of thin film Pt, Pd and Au surface alloys for oxygen reduction

DEFF Research Database (Denmark)

Tripkovic, Vladimir; Hansen, Heine Anton; Rossmeisl, Jan

2015-01-01

Further advances in fuel cell technologies are hampered by kinetic limitations associated with the sluggish cathodic oxygen reduction reaction. We have investigated a range of different formulations of binary and ternary Pt, Pd and Au thin films as electrocatalysts for oxygen reduction. The most...... active binary thin films are near-surface alloys of Pt with subsurface Pd and certain PdAu and PtAu thin films with surface and/or subsurface Au. The most active ternary thin films are with pure metal Pt or Pd skins with some degree of Au in the surface and/or subsurface layer and the near-surface alloys...

Hexadecacarbonylhexarhodium as a novel electrocatalyst for oxygen reduction and hydrogen oxidation in the presence of fuel cell contaminants

Energy Technology Data Exchange (ETDEWEB)

Uribe-Godinez, J.; Jimenez-Sandoval, O. [Centro de Investigacion y de Estudios Avanzados del Instituto Politecnico Nacional (Cinvestav), Unidad Queretaro. Apartado Postal 1-798, Queretaro, Qro. 76001 (Mexico); Hernandez-Castellanos, R. [Universidad Tecnologica de San Juan del Rio, Av. La Palma No. 125, Col. Vista Hermosa, San Juan del Rio, Qro. 76800 (Mexico)

2010-11-01

The electrocatalytic activity for oxygen reduction and hydrogen oxidation of a discrete metal carbonyl cluster with a well defined molecular and crystal structure, Rh{sub 6}(CO){sub 16}, is reported. The exchange current density of this compound for oxygen reduction is one order of magnitude higher than that of platinum, and its resistance degree to PEM fuel cell contaminants such as methanol and CO is as high as 2 mol L{sup -1} and 0.5%, respectively. These properties make the metal complex a potential alternative for use as electrode in polymer electrolyte membrane fuel cells. (author)

The gamma-ray induced chemisorption of oxygen on perovskite type catalysts: determination by reduction with hydrazine sulphate/hydroxylamine hydrochloride

International Nuclear Information System (INIS)

Srinivas, B.; Rao, V.R.S.; Kuriacose, J.C.

1986-01-01

Chemisorbed oxygen can be determined quantitatively by the measurement of gaseous N 2 /N 2 O liberated by treatment with hydrazine sulfate/hydroxylamine hydrochloride. The amount of chemisorbed oxygen depends on the degree of dispersion during irradiation and also on the γ-dose. The chemisorption is enhanced in the presence of moisture. The partial reduction of the transition metal ion favours the formation of chemisorbed oxygen. (author)

Role of the adsorbed oxygen species in the selective electrochemical reduction of CO{sub 2} to alcohols and carbonyls on copper electrodes

Energy Technology Data Exchange (ETDEWEB)

Le Duff, Cecile S.; Lawrence, Matthew J.; Rodriguez, Paramaconi [School of Chemistry, University of Birmingham, Edgbaston (United Kingdom)

2017-10-09

The electrochemical reduction of CO{sub 2} into fuels has gained significant attention recently as source of renewable carbon-based fuels. The unique high selectivity of copper in the electrochemical reduction of CO{sub 2} to hydrocarbons has called much interest in discovering its mechanism. In order to provide significant information about the role of oxygen in the electrochemical reduction of CO{sub 2} on Cu electrodes, the conditions of the surface structure and the composition of the Cu single crystal electrodes were controlled over time. This was achieved using pulsed voltammetry, since the pulse sequence can be programmed to guarantee reproducible initial conditions for the reaction at every fraction of time and at a given frequency. In contrast to the selectivity of CO{sub 2} reduction using cyclic voltammetry and chronoamperometric methods, a large selection of oxygenated hydrocarbons was found under alternating voltage conditions. Product selectivity towards the formation of oxygenated hydrocarbon was associated to the coverage of oxygen species, which is surface-structure- and potential-dependent. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

Marked reduction of cerebral oxygen metabolism in patients with advanced cirrhosis

International Nuclear Information System (INIS)

Kawatoko, Toshiharu; Murai, Koichiro; Ibayashi, Setsurou; Tsuji, Hiroshi; Nomiyama, Kensuke; Sadoshima, Seizo; Eujishima, Masatoshi; Kuwabara, Yasuo; Ichiya, Yuichi

1992-01-01

Regional cerebral blood flow (rCBF), cerebral metabolic rate of oxygen (rCMRO 2 ), and oxygen extraction fraction (rOEF) were measured using positron emission tomography (PET) in four patients with cirrhosis (two males and two females, aged 57 to 69 years) in comparison with those in five age matched controls with previous transient global amnesia. PET studies were carried out when the patients were fully alert and oriented after the episodes of encephalopathy. In the patients, rCBF tended to be lower, while rCMRO 2 was significantly lowered in almost all hemisphere cortices, more markedly in the frontal cortex. Our results suggest that the brain oxygen metabolism is diffusely impaired in patients with advanced cirrhosis, and the frontal cortex seems to be more susceptible to the systemic metabolic derangements induced by chronic liver disease. (author)

Electrochemical Reduction of Oxygen and Nitric Oxide at Low Temperature on La1−xSrxFeO3−δ Cathodes

DEFF Research Database (Denmark)

Kammer Hansen, Kent

2014-01-01

A series of six strontium-substituted lanthanum ferrites (La1-xSrxFeO3-delta, x = 0.00, 0.05, 0.15, 0.25, 0.35, and 0.50) were synthesized using the glycine-nitrate process and evaluated as cathodes for the electrochemical reduction of oxygen and nitric oxide in the temperature range 200 to 400...... degrees C, using cone-shaped electrodes and cyclic voltammetry. It was shown that the ferrites had a higher activity towards the electrochemical reduction of nitric oxide than towards the electrochemical reduction of oxygen, in the investigated temperature range. The highest activity towards...... the electrochemical reduction of nitric oxide was found for La0.95Sr0.05FeO3-delta at 400 degrees C. This compound also showed the highest activity towards the electrochemical reduction of oxygen at 400 degrees C. The highest apparent selectivity was found for the compound LaFeO3 at 200 degrees C. The materials...

Electron transfer study on graphene modified glassy carbon substrate via electrochemical reduction and the application for tris(2,2'-bipyridyl)ruthenium(II) electrochemiluminescence sensor fabrication.

Science.gov (United States)

Xu, Yuanhong; Cao, Mengmei; Liu, Huihui; Zong, Xidan; Kong, Na; Zhang, Jizhen; Liu, Jingquan

2015-07-01

In this study, electron transfer behavior of the graphene nanosheets attachment on glassy carbon electrode (GCE) via direct electrochemical reduction of graphene oxide (GO) is investigated for the first time. The graphene modified electrode was achieved by simply dipping the GCE in GO suspension, followed by cyclic voltammetric scanning in the potential window from 0V to -1.5V. Tris(2,2'-bipyridyl)ruthenium(II) [Ru(bpy)3(2+)] was immobilized on the graphene modified electrode and used as the redox probe to evaluate the electron transfer behavior. The electron transfer rate constant (Ks) was calculated to be 61.9±5.8s(-1), which is much faster than that of tiled graphene modified GCE (7.1±0.6s(-1)). The enhanced electron transfer property observed with the GCE modified by reductively deposited graphene is probably due to its standing configuration, which is beneficial to the electron transfer comparing with the tiled one. Because the abundant oxygen-containing groups are mainly located at the edges of GO, which should be much easier for the reduction to start from, the reduced GO should tend to stand on the electrode surface as evidenced by scanning electron microscopy analysis. In addition, due to the favored electron transfer and standing configuration, the Ru(bpy)3(2+) electrochemiluminescence sensor fabricated with standing graphene modified GCE provided much higher and more stable efficiency than that fabricated with tiled graphene. Copyright © 2015 Elsevier B.V. All rights reserved.

Density functional studies of functionalized graphitic materials with late transition metals for oxygen reduction reactions

DEFF Research Database (Denmark)

Vallejo, Federico Calle; Martinez, Jose Ignacio; Rossmeisl, Jan

2011-01-01

Low-temperature fuel cells are appealing alternatives to the conventional internal combustion engines for transportation applications. However, in order for them to be commercially viable, effective, stable and low-cost electrocatalysts are needed for the Oxygen Reduction Reaction (ORR) at the ca...

Enhanced Oxygen Reduction Reaction by In Situ Anchoring Fe2N Nanoparticles on Nitrogen-Doped Pomelo Peel-Derived Carbon

Directory of Open Access Journals (Sweden)

Yiqing Wang

2017-11-01

Full Text Available The development of effective oxygen electrode catalysts for renewable energy technologies such as metal-air batteries and fuel cells remains challenging. Here, we prepared a novel high-performance oxygen reduction reaction (ORR catalyst comprised of Fe2N nanoparticles (NPs in situ decorated over an N-doped porous carbon derived from pomelo peel (i.e., Fe2N/N-PPC. The decorated Fe2N NPs provided large quantities of Fe-N-C bonding catalytic sites. The as-obtained Fe2N/N-PPC showed superior onset and half-wave potentials (0.966 and 0.891 V, respectively in alkaline media (0.1 M KOH compared to commercial Pt/C through a direct four-electron reaction pathway. Fe2N/N-PPC also showed better stability and methanol tolerance than commercial Pt/C. The outstanding ORR performance of Fe2N/N-PPC was attributed to its high specific surface area and the synergistic effects of Fe2N NPs. The utilization of agricultural wastes as a precursor makes Fe2N/N-PPC an ideal non-precious metal catalyst for ORR applications.

Electron transfer number control of the oxygen reduction reaction on nitrogen-doped reduced graphene oxides for the air electrodes of zinc-air batteries and organic degradation

Energy Technology Data Exchange (ETDEWEB)

Wu, Sheng-Hui; Li, Po-Chieh; Hu, Chi-Chang, E-mail: cchu@che.nthu.edu.tw

2016-11-01

The mean electron transfer number (n) of the oxygen reduction reaction (ORR) on reduced graphene oxide (rGO) is controlled by nitrogen doping for the air electrodes of Zn-air batteries and electrochemical organic degradation. Melamine and pyrrole are employed as the nitrogen sources for fabricating N-doped rGO (N-rGO) by microwave-assisted hydrothermal synthesis (MAHS). The n value of the ORR is determined by the rotating ring-disk electrode (RRDE) voltammetry and is successfully controlled from 2.34 to 3.93 by preparation variables. The N-doped structures are examined by the x-ray photoelectron spectroscopic (XPS) analysis. The morphology and the defect degree of N-rGOs are characterized by high resolution transmission electron microscopy (HR-TEM) and Raman spectroscopy. N-rGOs with high and low n values are employed as the air electrode catalysts of zinc-air batteries and in-situ hydrogen peroxide (H{sub 2}O{sub 2}) generation, respectively. The highest discharge cell voltage of 1.235 V for a Zn-air battery is obtained at 2 mA cm{sup −2} meanwhile the current efficiency of H{sub 2}O{sub 2} generation in 1-h electrolysis at 0 V (vs. RHE) reaches 43%. The electrocatalytic degradation of orange G (OG), analyzed by UV-VIS absorption spectra, reveals a high decoloration degree from the relative absorbance of 0.38 for the azo π-conjugation structure of OG. - Highlights: • The mean electron transfer number (n) is controlled by nitrogen doping. • Melamine and pyrrole are used as the nitrogen sources for fabricating N-rGO. • The n value is successfully controlled from 2.34 to 3.93 by preparation variables. • The highest discharge cell voltage of 1.235 V for a Zn-air battery. • The current efficiency of H{sub 2}O{sub 2} generation 1-h electrolysis reaches 43%.

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

Energy Technology Data Exchange (ETDEWEB)

Liu, Bin [Energy; Xu, Wu [Energy; Zheng, Jianming [Energy; Yan, Pengfei [Environmental; Walter, Eric D. [Environmental; Isern, Nancy [Environmental; Bowden, Mark E. [Environmental; Engelhard, Mark H. [Environmental; Kim, Sun Tai [Energy; Department; Read, Jeffrey [Power; Adams, Brian D. [Energy; Li, Xiaolin [Energy; Cho, Jaephil [Department; Wang, Chongmin [Environmental; Zhang, Ji-Guang [Energy

2017-10-11

The temperature dependence of the oxygen reduction mechanism in Li-O₂ 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-O₂ 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 to 40C, the morphologies of the Li₂O₂ 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-O₂ battery and will enable a more rational design of Li-O₂ batteries.

Electronic-level interactions of tungsten oxide with unsupported Se/Ru electrocatalytic nanoparticles

Energy Technology Data Exchange (ETDEWEB)

Lewera, Adam; Miecznikowski, Krzysztof [Department of Chemistry, University of Warsaw, Pasteura 1, 02-093 Warsaw (Poland); Hunger, Ralf [Institute of Materials Science, Darmstadt University of Technology, Darmstadt (Germany); Kolary-Zurowska, Aneta [Department of Chemistry, University of Warsaw, Pasteura 1, 02-093 Warsaw (Poland); Wieckowski, Andrzej [Department of Chemistry, University of Illinois at Urbana-Champaign, Urbana, IL (United States); Kulesza, Pawel J., E-mail: pkulesza@chem.uw.edu.p [Department of Chemistry, University of Warsaw, Pasteura 1, 02-093 Warsaw (Poland)

2010-11-01

Se/Ru nanoparticles - a potent non-platinum catalyst towards oxygen reduction reaction - were modified by hydrated WO{sub 3} and investigated using the rotating disk/ring electrode methods and by synchrotron X-ray photoelectron spectroscopy. The modification resulted in an enhanced catalytic activity towards oxygen reduction reaction (ORR). Our data indicate that the oxygen reduction current starts ca. 70 mV more positive and formation of undesirable hydrogen peroxide has significantly decreased following the modification of Se/Ru with WO{sub 3}. X-ray photoelectron spectroscopy reveals that WO{sub 3} interacts electronically with Se/Ru as the W 4f and Se 3d line-shapes change. We therefore conclude that the electronic interactions between Se/Ru and WO{sub 3} are primarily responsible for the increase in activity and selectivity of the WO{sub 3}-modified Se/Ru towards ORR.

Electronic-level interactions of tungsten oxide with unsupported Se/Ru electrocatalytic nanoparticles

International Nuclear Information System (INIS)

Lewera, Adam; Miecznikowski, Krzysztof; Hunger, Ralf; Kolary-Zurowska, Aneta; Wieckowski, Andrzej; Kulesza, Pawel J.

2010-01-01

Se/Ru nanoparticles - a potent non-platinum catalyst towards oxygen reduction reaction - were modified by hydrated WO 3 and investigated using the rotating disk/ring electrode methods and by synchrotron X-ray photoelectron spectroscopy. The modification resulted in an enhanced catalytic activity towards oxygen reduction reaction (ORR). Our data indicate that the oxygen reduction current starts ca. 70 mV more positive and formation of undesirable hydrogen peroxide has significantly decreased following the modification of Se/Ru with WO 3 . X-ray photoelectron spectroscopy reveals that WO 3 interacts electronically with Se/Ru as the W 4f and Se 3d line-shapes change. We therefore conclude that the electronic interactions between Se/Ru and WO 3 are primarily responsible for the increase in activity and selectivity of the WO 3 -modified Se/Ru towards ORR.

From melamine sponge towards 3D sulfur-doping carbon nitride as metal-free electrocatalysts for oxygen reduction reaction

Science.gov (United States)

Xu, Jingjing; Li, Bin; Li, Songmei; Liu, Jianhua

2017-07-01

Development of new and efficient metal-free electrocatalysts for replacing Pt to improve the sluggish kinetics of oxygen reduction reaction (ORR) is of great importance to emerging renewable energy technologies such as metal-air batteries and polymer electrolyte fuel cells. Herein, 3D sulfur-doping carbon nitride (S-CN) as a novel metal-free ORR electrocatalyst was synthesized by exploiting commercial melamine sponge as raw material. The sulfur atoms were doping on CN networks uniformly through numerous S-C bonds which can provide additional active sites. And it was found that the S-CN exhibited high catalytic activity for ORR in term of more positive onset potential, higher electron transfer number and higher cathodic density. This work provides a novel choice of metal-free ORR electrocatalysts and highlights the importance of sulfur-doping CN in metal-free ORR electrocatalysts.

Electroreduction of oxygen on carbon-supported gold catalysts

International Nuclear Information System (INIS)

Erikson, Heiki; Juermann, Gea; Sarapuu, Ave; Potter, Robert J.; Tammeveski, Kaido

2009-01-01

The electrochemical reduction of oxygen was studied on Au/C catalysts (20 and 30 wt%) in 0.5 M H 2 SO 4 and 0.1 M KOH solutions using the rotating disk electrode (RDE) method. The thickness of the Au/C-Nafion layers was varied between 1.5 and 10 μm. The specific activity of Au was independent of catalyst loading in both solutions, indicating that the transport of reactants through the catalyst layer does not limit the process of oxygen reduction under these conditions. The mass activity of 20 wt% Au/C catalysts was higher due to smaller particle size. The number of electrons involved in the reaction and the Tafel slopes were found; the values of these parameters are similar to that of bulk polycrystalline gold and indicate that the mechanism of O 2 reduction is not affected by carbon support or the catalyst configuration.

Electro-deposition of Pd on Carbon paper and Ni foam via surface limited redox-replacement reaction for oxygen reduction reaction

International Nuclear Information System (INIS)

Modibedi, Remegia M.; Mathe, Mkhulu K.; Motsoeneng, Rapelang G.; Khotseng, Lindiwe E.; Ozoemena, Kenneth I.; Louw, Eldah K.

2014-01-01

Pd nanostructured catalysts were electrodeposited by surface-limited redox replacement reactions using the electrochemical atomic layer deposition technique. Carbon paper and Ni foam were used as substrates for the electrodeposition of the metal. Supported nanostructured Pd electrodes were characterized using electrochemical methods and scanning electron microscopy. Carbon paper and Ni foam produced good quality deposits with some agglomeration on Ni foam. The EDX profiles confirmed the presence of Pd particles. Cyclic voltammograms of the electrodeposited Pd on substrates showed features characteristic of polycrystalline Pd electrodes. In the acidic electrolyte a very weak oxygen reduction reaction (ORR) activity was observed on Pd/Carbon paper electrode when compared to Pd/Ni foam electrode. The Pd/Ni foam electrode showed improved ORR activity in alkaline medium

Nature and Distribution of Stable Subsurface Oxygen in Copper Electrodes During Electrochemical CO2 Reduction

DEFF Research Database (Denmark)

Cavalca, Filippo Carlo; Ferragut, Rafael; Aghion, Stefano

2017-01-01

Oxide-derived copper (OD-Cu) electrodes exhibit higher activity than pristine copper during the carbon dioxide reduction reaction (CO2RR) and higher selectivity towards ethylene. The presence of residual subsurface oxygen in OD-Cu has been proposed to be responsible for such improvements, although...

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

DEFF Research Database (Denmark)

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

2012-01-01

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

Nonadiabatic two-electron transfer mediated by an irregular bridge

International Nuclear Information System (INIS)

Petrov, E.G.; Shevchenko, Ye.V.; May, V.

2004-01-01

Nonadiabatic two-electron transfer (TET) mediated by a linear molecular bridge is studied theoretically. Special attention is put on the case of a irregular distribution of bridge site energies as well as on the inter-site Coulomb interaction. Based on the unified description of electron transfer reactions [J. Chem. Phys. 115 (2001) 7107] a closed set of kinetic equations describing the TET process is derived. A reduction of this set to a single exponential donor-acceptor (D-A) TET is performed together with a derivation of an overall D-A TET rate. The latter contains a contribution of the stepwise as well as of the concerted route of D-A TET. The stepwise contribution is determined by two single-electron steps each of them associated with a sequential and a superexchange pathway. A two-electron unistep superexchange transition between the D and A forms the concerted contribution to the overall rate. Both contributions are analyzed in their dependency on the bridge length. The irregular distribution of the bridge site energies as well as the influence of the Coulomb interaction facilitates the D-A TET via a modification of the stepwise and the concerted part of the overall rate. At low temperatures and for short bridges with a single or two units the concerted contribution exceeds the stepwise contribution. If the bridge contains more than two units, the stepwise contribution dominates the overall rate

Low content of Pt supported on Ni-MoCx/carbon black as a highly durable and active electrocatalyst for methanol oxidation, oxygen reduction and hydrogen evolution reactions in acidic condition

Science.gov (United States)

Zhang, Yan; Zang, Jianbing; Jia, Shaopei; Tian, Pengfei; Han, Chan; Wang, Yanhui

2017-08-01

Nickel and molybdenum carbide modified carbon black (Ni-MoCx/C) was synthesized by a two-step microwave-assisted deposition/carbonthermal reduction method and characterized by X-ray diffraction, transmission electron microscopy, energy dispersive spectroscopy and X-ray photoelectron spectroscopy. The as-prepared Ni-MoCx/C supported Pt (10 wt%) electrocatalyst (10Pt/Ni-MoCx/C) was synthesized through a microwave-assisted reduction method and 10Pt/Ni-MoCx/C exhibited high electrocatalytic activity for methanol oxidation, oxygen reduction and hydrogen evolution reactions. Results showed that 10Pt/Ni-MoCx/C electrocatalyst had better electrocatalytic activity and stability performance than 20 wt% Pt/C (20Pt/C) electrocatalyst. Among them, the electrochemical surface area of 10Pt/Ni-MoCx/C reached 68.4 m2 g-1, which was higher than that of 20Pt/C (63.2 m2 g-1). The enhanced stability and activity of 10Pt/Ni-MoCx/C electrocatalyst were attributed to: (1) an anchoring effect of Ni and MoCx formed during carbonthermal reduction process; (2) a synergistic effect among Pt, Ni, MoOx and MoCx. These findings indicated that 10Pt/Ni-MoCx/C was a promising electrocatalyst for direct methanol fuel cells.

Cadmium poisoning of oxygen reduction on platinum electrode in potassium hydroxide

Science.gov (United States)

Miller, R. O.

1972-01-01

Experiment with a rotating disk and ring apparatus showed no poisoning by cadmium in 8.5 M KOH, alone or with Cl(-) or CO3(=). Poisoning does not occur either in 0.1 M KOH supernatant at CdO, but a partially reversible poisoning results from .0001 M CdCl2 and traces of fatty acid are present. Evidence indicates that the catastrophic poisoning affects the four-electron O2 reduction more than it does the one-electron H3O(+) discharge.

Uric acid-derived Fe3C-containing mesoporous Fe/N/C composite with high activity for oxygen reduction reaction in alkaline medium

Science.gov (United States)

Ma, Jun; Xiao, Dejian; Chen, Chang Li; Luo, Qiaomei; Yu, Yue; Zhou, Junhao; Guo, Changding; Li, Kai; Ma, Jie; Zheng, Lirong; Zuo, Xia

2018-02-01

In this work, a category of Fe3C-containing Fe/N/C mesoporous material has been fabricated by carbonizing the mixture of uric acid, Iron (Ⅲ) chloride anhydrous and carbon support (XC-72) under different pyrolysis temperature. Of all these samples, pyrolysis temperature (800 °C) becomes the most crucial factor in forming Fe3C active sites which synergizes with high content of graphitic N to catalyze oxygen reduction reaction (ORR). X-ray absorption fine structure spectroscopy (XAFS) is used to exhibit that the space structure around Fe atoms in the catalyst. This kind of catalyst possesses comparable ORR properties with commercial 20% Pt/C (onset potential is 0 V vs. Ag/AgCl in 0.1 M KOH), the average transfer electron number is 3.84 reflecting the 4-electron process. Moreover, superior stability and methanol tolerance deserve to be mentioned.

Lanthanides-based graphene catalysts for high performance hydrogen evolution and oxygen reduction

International Nuclear Information System (INIS)

Shinde, S.S.; Sami, Abdul; Lee, Jung-Ho

2016-01-01

Highlights: • Facile, scalable in-situ synthesis of lanthanide (La, Eu, Yb) doped graphene frameworks. • Efficient electrocatalytic performance towards HER and ORR. • Eu-Gr hybrid shows HER performance; onset & overpotential (81 & 160 mV), & Tafel slope (52 mV dec −1 ). • Eu-Gr exhibits superior activity of ORR; onset potential (0.92 V), electron transfer number (4.03). • Excellent long-term stability in HER and ORR, comparable to those of commercial Pt/C catalysts. - Abstract: The design of efficient electrocatalysts for hydrogen evolution reaction (HER) and oxygen reduction reaction (ORR) has received enormous consideration due to their effectiveness in modern renewable energy technologies such as fuel cells, electrolyzers, and metal–air batteries. Herein, we present a facile method to fabricate lanthanides (L = La, Eu, Yb)-doped graphene materials as catalyst for the HER and ORR that show desirable electrocatalytic activities as well as long-term stability. The Eu-graphene hybrid has showed unbeatable HER performance such as small values of onset potential (81 mV), overpotential (160 mV), and Tafel slope (52 mV dec −1 ), along with a high exchange current density (7.55 × 10 −6 A cm −2 ). The L-graphenes also exhibit superior electrocatalytic activity for ORR, including small Tafel slopes (96, 66, and 105 mV dec −1 for La-Gr, Eu-Gr, and Yb-Gr, respectively), positive onset potential (∼0.83–0.92 V), high electron transfer numbers (∼3.84–4.03), and excellent enduring strength, analogous to those of viable Pt/C catalysts. The excellent electrocatalytic performance is attributed to the synergistic effect of abundant edges and doping sites, high electrical conductivity, large active surface areas and fast charge transfer; which renders lanthanide-based graphene hybrids as potentially great candidate for energy conversion systems.

Influences of dissolved oxygen concentration on biocathodic microbial communities in microbial fuel cells.

Science.gov (United States)

Rago, Laura; Cristiani, Pierangela; Villa, Federica; Zecchin, Sarah; Colombo, Alessandra; Cavalca, Lucia; Schievano, Andrea

2017-08-01

Dissolved oxygen (DO) at cathodic interface is a critical factor influencing microbial fuel cells (MFC) performance. In this work, three MFCs were operated with cathode under different DO conditions: i) air-breathing (A-MFC); ii) water-submerged (W-MFC) and iii) assisted by photosynthetic microorganisms (P-MFC). A plateau of maximum current was reached at 1.06±0.03mA, 1.48±0.06mA and 1.66±0.04mA, increasing respectively for W-MFC, P-MFC and A-MFC. Electrochemical and microbiological tools (Illumina sequencing, confocal microscopy and biofilm cryosectioning) were used to explore anodic and cathodic biofilm in each MFC type. In all cases, biocathodes improved oxygen reduction reaction (ORR) as compared to abiotic condition and A-MFC was the best performing system. Photosynthetic cultures in the cathodic chamber supplied high DO level, up to 16mg O2 L -1 , which sustained aerobic microbial community in P-MFC biocathode. Halomonas, Pseudomonas and other microaerophilic genera reached >50% of the total OTUs. The presence of sulfur reducing bacteria (Desulfuromonas) and purple non-sulfur bacteria in A-MFC biocathode suggested that the recirculation of sulfur compounds could shuttle electrons to sustain the reduction of oxygen as final electron acceptor. The low DO concentration limited the cathode in W-MFC. A model of two different possible microbial mechanisms is proposed which can drive predominantly cathodic ORR. Copyright © 2017 Elsevier B.V. All rights reserved.

Electron attachment to oxygen, ozone and other compounds of atmospheric relevance as studied with ultra-high energy resolution

International Nuclear Information System (INIS)

Maerk, T.D.; Matejcik, S.; Kiendler, A.; Cicman, P.; Senn, G.; Skalny, J.; Stampfli, P.; Illenberger, E.; Chu, Y.; Stamatovic, A.

1996-01-01

The processes of electron attachment to oxygen, ozone, ozone/oxygen cluster and oxygen cluster as well as other compounds of atmospheric relevance (CF 2 Cl 2 , CHCl 3 and CCl 3 Br) were studied with ultra-high energy resolution crossed beam technique

Determination of one-electron reduction potentials of some radiosensitive compounds by pulse radiolysis

International Nuclear Information System (INIS)

Zuo Zhihua; Yao Side; Li Hucheng; Lin Nianyun; Jin Yizun

1994-01-01

One-electron reduction potential (E 7 1 ) is one of the important parameters of radiosensitive compound with high electron affinity. In this work one-electron reduction potentials of some radiosensitizers, such as Miso, 911, CMNa, SMU-1, SMU-2, SMD, SNN, S 3 and BSO, were determined pulse radiolytically by using anthraquinone-2-sulfate (AQS), duroquinone (DQ) and methyl viologen (MV 2+ ) as references

Methanol as electron donor for thermophilic biological sulfate and sulfite reduction

OpenAIRE

Weijma, J.

2000-01-01

Sulfur oxyanions (e.g. sulfate, sulfite) can be removed from aqueous waste- and process streams by biological reduction with a suitable electron donor to sulfide, followed by partial chemical or biological oxidation of sulfide to elemental sulfur. The aim of the research described in this thesis was to make this biological process more broadly applicable for desulfurization of flue-gases and ground- and wastewaters by using the cheap chemical methanol as electron donor for the reduct...

Particle size dependence on oxygen reduction reaction activity of electrodeposited TaOx catalysts in acidic media

KAUST Repository

Seo, J.; Cha, Dong Kyu; Takanabe, Kazuhiro; Kubota, J.; Domen, K.

2013-01-01

The size dependence of the oxygen reduction reaction activity was studied for TaOx nanoparticles electrodeposited on carbon black for application to polymer electrolyte fuel cells (PEFCs). Compared with a commercial Ta2O5 material, the ultrafine

Pt catalysts on PANI coated WC/C nanocomposites for methanol electro-oxidation and oxygen electro-reduction in DMFC

International Nuclear Information System (INIS)

Yaldagard, Maryam; Jahanshahi, Mohsen; Seghatoleslami, Naser

2014-01-01

Highlights: • In this work nanosized WC/C were successfully coated by PANI. • Pt particles (10.56 nm) were uniformly dispersed on the surface of PANI/WC/C support. • The Pt/PANI/WC/C exhibited higher MOR activity and CO tolerance than Pt/C. • The Pt/PANI/WC/C exhibited higher activity for ORR than Pt/C in RDE experiments. • Pt/PANI/WC/C showed good stability than that of Pt/C in the presence of methanol. - Abstract: In the present study a Pt/PANI/WC/C electrocatalyst was developed to increase the methanol electro-oxidation and oxygen electro-reduction activity and stability of commercial Pt/C electrocatalyst. WC/C was coated with protonated polyaniline (PANI) in situ during the polymerization of aniline. Fourier transform infrared (FTIR) results illustrate the presence of PANI in the composite. The conductivity of PANI coated – WC/C has been compared with the conductivity of the corresponding mixtures of WC/C and Vulcan XC-72. X-ray diffraction results showed that Pt particles were dispersed on the support with mean particle size of about 10.56 nm. Transition electron microscopy images showed that the nanosized WC/C were successfully coated by PANI. Based on the electrochemical properties characterized by cyclic voltammetry, CO stripping and rotating disk electrode measurements it was found that the as prepared Pt/PANI/WC/C electrocatalyst exhibited a comparable activity for methanol oxidation reaction and oxygen reduction reaction with respect to the commercial one. A significant reduction in the potential of CO electro-oxidation peak from 0.75 V for Pt/C to 0.52 V for Pt/PANI/WC/C electrocatalyst indicates that an increase in the activity for CO electro-oxidation is achieved by replacing the carbon support by PANI coated WC/C. Chronoamerometry results also showed, in the presence of methanol the Pt/PANI/WC/C electrocatalyst still maintains a higher current density than Pt/WC/C and Pt/C

Pt catalysts on PANI coated WC/C nanocomposites for methanol electro-oxidation and oxygen electro-reduction in DMFC

Energy Technology Data Exchange (ETDEWEB)

Yaldagard, Maryam, E-mail: m_yaldagard@yahoo.com [Department of Chemical Engineering, Ferdowsi University of Mashhad, P.O. Box 91775-1111 (Iran, Islamic Republic of); Nanotechnology Research Institute, School of Chemical Engineering, Babol University of Technology (Iran, Islamic Republic of); Jahanshahi, Mohsen, E-mail: mjahan@nit.um.ac.ir [Nanotechnology Research Institute, School of Chemical Engineering, Babol University of Technology (Iran, Islamic Republic of); Seghatoleslami, Naser, E-mail: Slami@um.ac.ir [Department of Chemical Engineering, Ferdowsi University of Mashhad, P.O. Box 91775-1111 (Iran, Islamic Republic of)

2014-10-30

Highlights: • In this work nanosized WC/C were successfully coated by PANI. • Pt particles (10.56 nm) were uniformly dispersed on the surface of PANI/WC/C support. • The Pt/PANI/WC/C exhibited higher MOR activity and CO tolerance than Pt/C. • The Pt/PANI/WC/C exhibited higher activity for ORR than Pt/C in RDE experiments. • Pt/PANI/WC/C showed good stability than that of Pt/C in the presence of methanol. - Abstract: In the present study a Pt/PANI/WC/C electrocatalyst was developed to increase the methanol electro-oxidation and oxygen electro-reduction activity and stability of commercial Pt/C electrocatalyst. WC/C was coated with protonated polyaniline (PANI) in situ during the polymerization of aniline. Fourier transform infrared (FTIR) results illustrate the presence of PANI in the composite. The conductivity of PANI coated – WC/C has been compared with the conductivity of the corresponding mixtures of WC/C and Vulcan XC-72. X-ray diffraction results showed that Pt particles were dispersed on the support with mean particle size of about 10.56 nm. Transition electron microscopy images showed that the nanosized WC/C were successfully coated by PANI. Based on the electrochemical properties characterized by cyclic voltammetry, CO stripping and rotating disk electrode measurements it was found that the as prepared Pt/PANI/WC/C electrocatalyst exhibited a comparable activity for methanol oxidation reaction and oxygen reduction reaction with respect to the commercial one. A significant reduction in the potential of CO electro-oxidation peak from 0.75 V for Pt/C to 0.52 V for Pt/PANI/WC/C electrocatalyst indicates that an increase in the activity for CO electro-oxidation is achieved by replacing the carbon support by PANI coated WC/C. Chronoamerometry results also showed, in the presence of methanol the Pt/PANI/WC/C electrocatalyst still maintains a higher current density than Pt/WC/C and Pt/C.

Evaluation and Enhancement of the Oxygen Reduction Reaction Activity on Hafnium Oxide Nanoparticles Assisted by L(+)-lysine

International Nuclear Information System (INIS)

Chisaka, Mitsuharu; Itagaki, Noriaki

2016-01-01

Evaluation of the oxygen reduction reaction (ORR) on oxide compounds is difficult owing to the insulating nature of oxides. In this study, various amounts of L(+)-lysine were added to the precursor dispersion for the hydrothermal synthesis of hafnium oxide nanoparticles on reduced graphene oxide sheets (HfO_x–rGO) to coat the HfO_x catalysts with layers of carbon, thereby increasing the conductivity and number of active sites. When the mass ratio of L(+)-lysine to GO, R, was above 26, carbon layers were formed and the amount monotonically increased with increasing R, as noted by cyclic voltammogrametry. X-ray photoelectron spectroscopy and rotating disk electrode analyses revealed that pyrolysis produced ORR-active oxygen defects, whose formation was proposed to involve carbothermal reduction. When 53 ≤ R ≤ 210, HfO_x–rGO contained a similar amount of oxygen defects and ORR activity, as represented by an onset potential of 0.9 V versus the reversible hydrogen electrode in 0.1 mol dm"−"3 H_2SO_4. However, the number of active sites depended on R due to the amount of L(+)-lysine-derived carbon layers that increased both the number of active sites and resistivity towards oxygen diffusion.

Cytotoxicity of InP/ZnS quantum dots related to reactive oxygen species generation

Science.gov (United States)

Chibli, Hicham; Carlini, Lina; Park, Soonhyang; Dimitrijevic, Nada M.; Nadeau, Jay L.

2011-06-01

Indium phosphide (InP) quantum dots (QDs) have emerged as a presumably less hazardous alternative to cadmium-based particles, but their cytotoxicity has not been well examined. Although their constituent elements are of very low toxicity to cells in culture, they nonetheless exhibit phototoxicity related to generation of reactive oxygen species by excited electrons and/or holes interacting with water and molecular oxygen. Using spin-trap electron paramagnetic resonance (EPR) spectroscopy and reporter assays, we find a considerable amount of superoxide and a small amount of hydroxyl radical formed under visible illumination of biocompatible InP QDs with a single ZnS shell, comparable to what is seen with CdTe. A double thickness shell reduces the reactive oxygen species concentration approximately two-fold. Survival assays in five cell lines correspondingly indicate a distinct reduction in toxicity with the double-shell InP QDs. Toxicity varies significantly across cell lines according to the efficiency of uptake, being overall significantly less than what is seen with CdTe or CdSe/ZnS. This indicates that InP QDs are a useful alternative to cadmium-containing QDs, while remaining capable of electron-transfer processes that may be undesirable or which may be exploited for photosensitization applications.

Cytotoxicity of InP/ZnS quantum dots related to reactive oxygen species generation.

Energy Technology Data Exchange (ETDEWEB)

Chibli, H.; Carlini, L.; Park, S.; Dimitrijevic, N. M.; Nadeau, J. L. (Center for Nanoscale Materials); ( CSE); (McGill Univ.)

2011-01-01

Indium phosphide (InP) quantum dots (QDs) have emerged as a presumably less hazardous alternative to cadmium-based particles, but their cytotoxicity has not been well examined. Although their constituent elements are of very low toxicity to cells in culture, they nonetheless exhibit phototoxicity related to generation of reactive oxygen species by excited electrons and/or holes interacting with water and molecular oxygen. Using spin-trap electron paramagnetic resonance (EPR) spectroscopy and reporter assays, we find a considerable amount of superoxide and a small amount of hydroxyl radical formed under visible illumination of biocompatible InP QDs with a single ZnS shell, comparable to what is seen with CdTe. A double thickness shell reduces the reactive oxygen species concentration approximately two-fold. Survival assays in five cell lines correspondingly indicate a distinct reduction in toxicity with the double-shell InP QDs. Toxicity varies significantly across cell lines according to the efficiency of uptake, being overall significantly less than what is seen with CdTe or CdSe/ZnS. This indicates that InP QDs are a useful alternative to cadmium-containing QDs, while remaining capable of electron-transfer processes that may be undesirable or which may be exploited for photosensitization applications.

Oxygen reduction on carbon supported platinum catalysts in high temperature polymer electrolytes

DEFF Research Database (Denmark)

Qingfeng, Li; Hjuler, Hans Aage; Bjerrum, Niels

2000-01-01

Oxygen reduction on carbon supported platinum catalysts has been investigated in H3PO4, H3PO4-doped Nafion and polybenzimidazole (PBI) polymer electrolytes in a temperature range up to 190 degrees C. Compared with pure H3PO4, the combination of H3PO4 and polymer electrolytes can significantly...... membrane fuel cell based on H3PO4-doped PBI for operation at temperatures between 150 and 200 degrees C. (C) 2000 Elsevier Science Ltd. All rights reserved....

Microwave Assisted Synthesis of Osmium Electrocatalysts for the Oxygen Reduction Reaction in the Absence and Presence of Aqueous Methanol

Directory of Open Access Journals (Sweden)

Edgar Borja-Arco

2011-01-01

Full Text Available Osmium electrocatalysts for the oxygen reduction reaction (ORR were prepared by microwave irradiation of Os3(CO12 at different experimental conditions. The materials obtained were structurally characterized by FT-IR, micro-Raman spectroscopy and X-ray diffraction. Their chemical compositions were obtained by EDS. The electrocatalytic properties for the oxygen reduction reaction were evaluated by rotating disk electrode measurements in 0.5 mol L-1 H2SO4, in the absence and presence of aqueous methanol. The kinetic parameters, such as Tafel slope, exchange current density, and charge transfer coefficient are reported.

Structural, electronic, and magnetic properties of pristine and oxygen-adsorbed graphene nanoribbons

Energy Technology Data Exchange (ETDEWEB)

Miwa, R.H.; Veiga, R.G.A. [Instituto de Fisica, Universidade Federal de Uberlandia, Caixa Postal 593, CEP 38400-902, Uberlandia, MG (Brazil); Srivastava, G.P., E-mail: gps@excc.ex.ac.uk [School of Physics, University of Exeter, Stocker Road, Exeter EX4 4QL (United Kingdom)

2010-07-15

The structural, electronic and magnetic properties of pristine and oxygen-adsorbed (3,0) zigzag and (6,1) armchair graphene nanoribbons have been investigated theoretically, by employing the ab initio pseudopotential method within the density functional scheme. The zigzag nanoribbon is more stable with antiferromagnetically coupled edges, and is semiconducting. The armchair nanoribbon does not show any preference for magnetic ordering and is semiconducting. The oxygen molecule in its triplet state is adsorbed most stably at the edge of the zigzag nanoribbon. The Stoner metallic behaviour of the ferromagnetic nanoribbons and the Slater insulating (ground state) behaviour of the antiferromagnetic nanoribbons remain intact upon oxygen adsorption. However, the local magnetic moment of the edge carbon atom of the ferromagnetic zigzag ribbon is drastically reduced, due to the formation of a spin-paired C-O bond.

Metal-Organic-Framework-Derived Hybrid Carbon Nanocages as a Bifunctional Electrocatalyst for Oxygen Reduction and Evolution.

Science.gov (United States)

Liu, Shaohong; Wang, Zhiyu; Zhou, Si; Yu, Fengjiao; Yu, Mengzhou; Chiang, Chang-Yang; Zhou, Wuzong; Zhao, Jijun; Qiu, Jieshan

2017-08-01

The oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) are cornerstone reactions for many renewable energy technologies. Developing cheap yet durable substitutes of precious-metal catalysts, especially the bifunctional electrocatalysts with high activity for both ORR and OER reactions and their streamlined coupling process, are highly desirable to reduce the processing cost and complexity of renewable energy systems. Here, a facile strategy is reported for synthesizing double-shelled hybrid nanocages with outer shells of Co-N-doped graphitic carbon (Co-NGC) and inner shells of N-doped microporous carbon (NC) by templating against core-shell metal-organic frameworks. The double-shelled NC@Co-NGC nanocages well integrate the high activity of Co-NGC shells into the robust NC hollow framework with enhanced diffusion kinetics, exhibiting superior electrocatalytic properties to Pt and RuO 2 as a bifunctional electrocatalyst for ORR and OER, and hold a promise as efficient air electrode catalysts in Zn-air batteries. First-principles calculations reveal that the high catalytic activities of Co-NGC shells are due to the synergistic electron transfer and redistribution between the Co nanoparticles, the graphitic carbon, and the doped N species. Strong yet favorable adsorption of an OOH* intermediate on the high density of uncoordinated hollow-site C atoms with respect to the Co lattice in the Co-NGC structure is a vital rate-determining step to achieve excellent bifunctional electrocatalytic activity. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Oxygen reduction reaction on a highly-alloyed Pt-Ni supported carbon electrocatalyst in acid solution

CSIR Research Space (South Africa)

Zheng, H

2010-08-31

Full Text Available Alloyed electrocatalysts such as PtNi/C[1-2], PtCo/C[3], PtCr/C[4], PtFe/C [5-6], and non-alloyed Pt-TiO2/C were reportedly investigated for methanol tolerance during Oxygen reduction reaction (ORR). The high methanol tolerance...

Operando Soft X-ray Absorption Spectroscopic Study on a Solid Oxide Fuel Cell Cathode during Electrochemical Oxygen Reduction.

Science.gov (United States)

Nakamura, Takashi; Oike, Ryo; Kimura, Yuta; Tamenori, Yusuke; Kawada, Tatsuya; Amezawa, Koji

2017-05-09

An operando soft X-ray absorption spectroscopic technique, which enabled the analysis of the electronic structures of the electrode materials at elevated temperature in a controlled atmosphere and electrochemical polarization, was established and its availability was demonstrated by investigating the electronic structural changes of an La 2 NiO 4+δ dense-film electrode during an electrochemical oxygen reduction reaction. Clear O K-edge and Ni L-edge X-ray absorption spectra could be obtained below 773 K under an atmospheric pressure of 100 ppm O 2 /He, 0.1 % O 2 /He, and 1 % O 2 /He gas mixtures. Considerable spectral changes were observed in the O K-edge X-ray absorption spectra upon changing the PO2 and application of electrical potential, whereas only small spectral changes were observed in Ni L-edge X-ray absorption spectra. A pre-edge peak of the O K-edge X-ray absorption spectra, which reflects the unoccupied partial density of states of Ni 3d-O 2p hybridization, increased or decreased with cathodic or anodic polarization, respectively. The electronic structural changes of the outermost orbital of the electrode material due to electrochemical polarization were successfully confirmed by the operando X-ray absorption spectroscopic technique developed in this study. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Dissimilatory nitrate reduction by Aspergillus terreus isolated from the seasonal oxygen minimum zone in the Arabian Sea

OpenAIRE

Stief, Peter; Fuchs-Ocklenburg, Silvia; Kamp, Anja; Manohar, Cathrine-Sumathi; Houbraken, Jos; Boekhout, Teun; de Beer, Dirk; Stoeck, Thorsten

2014-01-01

Background A wealth of microbial eukaryotes is adapted to life in oxygen-deficient marine environments. Evidence is accumulating that some of these eukaryotes survive anoxia by employing dissimilatory nitrate reduction, a strategy that otherwise is widespread in prokaryotes. Here, we report on the anaerobic nitrate metabolism of the fungus Aspergillus terreus (isolate An-4) that was obtained from sediment in the seasonal oxygen minimum zone in the Arabian Sea, a globally important site of oce...

Oxygen Reduction Reaction for Generating H2 O2 through a Piezo-Catalytic Process over Bismuth Oxychloride.

Science.gov (United States)

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.

Solar fuel processing efficiency for ceria redox cycling using alternative oxygen partial pressure reduction methods

International Nuclear Information System (INIS)

Lin, Meng; Haussener, Sophia

2015-01-01

Solar-driven non-stoichiometric thermochemical redox cycling of ceria for the conversion of solar energy into fuels shows promise in achieving high solar-to-fuel efficiency. This efficiency is significantly affected by the operating conditions, e.g. redox temperatures, reduction and oxidation pressures, solar irradiation concentration, or heat recovery effectiveness. We present a thermodynamic analysis of five redox cycle designs to investigate the effects of working conditions on the fuel production. We focused on the influence of approaches to reduce the partial pressure of oxygen in the reduction step, namely by mechanical approaches (sweep gassing or vacuum pumping), chemical approaches (chemical scavenger), and combinations thereof. The results indicated that the sweep gas schemes work more efficient at non-isothermal than isothermal conditions, and efficient gas phase heat recovery and sweep gas recycling was important to ensure efficient fuel processing. The vacuum pump scheme achieved best efficiencies at isothermal conditions, and at non-isothermal conditions heat recovery was less essential. The use of oxygen scavengers combined with sweep gas and vacuum pump schemes further increased the system efficiency. The present work can be used to predict the performance of solar-driven non-stoichiometric redox cycles and further offers quantifiable guidelines for system design and operation. - Highlights: • A thermodynamic analysis was conducted for ceria-based thermochemical cycles. • Five novel cycle designs and various operating conditions were proposed and investigated. • Pressure reduction method affects optimal operating conditions for maximized efficiency. • Chemical oxygen scavenger proves to be promising in further increasing efficiency. • Formulation of quantifiable design guidelines for economical competitive solar fuel processing

Reductive dehalogenation of 5-bromouracil by aliphatic organic radicals in aqueous solutions; electron transfer and proton-coupled electron transfer mechanisms

Energy Technology Data Exchange (ETDEWEB)

Matasovic, Brunislav [Division of Physical Chemistry, ' Ruder Boskovic' Institute, Bijenicka c. 54, HR-10000 Zagreb (Croatia); Bonifacic, Marija, E-mail: bonifacic@irb.h [Division of Physical Chemistry, ' Ruder Boskovic' Institute, Bijenicka c. 54, HR-10000 Zagreb (Croatia)

2011-06-15

Reductive dehalogenation of 5-bromouracil by aliphatic organic radicals {sup {center_dot}C}O{sub 2}{sup -}, {sup {center_dot}C}H{sub 2}OH, {sup {center_dot}C}H(CH{sub 3})OH, and {sup {center_dot}C}H(CH{sub 3})O{sup -} have been studied in oxygen free aqueous solutions in the presence of organic additives: formate, methanol or ethanol. For radicals production {sup 60}Co {gamma}-radiolysis was employed and the yield of bromide was measured by means of ion chromatography. Both radical anions have reducing potential negative enough to transfer an electron to BrU producing bromide ion and U{sup {center_dot}} radical. High yields of bromide have been measured increasing proportional to the concentration of the corresponding organic additives at a constant dose rate. This is characteristic for a chain process where regeneration of radical ions occurs by H-atom abstraction by U{sup {center_dot}} radical from formate or ethanol. Results with the neutral radicals conformed earlier proposition that the reduction reaction of {alpha}-hydroxyalkyl radicals proceeds by the proton-coupled electron transfer mechanism (). Thus, while both {sup {center_dot}C}H{sub 2}OH and {sup {center_dot}C}H(CH{sub 3})OH did not react with BrU in water/alcohol solutions, addition of bicarbonate and acetate in mmol dm{sup -3} concentrations, pH 7, brought about chain debromination to occur in the case of {sup {center_dot}C}H(CH{sub 3})OH radical as reactant. Under the same conditions phosphate buffer, a base with higher bulk proton affinity, failed to have any influence. The results are taken as additional proofs for the specific complex formation of {alpha}-hydroxyalkyl radicals with suitable bases which enhances radicals' reduction potential in comparison with only water molecules as proton acceptors. Rate constants for the H-atom abstraction from ethanol and formate by U{sup {center_dot}} radicals have been estimated to amount to about {>=}85 and 1200 dm{sup 3} mol{sup -1} s{sup -1

Challenges in reduction of dinitrogen by proton and electron transfer.

Science.gov (United States)

van der Ham, Cornelis J M; Koper, Marc T M; Hetterscheid, Dennis G H

2014-08-07

Ammonia is an important nutrient for the growth of plants. In industry, ammonia is produced by the energy expensive Haber-Bosch process where dihydrogen and dinitrogen form ammonia at a very high pressure and temperature. In principle one could also reduce dinitrogen upon addition of protons and electrons similar to the mechanism of ammonia production by nitrogenases. Recently, major breakthroughs have taken place in our understanding of biological fixation of dinitrogen, of molecular model systems that can reduce dinitrogen, and in the electrochemical reduction of dinitrogen at heterogeneous surfaces. Yet for efficient reduction of dinitrogen with protons and electrons major hurdles still have to be overcome. In this tutorial review we give an overview of the different catalytic systems, highlight the recent breakthroughs, pinpoint common grounds and discuss the bottlenecks and challenges in catalytic reduction of dinitrogen.

First principles investigation of the activity of thin film Pt, Pd and Au surface alloys for oxygen reduction

DEFF Research Database (Denmark)

Tripkovic, Vladimir; Hansen, Heine Anton; Rossmeisl, Jan

2015-01-01

driving force for surface segregation, diffusion to defects or surface self-assembling. On the basis of stability and activity analysis we conclude that the near surface alloy of Pd in Pt and some PdAu binary and PtPdAu ternary thin films with a controlled amount of Au are the best catalysts for oxygen......Further advances in fuel cell technologies are hampered by kinetic limitations associated with the sluggish cathodic oxygen reduction reaction. We have investigated a range of different formulations of binary and ternary Pt, Pd and Au thin films as electrocatalysts for oxygen reduction. The most...... active binary thin films are near-surface alloys of Pt with subsurface Pd and certain PdAu and PtAu thin films with surface and/or subsurface Au. The most active ternary thin films are with pure metal Pt or Pd skins with some degree of Au in the surface and/or subsurface layer and the near-surface alloys...

General Solvent-dependent Strategy toward Enhanced Oxygen Reduction Reaction in Graphene/Metal Oxide Nanohybrids: Effects of Nitrogen-containing Solvent

Science.gov (United States)

Kao, Wei-Yao; Chen, Wei-Quan; Chiu, Yu-Hsiang; Ho, Yu-Hsuan; Chen, Chun-Hu

2016-11-01

A general solvent-dependent protocol directly influencing the oxygen reduction reaction (ORR) in metal oxide/graphene nanohybrids has been demonstrated. We conducted the two-step synthesis of cobalt oxide/N-doped graphene nanohybrids (CNG) with solvents of water, ethanol, and dimethylformamide (DMF), representing tree typical categories of aqueous, polar organic, and organic N-containing solvents commonly adopted for graphene nanocomposites preparation. The superior ORR performance of the DMF-hybrids can be attributed to the high nitrogen-doping, aggregation-free hybridization, and unique graphene porous structures. As DMF is the more effective N-source, the spectroscopic results support a catalytic nitrogenation potentially mediated by cobalt-DMF coordination complexes. The wide-distribution of porosity (covering micro-, meso-, to macro-pore) and micron-void assembly of graphene may further enhance the diffusion kinetics for ORR. As the results, CNG by DMF-synthesis exhibits the high ORR activities close to Pt/C (i.e. only 8 mV difference of half-wave potential with electron transfer number of 3.96) with the better durability in the alkaline condition. Additional graphene hybrids comprised of iron and manganese oxides also show the superior ORR activities by DMF-synthesis, confirming the general solvent-dependent protocol to achieve enhanced ORR activities.

Fe/N/C hollow nanospheres by Fe(iii)-dopamine complexation-assisted one-pot doping as nonprecious-metal electrocatalysts for oxygen reduction

Science.gov (United States)

Zhou, Dan; Yang, Liping; Yu, Linghui; Kong, Junhua; Yao, Xiayin; Liu, Wanshuang; Xu, Zhichuan; Lu, Xuehong

2015-01-01

In this work, a series of hollow carbon nanospheres simultaneously doped with N and Fe-containing species are prepared by Fe3+-mediated polymerization of dopamine on SiO2 nanospheres, carbonization and subsequent KOH etching of the SiO2 template. The electrochemical properties of the hollow nanospheres as nonprecious-metal electrocatalysts for oxygen reduction reaction (ORR) are characterized. The results show that the hollow nanospheres with mesoporous N-doped carbon shells of ~10 nm thickness and well-dispersed Fe3O4 nanoparticles prepared by annealing at 750 °C (Fe/N/C HNSs-750) exhibit remarkable ORR catalytic activity comparable to that of a commercial 20 wt% Pt/C catalyst, and high selectivity towards 4-electron reduction of O2 to H2O. Moreover, it displays better electrochemical durability and tolerance to methanol crossover effect in an alkaline medium than the Pt/C. The excellent catalytic performance of Fe/N/C HNSs-750 towards ORR can be ascribed to their high specific surface area, mesoporous morphology, homogeneous distribution of abundant active sites, high pyridinic nitrogen content, graphitic nitrogen and graphitic carbon, as well as the synergistic effect of nitrogen and iron species for catalyzing ORR.In this work, a series of hollow carbon nanospheres simultaneously doped with N and Fe-containing species are prepared by Fe3+-mediated polymerization of dopamine on SiO2 nanospheres, carbonization and subsequent KOH etching of the SiO2 template. The electrochemical properties of the hollow nanospheres as nonprecious-metal electrocatalysts for oxygen reduction reaction (ORR) are characterized. The results show that the hollow nanospheres with mesoporous N-doped carbon shells of ~10 nm thickness and well-dispersed Fe3O4 nanoparticles prepared by annealing at 750 °C (Fe/N/C HNSs-750) exhibit remarkable ORR catalytic activity comparable to that of a commercial 20 wt% Pt/C catalyst, and high selectivity towards 4-electron reduction of O2 to H2O

How oxygen attacks [FeFe] hydrogenases from photosynthetic organisms

Science.gov (United States)

Stripp, Sven T.; Goldet, Gabrielle; Brandmayr, Caterina; Sanganas, Oliver; Vincent, Kylie A.; Haumann, Michael; Armstrong, Fraser A.; Happe, Thomas

2009-01-01

Green algae such as Chlamydomonas reinhardtii synthesize an [FeFe] hydrogenase that is highly active in hydrogen evolution. However, the extreme sensitivity of [FeFe] hydrogenases to oxygen presents a major challenge for exploiting these organisms to achieve sustainable photosynthetic hydrogen production. In this study, the mechanism of oxygen inactivation of the [FeFe] hydrogenase CrHydA1 from C. reinhardtii has been investigated. X-ray absorption spectroscopy shows that reaction with oxygen results in destruction of the [4Fe-4S] domain of the active site H-cluster while leaving the di-iron domain (2FeH) essentially intact. By protein film electrochemistry we were able to determine the order of events leading up to this destruction. Carbon monoxide, a competitive inhibitor of CrHydA1 which binds to an Fe atom of the 2FeH domain and is otherwise not known to attack FeS clusters in proteins, reacts nearly two orders of magnitude faster than oxygen and protects the enzyme against oxygen damage. These results therefore show that destruction of the [4Fe-4S] cluster is initiated by binding and reduction of oxygen at the di-iron domain—a key step that is blocked by carbon monoxide. The relatively slow attack by oxygen compared to carbon monoxide suggests that a very high level of discrimination can be achieved by subtle factors such as electronic effects (specific orbital overlap requirements) and steric constraints at the active site. PMID:19805068

Interplay of oxygen octahedral rotations and electronic instabilities in strontium ruthenate Ruddlesden-Poppers from first principles

Science.gov (United States)

Voss, Johannes; Fennie, Craig J.

2011-03-01

The Ruddlesden-Popper ruthenates Sr n+1 Ru n O3 n + 1 display a broad range of electronic phases including p -wave superconductivity, electronic nematicity, and ferromagnetism. Elucidating the role of the number of perovskite blocks, n , in the realization of these differently ordered electronic states remains a challenge. Additionally dramatic experimental advances now enable the atomic scale growth of these complex oxide thin films on a variety of substrates coherently, allowing for the application of tunable epitaxial strain and subsequently the ability to control structural distortions such as oxygen octahedral rotations. Here we investigate from first principles the effect of oxygen octahedral rotations on the electronic structure of Sr 2 Ru O4 and Sr 3 Ru 2 O7 . We discuss possible implications for the physics of the bulk systems and point towards new effects in thin films.

Resonant electron attachment to mixed hydrogen/oxygen and deuterium/oxygen clusters

Science.gov (United States)

Renzler, Michael; Kranabetter, Lorenz; Barwa, Erik; Grubwieser, Lukas; Scheier, Paul; Ellis, Andrew M.

2017-11-01

Low energy electron attachment to mixed (H2)x/(O2)y clusters and their deuterated analogs has been investigated for the first time. These experiments were carried out using liquid helium nanodroplets to form the clusters, and the effect of the added electron was then monitored via mass spectrometry. There are some important differences between electron attachment to the pure clusters and to the mixed clusters. A particularly notable feature is the formation of HO2- and H2O- ions from an electron-induced chemical reaction between the two dopants. The chemistry leading to these anions appears to be driven by electron resonances associated with H2 rather than O2. The electron resonances for H2 can lead to dissociative electron attachment (DEA), just as for the free H2 molecule. However, there is evidence that the resonance in H2 can also lead to rapid electron transfer to O2, which then induces DEA of the O2. This kind of excitation transfer has not, as far as we are aware, been reported previously.

Reactivity of Trapped and Accumulated Electrons in Titanium Dioxide Photocatalysis

Directory of Open Access Journals (Sweden)

Shigeru Kohtani

2017-10-01

Full Text Available Electrons, photogenerated in conduction bands (CB and trapped in electron trap defects (Tids in titanium dioxide (TiO2, play crucial roles in characteristic reductive reactions. This review summarizes the recent progress in the research on electron transfer in photo-excited TiO2. Particularly, the reactivity of electrons accumulated in CB and trapped at Tids on TiO2 is highlighted in the reduction of molecular oxygen and molecular nitrogen, and the hydrogenation and dehalogenation of organic substrates. Finally, the prospects for developing highly active TiO2 photocatalysts are discussed.

2D molybdenum disulphide (2D-MoS2) modified electrodes explored towards the oxygen reduction reaction

Science.gov (United States)

Rowley-Neale, Samuel J.; Fearn, Jamie M.; Brownson, Dale A. C.; Smith, Graham C.; Ji, Xiaobo; Banks, Craig E.

2016-08-01

Two-dimensional molybdenum disulphide nanosheets (2D-MoS2) have proven to be an effective electrocatalyst, with particular attention being focused on their use towards increasing the efficiency of the reactions associated with hydrogen fuel cells. Whilst the majority of research has focused on the Hydrogen Evolution Reaction (HER), herein we explore the use of 2D-MoS2 as a potential electrocatalyst for the much less researched Oxygen Reduction Reaction (ORR). We stray from literature conventions and perform experiments in 0.1 M H2SO4 acidic electrolyte for the first time, evaluating the electrochemical performance of the ORR with 2D-MoS2 electrically wired/immobilised upon several carbon based electrodes (namely; Boron Doped Diamond (BDD), Edge Plane Pyrolytic Graphite (EPPG), Glassy Carbon (GC) and Screen-Printed Electrodes (SPE)) whilst exploring a range of 2D-MoS2 coverages/masses. Consequently, the findings of this study are highly applicable to real world fuel cell applications. We show that significant improvements in ORR activity can be achieved through the careful selection of the underlying/supporting carbon materials that electrically wire the 2D-MoS2 and utilisation of an optimal mass of 2D-MoS2. The ORR onset is observed to be reduced to ca. +0.10 V for EPPG, GC and SPEs at 2D-MoS2 (1524 ng cm-2 modification), which is far closer to Pt at +0.46 V compared to bare/unmodified EPPG, GC and SPE counterparts. This report is the first to demonstrate such beneficial electrochemical responses in acidic conditions using a 2D-MoS2 based electrocatalyst material on a carbon-based substrate (SPEs in this case). Investigation of the beneficial reaction mechanism reveals the ORR to occur via a 4 electron process in specific conditions; elsewhere a 2 electron process is observed. This work offers valuable insights for those wishing to design, fabricate and/or electrochemically test 2D-nanosheet materials towards the ORR.Two-dimensional molybdenum disulphide nanosheets

Oxygen permeation flux through 10Sc1YSZ-MnCo2O4 asymmetric membranes prepared by two-step sintering

DEFF Research Database (Denmark)

Pirou, Stéven; Gurauskis, Jonas; Gil, Vanesa

2016-01-01

Asymmetric membranes based on a dual phase composite consisting of (Y2O3)0.01(Sc2O3)0.10(ZrO2)0.89 (10Sc1YSZ) as ionic conductor and MnCo2O4 as electronic conductor were prepared and characterized with respect to sinterability, microstructure and oxygen transport properties. The composite membranes...... were prepared by tape casting, lamination and fired in a two-step sintering process. Microstructural analysis showed that a gastight thin membrane layer with the desired ratio of ionic/electronic conducting phases could be fabricated. Oxygen permeation fluxes across the 10SclYSZ/MnCo2O4 (70/30 vol......%) composite membrane were measured from 750 to 940 degrees C using air or pure oxygen as feed gases and N2 or CO2 as sweep gases. Fluxes up to 2.3 mlN min-1 cm-2 were obtained for the 7 μm thick membrane. A degradation test over 1730 h showed an initial degradation of 21% during the first 1100 h after which...

One-step Synthesis of Pt Nanoparticles Highly Loaded on Graphene Aerogel as Durable Oxygen Reduction Electrocatalyst

International Nuclear Information System (INIS)

Huang, Qinghong; Tao, Feifei; Zou, Liangliang; Yuan, Ting; Zou, Zhiqing; Zhang, Haifeng; Zhang, Xiaogang; Yang, Hui

2015-01-01

Synthesis of highly active and durable Pt based catalysts with a high metal loading for fuel cells’ applications still remains a big challenge. The three-dimensional (3D) graphene aerogel (GA) not only possess the intrinsic property of graphene, but also have abundant pore architecture for anchoring metal nanoparticles, thus would be suitable as metal catalysts’ support. This work reports a simple and mild one-step co-reduction synthesis of Pt nanoparticles highly loaded on 3D GA and the use as durable oxygen reduction catalyst. Both X-ray diffraction and TEM measurements confirm that Pt nanoparticles (ca. 60 wt.% Pt loading) with an average diameter of ca. 3.2 nm are uniformly decorated on the homogeneously interconnected pores of 3D GA even after a heat treatment at 300 °C. Such a Pt/GA catalyst exhibits significantly enhanced electrocatalytic activity and improved durability for the oxygen reduction reaction. The enhancement in both catalytic activity and durability may result from the unique 3-D architecture structure of GA, the uniform dispersion of Pt nanoparticles, and the interaction between the Pt nanoparticles and GA. The GA-supported Pt can serve as a highly active catalyst for fuel cell applications

Enhancing photocatalytic CO{sub 2} reduction by coating an ultrathin Al{sub 2}O{sub 3} layer on oxygen deficient TiO{sub 2} nanorods through atomic layer deposition

Energy Technology Data Exchange (ETDEWEB)

Zhao, Huilei; Chen, Jiatang; Rao, Guiying; Deng, Wei; Li, Ying, E-mail: yingli@tamu.edu

2017-05-15

Highlights: • Oxygen deficient TiO{sub 2} anatase nanorods are coated with an ultrathin Al{sub 2}O{sub 3} layer by ALD. • Exposed {100} facets and oxygen vacancies promote CO{sub 2} photoreduction to CO and CH{sub 4}. • Al{sub 2}O{sub 3} overlayer passivates surface states and mitigates surface charge recombination. • Two cycles of ALD coating lead to maximum photocatalytic CO{sub 2} reduction. • More than five cycles of ALD coating prohibits electron transfer to the surface. - Abstract: In this work, anatase nanorods (ANR) of TiO{sub 2} with active facet {100} as the major facet were successfully synthesized, and reducing the ANR by NaBH{sub 4} led to the formation of gray colored oxygen deficient TiO{sub 2-x} (ReANR). On the surface of ReANR, a thin layer of Al{sub 2}O{sub 3} was deposited using atomic layer deposition (ALD), and the thickness of Al{sub 2}O{sub 3} varied by the number of ALD cycles (1, 2, 5, 10, 50, 100, or 200). The growth rate of Al{sub 2}O{sub 3} was determined to be 0.25 Å per cycle based on high-resolution TEM analysis, and the XRD result showed the amorphous structure of Al{sub 2}O{sub 3}. All the synthesized photocatalysts (ANR, ReANR, and Al{sub 2}O{sub 3} coated ReANR) were tested for CO{sub 2} photocatalytic reduction in the presence of water vapor, with CO detected as the major reduction product and CH{sub 4} as the minor product. Compared with ANR, ReANR had more than 50% higher CO production and more than ten times higher CH{sub 4} production due to the oxygen vacancies that possibly enhanced CO{sub 2} adsorption and activation. By applying less than 5 cycles of ALD, the Al{sub 2}O{sub 3} coated ReANR had enhanced overall production of CO and CH{sub 4} than uncoated ReANR, with 2 cycles being the optimum, about 40% higher overall production than ReANR. Whereas, both CO and CH{sub 4} production decreased with increasing number of ALD cycles when more than 5 cycles were applied. Photoluminescence (PL) analysis showed an

Factors Controlling the Redox Activity of Oxygen in Perovskites: From Theory to Application for Catalytic Reactions

Directory of Open Access Journals (Sweden)

Chunzhen Yang

2017-05-01

Full Text Available Triggering the redox reaction of oxygens has become essential for the development of (electro catalytic properties of transition metal oxides, especially for perovskite materials that have been envisaged for a variety of applications such as the oxygen evolution or reduction reactions (OER and ORR, respectively, CO or hydrocarbons oxidation, NO reduction and others. While the formation of ligand hole for perovskites is well-known for solid state physicists and/or chemists and has been widely studied for the understanding of important electronic properties such as superconductivity, insulator-metal transitions, magnetoresistance, ferroelectrics, redox properties etc., oxygen electrocatalysis in aqueous media at low temperature barely scratches the surface of the concept of oxygen ions oxidation. In this review, we briefly explain the electronic structure of perovskite materials and go through a few important parameters such as the ionization potential, Madelung potential, and charge transfer energy that govern the oxidation of oxygen ions. We then describe the surface reactivity that can be induced by the redox activity of the oxygen network and the formation of highly reactive surface oxygen species before describing their participation in catalytic reactions and providing mechanistic insights and strategies for designing new (electro catalysts. Finally, we give a brief overview of the different techniques that can be employed to detect the formation of such transient oxygen species.

Optimization of Ru{sub x}Se{sub y} electrocatalyst loading for oxygen reduction in a PEMFC

Energy Technology Data Exchange (ETDEWEB)

Gonzalez-Huerta, R.G. [Instituto Politecnico Nacional, Laboratorio de Electroquimica y Corrosion ESIQIE, UPALP, 07738 Mexico, D.F., Mexico (Mexico); Guzman-Guzman, A.; Solorza-Feria, O. [Depto. Quimica, Centro de Investigacion y de Estudios Avanzados del IPN, A. Postal 14-740, 07360 Mexico D.F., Mexico (Mexico)

2010-11-15

The synthesis, characterization and optimization of Ru{sub x}Se{sub y} catalyst loading as a cathode electrode for a single polymer electrolyte membrane fuel cell, PEMFC were investigated. Ru{sub x}Se{sub y} catalyst was synthesized via a decarbonylation of Ru{sub 3}(CO){sub 12} and elemental selenium in 1,6-hexanediol under refluxing conditions for 2 h. The powder electrocatalyst was characterized by scanning electron microscopy (SEM), atomic force microscopy (AFM), and examined for the oxygen reduction reaction (ORR) in 0.5M H{sub 2}SO{sub 4} by rotating disk electrode (RDE) and in membrane-electrode assemblies, MEAs for a single PEMFC. Results indicate the formation of agglomerates of crystalline particles with nanometric size embedded in an amorphous phase. The catalyst exhibited high current density and lower overpotential for the ORR compared to that of Ru{sub x} cluster catalyst. Dispersed Ru{sub x}Se{sub y} catalyst loading on Vulcan carbon was optimized as a cathode electrode by performance testing in a single H{sub 2}-O{sub 2} fuel cell. (author)

Catalyst evaluation for oxygen reduction reaction in concentrated phosphoric acid at elevated temperatures

Science.gov (United States)

Hu, Yang; Jiang, Yiliang; Jensen, Jens Oluf; Cleemann, Lars N.; Li, Qingfeng

2018-01-01

Phosphoric acid is the common electrolyte for high-temperature polymer electrolyte fuel cells (HT-PEMFCs) that have advantages such as enhanced CO tolerance and simplified heat and water management. The currently used rotating disk electrode technique is limited to tests in dilute solutions at low temperatures and hence is not suitable for catalyst evaluation for HT-PEMFCs. In this study, we have designed and constructed a half-cell setup to measure the intrinsic activities of catalysts towards the oxygen reduction reaction (ORR) in conditions close to HT-PEMFC cathodes. By optimization of the hydrophobic characteristics of electrodes and the catalyst layer thickness, ORR activities of typical Pt/C catalysts are successfully measured in concentrated phosphoric acid at temperatures above 100 °C. In terms of mass-specific activities, the catalyst exhibits about two times higher activity in the half-cell electrode than that observed in fuel cells, indicating the feasibility of the technique as well as the potential for further improvement of fuel cell electrode performance.

Radiation chemistry of alternative fuel oxygenates - substituted ethers

International Nuclear Information System (INIS)

Mezyk, S. P.; Cooper, W. J.; Bartels, D. M.; Tobien, T.; O'Shea, K. E.

1999-01-01

The electron beam process, an advanced oxidation and reduction technology, is based in the field of radiation chemistry. Fundamental to the development of treatment processes is an understanding of the underlying chemistry. The authors have previously evaluated the bimolecular rate constants for the reactions of methyl tert-butyl ether (MTBE) and with this study have extended their studies to include ethyl tert-butyl ether (ETBE), di-isopropyl ether (DIPE) and tert-amyl methyl ether (TAME) with the hydroxyl radical, hydrogen atom and solvated electron using pulse radiolysis. For all of the oxygenates the reaction with the hydroxyl radical appears to be of primary interest in the destruction of the compounds in water. The rates with the solvated electron are limiting values as the rates appear to be relatively low. The hydrogen atom rate constants are relatively low, coupled with the low yield in radiolysis, they concluded that these are of little significance in the destruction of the alternative fuel oxygenates (and MTBE)

Nitric Oxide is Required for Homeostasis of Oxygen and Reactive Oxygen Species in Barley Roots under Aerobic Conditions

DEFF Research Database (Denmark)

Gupta, Kapuganti J; Hebelstrup, Kim; Kruger, Nicholas J

2014-01-01

Oxygen, the terminal electron acceptor for mitochondrial electron transport, is vital for plants because of its role in the production of ATP by oxidative phosphorylation. While photosynthetic oxygen production contributes to the oxygen supply in leaves, reducing the risk of oxygen limitation of ...... electron transport chain (Gupta et al., 2011). Thus, NO could influence oxygen consumption under normal aerobic conditions in roots, and it is this specific function that is assessed here.......Oxygen, the terminal electron acceptor for mitochondrial electron transport, is vital for plants because of its role in the production of ATP by oxidative phosphorylation. While photosynthetic oxygen production contributes to the oxygen supply in leaves, reducing the risk of oxygen limitation...

Highly regenerable carbon-Fe{sub 3}O{sub 4} core–satellite nanospheres as oxygen reduction electrocatalyst and magnetic adsorbent

Energy Technology Data Exchange (ETDEWEB)

Zhou, Wenqiang [Key Laboratory of Advanced Civil Engineering Materials of Ministry of Education, School of Materials Science and Engineering, and Institute for Advanced Study, Tongji University, Shanghai 201804 (China); School of Materials Science and Engineering, Jiangsu University of Science and Technology, Zhenjiang 212003 (China); Liu, Minmin; Cai, Chao [Key Laboratory of Advanced Civil Engineering Materials of Ministry of Education, School of Materials Science and Engineering, and Institute for Advanced Study, Tongji University, Shanghai 201804 (China); Zhou, Haijun, E-mail: zhouhaijun@just.edu.cn [School of Materials Science and Engineering, Jiangsu University of Science and Technology, Zhenjiang 212003 (China); Liu, Rui, E-mail: ruiliu@tongji.edu.cn [Key Laboratory of Advanced Civil Engineering Materials of Ministry of Education, School of Materials Science and Engineering, and Institute for Advanced Study, Tongji University, Shanghai 201804 (China)

2017-02-15

We present the synthesis and multifunctional utilization of core-satellite carbon-Fe{sub 3}O{sub 4} nanoparticles to serve as the enabling platform for a range of applications including oxygen reduction reaction (ORR) and magnetic adsorbent. Starting from polydopamine (PDA) nanoparticles and Fe(NO{sub 3}){sub 3}, carbon-Fe{sub 3}O{sub 4} core–satellite nanospheres are synthesized through successive steps of impregnation, ammoniation and carbonization. The synergistic combination of Fe{sub 3}O{sub 4} and N-doped carbon endows the nanocomposite with high electrochemical activity in ORR and mainly four electrons transferred in reaction process. Furthermore, carbon-Fe{sub 3}O{sub 4} nanoparticles used as magnetic adsorbent exhibit the efficient removal of Rhodamine B from an aqueous solution. The recovery and reuse of the adsorbent is demonstrated 5 times without any detectible loss in activity. - Graphical abstract: Starting from polydopamine (PDA) nanoparticles and Fe(NO{sub 3}){sub 3}, carbon-Fe{sub 3}O{sub 4} core–satellite nanospheres are synthesized through successive steps of impregnation, ammoniation and carbonization. The nanocomposites serve as the enabling platform for a range of applications including oxygen reduction reaction (ORR) and magnetic adsorbent. - Highlights: • Carbon-Fe{sub 3}O{sub 4} core–satellite nanospheres are synthesized through successive steps of impregnation, ammoniation and carbonization. • Polydopamine and Fe(NO{sub 3}){sub 3} are precursors for N-doped carbon source and Fe{sub 3}O{sub 4} nanoparticles, respectively. • The nanocomposites exhibit high electrochemical activity in ORR. • The nanocomposites effectively adsorb organic dyes with magnetic recovery and good recycle property.

Dissimilatory nitrate reduction by Aspergillus terreus isolated from the seasonal oxygen minimum zone in the Arabian Sea

DEFF Research Database (Denmark)

Stief, Peter; Fuchs-Ocklenburg, Silvia; Kamp, Anja

2014-01-01

Background: A wealth of microbial eukaryotes is adapted to life in oxygen-deficient marine environments. Evidence is accumulating that some of these eukaryotes survive anoxia by employing dissimilatory nitrate reduction, a strategy that otherwise is widespread in prokaryotes. Here, we report...... the dissimilatory nature of nitrate reduction. Interestingly, An-4 used intracellular nitrate stores (up to 6-8 μmol NO3 - g-1 protein) for dissimilatory nitrate reduction. Conclusions: Our findings expand the short list of microbial eukaryotes that store nitrate intracellularly and carry out dissimilatory nitrate...

Studies Of Oxidation And Thermal Reduction Of The Cu(100) Surface Using Positron Annihilation Induced Auger Electron Spectroscopy

Science.gov (United States)

Fazleev, N. G.; Nadesalingam, M. P.; Maddox, W.; Weiss, A. H.

2011-06-01

Positron annihilation induced Auger electron spectroscopy (PAES) measurements from the surface of an oxidized Cu(100) single crystal show a large increase in the intensity of the annihilation induced Cu M2,3VV Auger peak as the sample is subjected to a series of isochronal anneals in vacuum up to annealing temperature 300 °C. The PAES intensity then decreases monotonically as the annealing temperature is increased to ˜550 °C. Experimental positron annihilation probabilities with Cu 3p and O 1s core electrons are estimated from the measured intensities of the positron annihilation induced Cu M2,3VV and O KLL Auger transitions. PAES results are analyzed by performing calculations of positron surface states and annihilation probabilities of the surface-trapped positrons with relevant core electrons taking into account the charge redistribution at the surface and various surface structures associated with low and high oxygen coverages. The variations in atomic structure and chemical composition of the topmost layers of the oxidized Cu(100) surface are found to affect localization and spatial extent of the positron surface state wave function. The computed positron binding energy and annihilation characteristics reveal their sensitivity to charge transfer effects, atomic structure and chemical composition of the topmost layers of the oxidized Cu(100) surface. Theoretical positron annihilation probabilities with Cu 3p and O 1s core electrons computed for the oxidized Cu(100) surface are compared with experimental ones. The obtained results provide a demonstration of thermal reduction of the copper oxide surface after annealing at 300 °C followed by re-oxidation of the Cu(100) surface at higher annealing temperatures presumably due to diffusion of subsurface oxygen to the surface.

Studies Of Oxidation And Thermal Reduction Of The Cu(100) Surface Using Positron Annihilation Induced Auger Electron Spectroscopy

International Nuclear Information System (INIS)

Fazleev, N. G.; Nadesalingam, M. P.; Maddox, W.; Weiss, A. H.

2011-01-01

Positron annihilation induced Auger electron spectroscopy (PAES) measurements from the surface of an oxidized Cu(100) single crystal show a large increase in the intensity of the annihilation induced Cu M2,3VV Auger peak as the sample is subjected to a series of isochronal anneals in vacuum up to annealing temperature 300 deg. C. The PAES intensity then decreases monotonically as the annealing temperature is increased to ∼550 deg. C. Experimental positron annihilation probabilities with Cu 3p and O 1s core electrons are estimated from the measured intensities of the positron annihilation induced Cu M 2,3 VV and O KLL Auger transitions. PAES results are analyzed by performing calculations of positron surface states and annihilation probabilities of the surface-trapped positrons with relevant core electrons taking into account the charge redistribution at the surface and various surface structures associated with low and high oxygen coverages. The variations in atomic structure and chemical composition of the topmost layers of the oxidized Cu(100) surface are found to affect localization and spatial extent of the positron surface state wave function. The computed positron binding energy and annihilation characteristics reveal their sensitivity to charge transfer effects, atomic structure and chemical composition of the topmost layers of the oxidized Cu(100) surface. Theoretical positron annihilation probabilities with Cu 3p and O 1s core electrons computed for the oxidized Cu(100) surface are compared with experimental ones. The obtained results provide a demonstration of thermal reduction of the copper oxide surface after annealing at 300 deg. C followed by re-oxidation of the Cu(100) surface at higher annealing temperatures presumably due to diffusion of subsurface oxygen to the surface.