Polarographic studies on the nature of cadmium in scallop, oyster, and lobster

Energy Technology Data Exchange (ETDEWEB)

Chou, C L; Uthe, J F; Zook, E G

1978-04-01

Free and bound forms of cadmium were determined in raw shellfish by use of differential pulse polarography and atomic absorption spectrophotometry. Free cadmium is defined by its polarographic peak potential of -0.62 +- 0.02 V (saturated calomel electrode) in solvent washed ammonium sulfate extracts. Bound cadmium was determined by subtracting the free cadmium from the total cadmium present in the meat. Both scallop (various species) and American lobster (Homarus americanus) muscle tissues contain no free cadmium. Oyster (various species), on the other hand, had a considerable percentage (approximately 50%) of its total cadmium present as free cadmium, a phenomena as yet unexplained. The detection limit for free cadmium is approximately 0.05 ..mu..g/g raw tissue.

Variation of pHS value of mercury-dropping electrode layer in the process of molecular oxygen electro-reduction in polarographic determination of indium(3), cadmium(2), and thallium(1)

International Nuclear Information System (INIS)

Statsyuk, V.N.; Dergacheva, M.B.

1998-01-01

Quantitative evaluation of the pH S variation of an electrode layer in the process of molecular oxygen electroreduction in the indium(3), cadmium(2) and thallium(1) solutions by means of gallium introduction is carried out. the accomplished studied showed the possibility for determination of small amounts 10 -5 -10 -4 mole/l of indium at the background of the gallium concentrated solutions without removal of dissolved oxygen

Analysis of molybdenum, chromium, vanadium and iron by polarographic techniques

International Nuclear Information System (INIS)

Al-Zand, T.K.

1986-01-01

The application of direct current Tast polarograph, differential pulse polarography and phase-selective alternative current Tast polarography to the problem of determining molybdenum, chromium, vanadium and iron in various supporting electrolytes is reported. The effect of the supporting electrolyte on the wave/peak potential and sensitivity of the metal ion have been examined. The polarographic methods were applied for simultaneous determination of chromium (3)/chromium (6), vanadium (4), vanadium (5) and iron (2)/iron (3) in different supporting electrolytes

Molecular Orbital Principles of Oxygen-Redox Battery Electrodes.

Science.gov (United States)

Okubo, Masashi; Yamada, Atsuo

2017-10-25

Lithium-ion batteries are key energy-storage devices for a sustainable society. The most widely used positive electrode materials are LiMO 2 (M: transition metal), in which a redox reaction of M occurs in association with Li + (de)intercalation. Recent developments of Li-excess transition-metal oxides, which deliver a large capacity of more than 200 mAh/g using an extra redox reaction of oxygen, introduce new possibilities for designing higher energy density lithium-ion batteries. For better engineering using this fascinating new chemistry, it is necessary to achieve a full understanding of the reaction mechanism by gaining knowledge on the chemical state of oxygen. In this review, a summary of the recent advances in oxygen-redox battery electrodes is provided, followed by a systematic demonstration of the overall electronic structures based on molecular orbitals with a focus on the local coordination environment around oxygen. We show that a π-type molecular orbital plays an important role in stabilizing the oxidized oxygen that emerges upon the charging process. Molecular orbital principles are convenient for an atomic-level understanding of how reversible oxygen-redox reactions occur in bulk, providing a solid foundation toward improved oxygen-redox positive electrode materials for high energy-density batteries.

Polarographic study of Cd(II)-Schiff base complexes and d.m.e. menthanol-water medium

International Nuclear Information System (INIS)

Patel, M.S.; Trivedi, T.; Vyas, D.N.

1978-01-01

Three Schiff base complexes of Cd 2+ have been investigated polarographically in 60% menthanol-water medium at 26 0 C. The Schiff bases used are salicyladehyde tris buffer (ST), benzaldehydetris buffer (BT) and vanillin tris buffer (VT). Cd-ST and Cd-VT complexes produce reversible reduction wave at dme, while Cd-BT gives a quasi reversible wave. Stability constants of the complexes have been determined and the standard overall electrode reaction rate constant (ksub(e)sup(o)) B of the Cd-BT complex is determined by three different methods. The log β values of complexes are : Cd-ST, 2.72; Cd-VT, 4.90; and Cd-BT, 4.41. (author)

Electrode-electrolyte BIMEVOX system for moderate temperature oxygen separation

Energy Technology Data Exchange (ETDEWEB)

Boivin, J.C.; Pirovano, C.; Nowogrocki, G.; Mairesse, G. [Laboratoire de Cristallochimie et Physicochimie du Solide, URA CNRS 452, USTL-ENSCL BP 108, 59652 Villeneuve d`Ascq (France); Labrune, Ph.; Lagrange, G. [Centre de recherches Claude Delorme, Air Liquide, Jouy en Josas (France)

1998-12-01

Electrochemical separation of oxygen from air is a promising application for oxide conductor solid electrolytes. However, several important specifications are required in order to obtain an efficient separation device. First of all, the electrolyte material must exhibit a high conductivity at moderate temperature. From this point of view, a new family of materials called BIMEVOX ideally fulfils this condition. Secondly, a typical separation device must comport two electrodes on opposite faces of the electrolyte. These electrodes must act as electronic collectors but also, at the cathodic side, as an oxygen dissociation catalyst. BIMEVOX electrolytes exhibit ionic conductivity values that can allow work at temperature below 500C. The classical electrode approach, like in solid oxide fuel cells, consists in using a specific mixed oxide, for instance strontium lanthanum manganite or cobaltite. However, the lower the temperature, the lower the efficiency of these electrodes which quickly appears as the limiting factor. In previous work on bismuth lead oxide electrolytes, we proposed a new approach that consists of using the surface of the bismuth-based electrolyte itself as the catalyst, the electron collection being then performed by a co-sintered metallic grid. This `in-situ` electrode system provides many advantages, particularly it eliminates the problem of the chemical compatibility between electrode and electrolyte materials. Taking into account the presence of both catalytic vanadium and bismuth cations in BIMEVOX, we checked under these conditions the separation of oxygen from air for different electrolytes (BICOVOX, BICUVOX, BIZNVOX) at various temperatures in the range 430-600C. For instance, using a BICOVOX pellet with a gold grid inserted on each side makes it possible to separate oxygen with nearly 100% efficiency for current density values up to 1000 mA/cm{sup -2}. For higher intensity values, the faradic efficiency progressively but reversibly decreases

High performance methanol-oxygen fuel cell with hollow fiber electrode

Science.gov (United States)

Lawson, Daniel D. (Inventor); Ingham, John D. (Inventor)

1983-01-01

A methanol/air-oxygen fuel cell including an electrode formed by open-ended ion-exchange hollow fibers having a layer of catalyst deposited on the inner surface thereof and a first current collector in contact with the catalyst layer. A second current collector external of said fibers is provided which is immersed along with the hollow fiber electrode in an aqueous electrolyte body. Upon passage of air or oxygen through the hollow fiber electrode and introduction of methanol into the aqueous electrolyte, a steady current output is obtained. Two embodiments of the fuel cell are disclosed. In the first embodiment the second metal electrode is displaced away from the hollow fiber in the electrolyte body while in the second embodiment a spiral-wrap electrode is provided about the outer surface of the hollow fiber electrode.

Investigation of complexing equilibrium of polyacrylate-anion with cadmium ions by polarographic method

Energy Technology Data Exchange (ETDEWEB)

Avlyanov, Zh K; Kabanov, N M; Zezin, A B

1985-01-01

Polarographic investigation of cadmium complex with polyacrylate-anion in aqueous KCl solution is carried out. It is shown that the polarographic method allows one to define equilibrium constants of polymer metallic complex (PMC) formation even in the case when current magnitudes are defined by PMC dissociation reaction kinetic characteristics. The obtained equilibrium constants of stepped complexing provide the values of mean coordination PAAxCd complex number of approximately 1.5, that coincides with the value obtained by the potentiometric method.

Investigation of complexing equilibrium of polyacrylate-anion with cadmium ions by polarographic method

International Nuclear Information System (INIS)

Avlyanov, Zh.K.; Kabanov, N.M.; Zezin, A.B.

1985-01-01

Polarographic investigation of cadmium complex with polyacrylate-anion in aqueous KCl solution is carried out. It is shown that the polarographic method allows one to define equilibrium constants of polymer metallic complex (PMC) formation even in the case, when current magnitudes are defined by PMC dissociation reaction kinetic characteristics. The obtained equilibrium constants of stepped complexing provide the values of mean coordination PAAxCd complex number of approximately 1.5, that coinsides with the value obtained by the potentiometric method

Electrode reactions of iron oxide-hydroxide colloids.

Science.gov (United States)

Mahmoudi, Leila; Kissner, Reinhard

2014-11-07

Small-sized FeO(OH) colloids stabilised by sugars, commercially available for the clinical treatment of iron deficiency, show two waves during cathodic polarographic sweeps, or two current maxima with stationary electrodes, in neutral to slightly alkaline aqueous medium. Similar signals are observed with Fe(III) in alkaline media, pH > 12, containing citrate in excess. Voltammetric and polarographic responses reveal a strong influence of fast adsorption processes on gold and mercury. Visible spontaneous accumulation was also observed on platinum. The voltammetric signal at more positive potential is caused by Fe(III)→Fe(II) reduction, while the one at more negative potential has previously been assigned to Fe(II)→Fe(0) reduction. However, the involvement of adsorption phenomena leads us to the conclusion that the second cathodic current is caused again by Fe(III)→Fe(II), of species deeper inside the particles than those causing the first wave. This is further supported by X-ray photoelectron spectra obtained after FeO(OH) particle adsorption and reduction on a gold electrode surface. The same analysis suggests that sucrose stabilising the colloid is still bound to the adsorbed material, despite dilution and rinsing.

Using oxygen plasma treatment to improve the performance of electrodes for capacitive water deionization

International Nuclear Information System (INIS)

Hojati-Talemi, Pejman; Zou, Linda; Fabretto, Manrico; Short, Robert D.

2013-01-01

An oxygen plasma treatment was employed to modify the surface of carbon electrodes used in capacitive deionization (CDI). X-ray photoelectron spectroscopy analysis of samples showed that oxygen plasma is mainly attaching oxygenated groups on the PTFE binder used in these electrodes. By functionalizing the binder it can increase the hydrophilicity of the electrode surface and increase the available specific surface area. 2.5 min of plasma treatment resulted in the largest improvement of CDI performance of electrodes. Thermodynamic study of CDI performance showed that the modified electrodes followed Langmuir and Freundlich isotherms resulting from the increased interaction between the enhanced electrodes and water. The kinetic study showed that the CDI process followed a pseudo-first order adsorption kinetics. The calculated adsorption rate constants suggested that plasma modification can accelerate ion adsorption of electrodes

Composite Sr- and V-doped LaCrO3/YSZ sensor electrode operating at low oxygen levels

DEFF Research Database (Denmark)

Lund, Anders; Jacobsen, Torben; Hansen, Karin Vels

2012-01-01

A porous composite electrode of La0.8Sr0.2Cr0.97V0.03O3 -delta (LSCV) and yttria-stabilised zirconia (YSZ) was evaluated as a possible candidate for high-temperature potentiometric oxygen sensor measuring electrodes. The oxygen processes at the electrode were characterised by performing electroch....... The relatively low response time at 700º C at an oxygen partial pressure of around 5x10-6 bar and an inlet gas flow rate of 8 L h-1 makes the LSCV/YSZ electrode suitable for use as an potentiometric oxygen sensor electrodes.......A porous composite electrode of La0.8Sr0.2Cr0.97V0.03O3 -delta (LSCV) and yttria-stabilised zirconia (YSZ) was evaluated as a possible candidate for high-temperature potentiometric oxygen sensor measuring electrodes. The oxygen processes at the electrode were characterised by performing...... and 400 nm. At oxygen partial pressures around 0.2 bar at 700º C, the oxygen reaction is dominated by solid-state diffusion of oxide ions and surface reaction kinetics. At oxygen partial pressures around 10-5 bar above 800º C, gas phase mass transport processes dominate the impedance spectra...

Polarographic determination of the titanium and niobium content of zirconium alloys

International Nuclear Information System (INIS)

Levin, R; Gabra, J.

1978-03-01

A method is described for the polarographic determination of titanium and niobium in zirconium alloys in the concentration range of 0.1% to 4% of each of the determined metals. To assure the complete dissolution of the sample a mixture of nitric acid and hydrofluoric acid is used. After evaporating these acids in the presence of sulphuric acid, the contents are determined polarographically with a supporting electrolyte solution of 0.1M EDTA, 0.33M potassium sulfate and 0.4M sodium acetate, buffered to pH 4 with acetic acid. The half-wave potential (Esub(1/2)) of titanium is -0.35V and that of niobium is -0.67 V. (author)

Improved Internal Reference Oxygen Sensors with Composite Ceramic Electrodes

DEFF Research Database (Denmark)

Hu, Qiang; Jacobsen, Torben; Hansen, Karin Vels

2012-01-01

Potentiometric oxygen sensors with an internal reference electrode, which uses the equilibrium pO2 of the binary mixture of Ni/NiO as the reference, are demonstrated. The cells employ Pt or composite ceramics as the sensing electrode. The cells are fabricated by a flexible and potentially low cost...... and performance are highly reproducible. The composite ceramics, based on strontium doped manganite and yttria doped zirconia, are proven superior over Pt to serve as the electrode material....

Differential pulse polarographic determination of molybdenum (VI) in phosphoric medium by benzoin alpha oxime

International Nuclear Information System (INIS)

Chergouche, S.

1992-02-01

The extraction of Molybdenum (VI) using both 4-Methylpentane-2-one (hexone) and chloroform dissolved Benzoin-alpha-oxime has been investigated in order to develop a simple and sensitive polarographic method allowing the analysis of Molybdenum (VI) contained in industrial phosphoric acid produced in ANNABA (Eastern Algeria). The investigation takes into account various parameters such as: The stirring time, solvent rate, the number of stages ... as well as the organic phase conditioning during the polarographic analysis

Polarographic determination of ruthenium

International Nuclear Information System (INIS)

Li Jifu; Duan Shirong; Wu Xi

1989-01-01

It is suggested to use 0.5 mol/l HClO 4 -0.5 mol/l NaNO 3 -0.1 mol/l NaClO 4 as supporting electrolyte for determining ruthenium. In the supporting electrolyte there is a clear polarographic wave of ruthenium (IV) at -0.8 V vs. SCE. The wave height of ruthenium(IV) is linear in the range from 0.1 to 0.4 μg. ml -1 . The effect of the component of supporting electroylte and the other ion in the samples on the measurement of ruthenium are studied. The analysis methods for measuring ruthenium in both acidic or basic imitative radioactive waste solutions which is used in study of glass solidification are worked out. Imitative samples are analysised

Polarographic study of the electrochemical properties of plutonium; Etude polarographique des proprietes electrochimiques du plutonium

Energy Technology Data Exchange (ETDEWEB)

Guichard, C [Commissariat a l' Energie Atomique, Fontenay-aux-Roses (France). Centre d' Etudes Nucleaires

1968-07-01

The behaviour of the different degrees of oxidation of plutonium have been studied using a falling drop mercury electrode in a non-complexing medium: dilute perchloric acid. In this medium it is possible to carry out the polarographic determination of plutonium using the reduction step situated at - 0.54 V/ECS which corresponds to the passage from the degree of oxidation(V) to the degree(III). The modifications brought about by a complexing ion, acetate, are then observed and interpreted. The existence of two plutonium(IV) acetic complexes has been shown; one is a polymerized substance. (author) [French] Le comportement des differents degres d'oxydation du plutonium est etudie a l'electrode a gouttes de mercure dans un milieu non complexant: l'acide perchlorique dilue. Il est possible dans ce milieu d'effectuer le dosage polarographique du plutonium en utilisant la vague de reduction situee a - 0.54 V/ECS qui correspond au passage du degre d'oxydation(V) au degre(III). Les modifications apportees par un ion complexant, l'acetate, sont ensuite observees et interpretees. Deux complexes acetiques du plutonium(IV) ont ete mis en evidence, dont l'un est un compose polymerise. (auteur)

Perovskites as electrodes of solid cells in sensitive elements of oxygen ion

International Nuclear Information System (INIS)

Gandurska, J.; Sniezynska, I.; Marek, A.; Szwagierczak, D.; Kulawik, J.

1997-01-01

The perovskite family comprises many compounds used in electronic applications. In this work perovskite materials based on LaCrO 3 were investigated, destined for electrodes of solid electrolyte oxygen sensors. lanthanum chromite powders modified by calcium, strontium and aluminium were prepared by the coprecipitation-calcination technique. The powders were examined using thermal analysis, x-ray diffraction analysis, scanning electron microscopy and transmission electron microscopy. Introductory studies of electromotive force of oxygen cells with yttria stabilized zirconia as solid electrolyte and perovskite-based electrodes proved that it is possible to replace expensive Pt electrodes by much cheaper perovskite ones. (author)

System Li2O-MoO3 as a catalyst of oxygen (air) electrode

International Nuclear Information System (INIS)

Gavdzik, A.; Gajda, S.; Sofronkov, A.

2000-01-01

Potential of electrode on the basis of system Li x Mo 2-x O 6 (x 0.1-0.5) in alkaline solution saturated by oxygen was studied by the method of polarization curves recording. It is ascertained that the value of stationary potential characteristic of the electrode described under the conditions mentioned is determined by reversible reaction between oxygen and water molecules, resulting in formation of hydroxyl and hydrogen peroxide anions. Practicability of using the solid solutions on the basis of molybdenum oxide with additions of lithium oxide as a catalyst of oxygen (air) electrode in electrochemical current sources is demonstrated [ru

Tumour oxygenation assessed by 18F-fluoromisonidazole PET and polarographic needle electrodes in human soft tissue tumours

DEFF Research Database (Denmark)

Bentzen, L.; Keiding, S.; Nordsmark, M.

2003-01-01

Background and purpose: The aim of the study was to identify hypoxia in human soft tissue sarcomas (STS) by PET scanning using the hypoxia marker [F-18]-fluoromisonidazole ([F-18]FMISO) and invasive oxygen sensitive probes (Eppendorf pO(2) Histograph, Germany). Materials and methods: Thirteen pat...

Polarographic methods for the analysis of beryllium metal and its alloys

International Nuclear Information System (INIS)

Wells, J.M.

1975-10-01

This report describes polarographic methods for the analysis of beryllium metal and its alloys. The elements covered by these methods are aluminium, bismuth, cadmium, cobalt, copper, iron, lead, molybdenum, nickel, thallium, tungsten, uranium, vanadium and zinc. (author)

New Hypothesis for SOFC Ceramic Oxygen Electrode Mechanisms

DEFF Research Database (Denmark)

Mogensen, Mogens Bjerg; Chatzichristodoulou, Christodoulos; Graves, Christopher R.

2016-01-01

A new hypothesis for the electrochemical reaction mechanism in solid oxide cell ceramic oxygen electrodes is proposed based on literature including our own results. The hypothesis postulates that the observed thin layers of SrO-La2O3 on top of ceramic perovskite and other Ruddlesden-Popper...

High performance electrode for electrochemical oxygen generator cell based on solid electrolyte ion transport membrane

Energy Technology Data Exchange (ETDEWEB)

Zhou, Wei; Shao, Zongping; Ran, Ran; Chen, Zhihao; Zeng, Pingying; Gu, Hongxia; Jin, Wanqin; Xu, Nanping [College of Chemistry and Chemical Engineering, Nanjing University of Technology, No. 5 Xin Mofan Road, Nanjing 210009, JiangSu (China)

2007-06-30

A double-layer composite electrode based on Ba{sub 0.5}Sr{sub 0.5}Co{sub 0.8}Fe{sub 0.2}O{sub 3-{delta}} + Sm{sub 0.2}Ce{sub 0.8}O{sub 1.9} (BSCF + SDC) and BSCF + SDC + Ag was investigated to be a promising cathode and also anode for the electrochemical oxygen generator based on samaria doped ceria electrolyte. The Ag particles in the second layer were not only the current collector but also the improver for the oxygen adsorption at the electrode. a.c. impedance results indicated that the electrode polarization resistance, as low as 0.0058 {omega} cm{sup 2} was reached at 800 C under air. In oxygen generator cell performance test, the electrode resistance dropped to half of the value at zero current density under an applied current density of 2.34 A cm{sup -2} at 700 C, and on the same conditions the oxygen generator cell was continual working for more than 900 min with a Faradic efficiency of {proportional_to}100%. (author)

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.

The effect of loading and particle size on the oxygen reaction in CGO impregnated Pt electrodes

DEFF Research Database (Denmark)

Lund, Anders; Hansen, Karin Vels; Jacobsen, Torben

2012-01-01

Porous platinum electrodes impregnated with Gd x Ce1−x O2−δ (CGO) are investigated to characterise how nano-sized CGO grains affect the oxygen reaction. Impedance measurements were performed at temperatures between 450 and 750 °C and at oxygen partial pressures of 0.2 and 5 × 10−5 bar for electro......Porous platinum electrodes impregnated with Gd x Ce1−x O2−δ (CGO) are investigated to characterise how nano-sized CGO grains affect the oxygen reaction. Impedance measurements were performed at temperatures between 450 and 750 °C and at oxygen partial pressures of 0.2 and 5 × 10−5 bar...... for electrodes with various CGO loadings and electrodes annealed at various temperatures. The morphology was characterised by scanning electron microscopy and the CGO grain size was determined from X-ray diffraction peak broadening. The results showed that the polarisation resistance decreased with increasing...

Oxygen-deficient hematite nanorods as high-performance and novel negative electrodes for flexible asymmetric supercapacitors.

Science.gov (United States)

Lu, Xihong; Zeng, Yinxiang; Yu, Minghao; Zhai, Teng; Liang, Chaolun; Xie, Shilei; Balogun, Muhammad-Sadeeq; Tong, Yexiang

2014-05-21

Oxygen-deficient α-Fe2 O3 nanorods with outstanding capacitive performance are developed and demonstrated as novel negative electrodes for flexible asymmetric supercapacitors. The asymmetric-supercapacitor device based on the oxygen-deficient α-Fe2 O3 nanorod negative electrode and a MnO2 positive electrode achieves a maximum energy density of 0.41 mW·h/cm(3) ; it is also capable of charging a mobile phone and powering a light-emitting diode indicator. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Optic nerve pH and PO2

DEFF Research Database (Denmark)

Pedersen, Daniella B; Stefánsson, Einar; Kiilgaard, Jens Folke

2006-01-01

Earlier studies have demonstrated that carbonic anhydrase inhibitors (CAIs) increase optic nerve oxygen tension (ONPO(2)) in pigs. We hypothesized that the mechanism of this effect was either a CO(2) increase or a pH decrease in tissue and blood. To test this hypothesis we investigated and compared...... how optic nerve pH (ONpH) and ONPO(2) are affected by: (1) carbonic anhydrase inhibition; (2) respiratory acidosis, and (3) metabolic acidosis. We measured ONpH with a glass pH electrode and ONPO(2) with a polarographic oxygen electrode. One of the electrodes was placed in the vitreous cavity 0.5 mm...

Fluctuations in pO2 in poorly and well-oxygenated spontaneous canine tumors before and during fractionated radiation therapy.

Science.gov (United States)

Brurberg, Kjetil G; Skogmo, Hege K; Graff, Bjørn A; Olsen, Dag R; Rofstad, Einar K

2005-11-01

The spatial heterogeneity in oxygen tension (pO2) in tumor tissue has been studied extensively, whereas, the information about the temporal heterogeneity is sparse. The purpose of the present study was to search for pO2 fluctuations in untreated and irradiated spontaneous canine tumors, and to investigate whether there is a relationship between overall tumor oxygenation status and pO2 fluctuation pattern. Six dogs scheduled for radiation therapy of head and neck cancer were included in the study. The primary tumors were irradiated with 18 fractions of 3 Gy. Eppendorf polarographic electrodes and OxyLite fluorescence probes were used to measure overall oxygenation status and pO2 fluctuation pattern, respectively. Tissue pO2 was recorded at three subsequent days prior to treatment, and immediately before radiation fraction 4, 7, and 10. Overall oxygenation status differed substantially among the tumors. Radiation therapy had no consistent effect on overall oxygenation status. Fluctuations in pO2 were detected in untreated as well as irradiated tumors, and independent of whether the tumors were poorly or well oxygenated. Fluctuations in pO2 can occur in untreated and irradiated spontaneous canine tumors. There is no correlation between pO2 fluctuation pattern and overall tumor oxygenation status.

Microfabricated Collector-Generator Electrode Sensor for Measuring Absolute pH and Oxygen Concentrations.

Science.gov (United States)

Dengler, Adam K; Wightman, R Mark; McCarty, Gregory S

2015-10-20

Fast-scan cyclic voltammetry (FSCV) has attracted attention for studying in vivo neurotransmission due to its subsecond temporal resolution, selectivity, and sensitivity. Traditional FSCV measurements use background subtraction to isolate changes in the local electrochemical environment, providing detailed information on fluctuations in the concentration of electroactive species. This background subtraction removes information about constant or slowly changing concentrations. However, determination of background concentrations is still important for understanding functioning brain tissue. For example, neural activity is known to consume oxygen and produce carbon dioxide which affects local levels of oxygen and pH. Here, we present a microfabricated microelectrode array which uses FSCV to detect the absolute levels of oxygen and pH in vitro. The sensor is a collector-generator electrode array with carbon microelectrodes spaced 5 μm apart. In this work, a periodic potential step is applied at the generator producing transient local changes in the electrochemical environment. The collector electrode continuously performs FSCV enabling these induced changes in concentration to be recorded with the sensitivity and selectivity of FSCV. A negative potential step applied at the generator produces a transient local pH shift at the collector. The generator-induced pH signal is detected using FSCV at the collector and correlated to absolute solution pH by postcalibration of the anodic peak position. In addition, in oxygenated solutions a negative potential step at the generator produces hydrogen peroxide by reducing oxygen. Hydrogen peroxide is detected with FSCV at the collector electrode, and the magnitude of the oxidative peak is proportional to absolute oxygen concentrations. Oxygen interference on the pH signal is minimal and can be accounted for with a postcalibration.

Oxygenation of spontaneous canine tumors during fractionated radiation therapy

International Nuclear Information System (INIS)

Achermann, R.E.; Ohlerth, S.M.; Bley, C.R.; Inteeworn, N.; Schaerz, M.; Wergin, M.C.; Kaser-Hotz, B.; Gassmann, M.; Roos, M.

2004-01-01

Background and purpose: tumor oxygenation predicts treatment outcome, and reoxygenation is considered important in the efficacy of fractionated radiation therapy. Therefore, the purpose of this study was to document the changes of the oxygenation status in spontaneous canine tumors during fractionated radiation therapy using polarographic needle electrodes. Material and methods: tumor oxygen partial pressure (pO 2 ) measurements were performed with the eppendorf-pO 2 -Histograph. The measurements were done under general anesthesia, and probe tracks were guided with ultrasound. pO 2 was measured before radiation therapy in all dogs. In patients treated with curative intent, measurements were done sequentially up to eight times (total dose: 45-59.5 Gy). Oxygenation status of the palliative patient group was examined before each fraction of radiation therapy up to five times (total dose: 24-30 Gy). Results: 15/26 tumors had a pretreatment median pO 2 ≤ 10 mmHg. The pO 2 values appeared to be quite variable in individual tumors during fractionated radiation therapy. The pO 2 of initially hypoxic tumors (pretreatment median pO 2 ≤ 10 mmHg) remained unchanged during fractionated radiotherapy, whereas in initially normoxic tumors the pO 2 decreased. Conclusion: hypoxia is common in spontaneous canine tumors, as 57.7% of the recorded values were ≥ 10 mmHg. The data of this study showed that initially hypoxic tumors remained hypoxic, whereas normoxic tumors became more hypoxic. (orig.)

Polarographic, spectrophotometric and coulometric studies of MoO=4 in H2SO4

International Nuclear Information System (INIS)

Tokoro, R.; Bertotti, M.

1990-01-01

This study characterizes the polarographic process of Mo O sup(=) sub(4) in H sub(2)SO sub(4) medium, determining which species is responsible by catalytic cycle. Spectrophotometric and coulometric studies are also described. (author)

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.

Electrocatalysis of oxygen reduction on nitrogen-containing multi-walled carbon nanotube modified glassy carbon electrodes

International Nuclear Information System (INIS)

Vikkisk, Merilin; Kruusenberg, Ivar; Joost, Urmas; Shulga, Eugene; Tammeveski, Kaido

2013-01-01

Highlights: ► Pyrolysis in the presence of urea was used for nitrogen doping of carbon nanotubes. ► N-doped carbon nanotubes were used as catalysts for the oxygen reduction reaction. ► N-doped carbon material showed a high catalytic activity for ORR in alkaline media. ► N-containing CNT material is an attractive cathode catalyst for alkaline membrane fuel cells. - Abstract: The electrochemical reduction of oxygen was studied on nitrogen-doped multi-walled carbon nanotube (NCNT) modified glassy carbon (GC) electrodes employing the rotating disk electrode (RDE) method. Nitrogen doping was achieved by simple pyrolysis of the carbon nanotube material in the presence of urea. The surface morphology and composition of the NCNT samples were investigated by scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). The SEM images revealed a rather uniform distribution of NCNTs on the GC electrode substrate. The XPS analysis showed a successful doping of carbon nanotubes with nitrogen species. The RDE results revealed that in alkaline solution the N-doped nanotube materials showed a remarkable electrocatalytic activity towards oxygen reduction. At low overpotentials the reduction of oxygen followed a two-electron pathway on undoped carbon nanotube modified GC electrodes, whereas on NCNT/GC electrodes a four-electron pathway of O 2 reduction predominated. The results obtained are significant for the development of nitrogen-doped carbon-based cathodes for alkaline membrane fuel cells.

Simultaneous polarographic determination of micro amounts of vanadium(V) and molybdenum(VI)

International Nuclear Information System (INIS)

Rao, V.S.N.; Rao, S.B.

1979-01-01

A simple and sensitive polarographic method has been developed for the determination of micro quantities of vanadium(V) and molybdenum(VI), based on the reduction of bromate, which is catalysed by these metal ions in the presence of 2,4-dihydroxyacetophenone oxime. Interference by various cations and anions has been investigated. (author)

Influence of the oxygen electrode and inter-diffusion barrier on the degradation of solid oxide electrolysis cells

DEFF Research Database (Denmark)

Hjalmarsson, Per; Sun, Xiufu; Liu, Yi-Lin

2013-01-01

-diffusion barrier sandwiched between the YSZ electrolyte and an LSCF:CGO oxygen electrode. Impedance Spectroscopy was used during the tests to diagnose the change in electrochemical response of the different components of the SOECs. The results showed a significantly lower degradation rate for the cell with an LSCF......Two Solid Oxide Electrolysis Cells (SOECs) with different oxygen electrodes have been tested in galvanostatic tests carried out at −1.5 Acm−2 and 800 °C converting 60% of a 50:50% mixture of H2O and CO2 (co-electrolysis). One of the cells had an LSM:YSZ oxygen electrode. The other had an CGO inter...

Optic nerve pH and PO2

DEFF Research Database (Denmark)

Pedersen, Daniella B; Stefánsson, Einar; Kiilgaard, Jens Folke

2006-01-01

Earlier studies have demonstrated that carbonic anhydrase inhibitors (CAIs) increase optic nerve oxygen tension (ONPO(2)) in pigs. We hypothesized that the mechanism of this effect was either a CO(2) increase or a pH decrease in tissue and blood. To test this hypothesis we investigated and compared...... how optic nerve pH (ONpH) and ONPO(2) are affected by: (1) carbonic anhydrase inhibition; (2) respiratory acidosis, and (3) metabolic acidosis. We measured ONpH with a glass pH electrode and ONPO(2) with a polarographic oxygen electrode. One of the electrodes was placed in the vitreous cavity 0.5 mm...... over the optic nerve in the eyes of domestic pigs....

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.

Electrochemical Reduction of Oxygen on Anthraquinone/Carbon Nanotubes Nanohybrid Modified Glassy Carbon Electrode in Neutral Medium

Directory of Open Access Journals (Sweden)

Zheng Gong

2013-01-01

Full Text Available The electrochemical behaviors of monohydroxy-anthraquinone/multiwall carbon nanotubes (MHAQ/MWCNTs nanohybrid modified glassy carbon (MHAQ/MWCNTs/GC electrodes in neutral medium were investigated; also reported was their application in the electrocatalysis of oxygen reduction reaction (ORR. The resulting MHAQ/MWCNTs nanohybrid was characterized by scanning electron microscope (SEM and transmission electron microscope (TEM. It was found that the ORR at the MHAQ/MWCNTs/GC electrode occurs irreversibly at a potential about 214 mV less negative than at a bare GC electrode in pH 7.0 buffer solution. Cyclic voltammetric and rotating disk electrode (RDE techniques indicated that the MHAQ/MWCNTs nanohybrid has high electrocatalytic activity for the two-electron reduction of oxygen in the studied potential range. The kinetic parameters of ORR at the MHAQ/MWCNTs nanohybrid modified GC electrode were also determined by RDE and EIS techniques.

Reduction of skin damage from transcutaneous oxygen electrodes using a spray on dressing.

Science.gov (United States)

Evans, N J; Rutter, N

1986-09-01

A spray on, copolymer acrylic dressing (Op-Site) was used to limit the skin damage caused by a transcutaneous oxygen electrode and its adhesive ring. Two identical electrodes were applied to the abdominal skin of 10 preterm infants, one on untreated skin, the other after application of Op-Site. It was found that Op-Site prevented the epidermal damage (as measured by transepidermal water loss) that occurs when the adhesive ring is removed from untreated skin. It did not interfere with transcutaneous oxygen measurements; absolute values and response times were unchanged. Op-Site is therefore useful in preventing the skin trauma that occurs when transcutaneous oxygen monitoring is being performed in preterm infants below 30 weeks' gestation in the first week of life. Care must be taken, however, to prevent a build up of Op-Site--it should be applied as a single layer, allowed to dry, and removed after use.

The relationship between tumor oxygenation and cell proliferation in human soft tissue sarcomas

International Nuclear Information System (INIS)

Nordsmark, Marianne; Hoeyer, Morten; Keller, Johnny; Nielsen, Ole Steen; Jensen, Oluf Myhre; Overgaard, Jens

1996-01-01

Purpose: In malignant tumors the oxygenation status and tumor cell proliferation are known to influence local tumor control after radiotherapy. However, the relationship between oxygenation status and tumor cell kinetics in human tumors has not yet been described. Newly developed clinically applicable techniques such as oxygen electrode measurements and assessment of tumor cell proliferation rates have been suggested as promising predictive assays. The purpose of the present study was to characterize tumor oxygenation status in soft tissue sarcomas and to compare this with tumor cell kinetics and clinical parameters. Methods and Materials: Pretreatment tumor oxygenation status was measured by polarographic oxygen needle electrodes and evaluated as the median pO 2 and the percentage of pO 2 values ≤ 5 mmHg and ≤ 2.5 mmHg in 22 patients with primary soft tissue sarcomas. All tumors were characterized by histology, grade of malignancy, the level of microscopic necrosis, the level of effective hemoglobin, and magnetic resonance imaging estimation of tumor volume. The tumor cell potential doubling time and labeling index were measured by flow cytometric and immunohistochemical analysis of tumor biopsy specimens after in vivo incorporation of iododeoxyuridine. Results: There was a significant correlation between the median pO 2 and the tumor cell potential doubling time (p = 0.041), whereas no correlation was found between the level of hypoxia expressed by the percentage of pO 2 values ≤ 2.5 and ≤ 5 mmHg, respectively, and tumor cell potential doubling time. Furthermore, no correlation was found between either of the three tumor oxygenation parameters and labeling index. The material represented large intertumor heterogeneity in oxygenation status, cell kinetics, and tumor volume, and no correlation was found between oxygenation status and either volume, histopathology, grade of malignancy, or effective hemoglobin. Conclusion: This report is the first to suggest

Polarographic determination of trace amounts of thorium

Energy Technology Data Exchange (ETDEWEB)

Zaofan Zhao; Xiaohua Cai; Peibiao Li; Handong Yang

1986-07-01

A sensitive linear-sweep polarographic method for the determination of thorium is described. It is based on the thorium complex with Xylidyl Blue I (XBI) in a medium containing ethylenediamine, 1, 10-phenanthroline, oxalic acid and ninhydrin, at pH 10.5-11.5. The complex has been proved to be Th(XBI)/sub 2/, with log ..beta..'=9.6. The method can be used to determine trace amounts of thorium over the range 3.5x10/sup -8/-3x10/sup -6/M. The detection limit is 1x10/sup -8/M. A solvent extraction procedure is necessary to eliminate interference from several cations. The method has been applied to determination of traces of thorium in minerals, with good results.

Communications: Elementary oxygen electrode reactions in the aprotic Li-air battery

DEFF Research Database (Denmark)

Hummelshøj, Jens Strabo; Blomquist, Jakob; Datta, Soumendu

2010-01-01

We discuss the electrochemical reactions at the oxygen electrode of an aprotic Li-air battery. Using density functional theory to estimate the free energy of intermediates during the discharge and charge of the battery, we introduce a reaction free energy diagram and identify possible origins...

Linear sweep polarographic determination of nucleic acids using acridine orange as a bioprobe

Directory of Open Access Journals (Sweden)

WEI SUN

2007-11-01

Full Text Available The interaction of acridine orange (AO with double-stranded (ds DNA in aqueous solution was investigated by linear sweep polarography (LSP on a dropping mercury working electrode (DME. In pH 2.5 Britton–Robinson (B–R buffer solution, AO had a sensitive linear sweep polarographic reductive peak at –0.89 V (vs. SCE, which could be greatly inhibited by the addition of dsDNA, with a positive shift of the peak potential. Based on the decrease of the reductive peak current, a new quantitative electrochemical determination method for dsDNA was developed with a linear range of 2.0−20.0 mg l-1 and the linear regression equation: ΔIp” (nA = 111.90 C (mg l-1+125.32 (n = 9, γ = 0.997. The influences of commonly co-existing substances, such as metal ions, amino acid, etc., on the determination were also investigated. The method is sensitive, rapid and simple with good selectivity. The new proposed method was further applied to the detection of RNA and three synthetic samples containing dsDNA with satisfactory results. The binding number and the equilibrium constant between dsDNA and AO were calculated by an electrochemical method.

Dosing of traces of oxygenated water by polarography

International Nuclear Information System (INIS)

Faure, A.M.; Malterre, J.

1960-01-01

As dosing oxygenated water by using polarography has been envisaged within the framework of water purity controls for the Melusine pile, the objective of the authors is here to see whether the polarographic method could be satisfying for routine analyses, and would result in a higher dosing sensitivity. They describe the polarography principle, indicate devices which are used, specify and comment conditions under which polarography is performed [fr

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

Improvement of Electrochemical Properties of Lithium–Oxygen Batteries Using a Silver Electrode

Energy Technology Data Exchange (ETDEWEB)

Park, Jin-Bum; Luo, Xiangyi; Lu, Jun; Shin, Chang Dae; Yoon, Chong Seung; Amine, Khalil; Sun, Yang-Kook

2015-07-09

Silver (Ag) electrodes are prepared by an electrodeposition method at -0.25 V versus SCE. To evaluate the effect of particle size on Li–air cells, deposition times are 3, 10, 30, and 300 s. When cycled at a current density of 0.032 mA cm–2, the Ag-deposited electrode for 300 s shows very low polarization corresponding to the oxygen evolution reaction potential at 3.6 V. X-ray diffraction studies confirm that the main discharge product is Li2O2, and the results of scanning electron microscopy and transmission electron microscopy of the discharged electrodes show lithium peroxides at different positions due to the limitation of active sites on silver particles.

Surface oxygenation of polypropylene using an air dielectric barrier discharge: the effect of different electrode-platen combinations

International Nuclear Information System (INIS)

Upadhyay, D.J.; Cui, N.-Y.; Anderson, C.A.; Brown, N.M.D.

2004-01-01

Polypropylene film has been modified in an air dielectric barrier discharge using two different electrode-platen configurations: stainless steel wire electrode-rubber platen or ceramic electrode-aluminium platen combinations. Modified films were characterised by static contact angle measurements, X-ray photoelectron spectroscopy (XPS), secondary ion mass spectrometry (SIMS) and Fourier transform infrared spectroscopy (ATR-FT-IR). Surface hydrophilic modification appears to be governed by the presence of low-molecular weight oxidised functionalities using XPS and SIMS techniques. Irrespective of the type of electrode-platen combination used to obtain the discharge, oxygenated functionalities of identical nature are formed on the polymer surface. However, the degree of oxidation obtained by the discharge using the wire electrodes with the rubber platen was considerably greater. Further increase in the observed hydrophilicity due to molecular rearrangement and development of stable oxygenated functionalities was evident after 1 month of post-processing analysis

The electrode kinetics of the evolution and dissolution of oxygen at the urania-zirconia interfaces

International Nuclear Information System (INIS)

Badwal, S.P.S.; Bevan, D.J.M.; Bockris, J.O'M.

1980-01-01

In order to assess the potential of urania-yttria fluorite-type solid solutions as electrodes for high-temperature electrolysis of steam, oxygen evolution and dissolution reactions have been studied at the (Usub(0.7)Ysub(0.3))Osub (2+x)/YSZ interface. A current-interruption technique was used to separate overpotential and resistive potential drop. In oxygen and air the overpotential-current curves obey the Tafel law, suggesting that a charge-transfer process is rate determining. Activation energies of 120 kJ mole -1 and 165 kJ mole -1 were obtained for the cathodic reaction in oxygen and air respectively. The capacitance obtained from galvanostatic transients varied with potential, temperature, and oxygen partial pressure. The average value of n, the number of electrons involved in the overall charge-transfer reaction, was determined to be 4.01 from reversible potential measurements. The overpotential losses are small for porous electrodes at high psub(O 2 ). A mechanism for the oxygen transfer reaction has been proposed and its limitations discussed. (author)

Electrochemical reduction of oxygen on gold and boron-doped diamond electrodes in ambient temperature, molten acetamide-urea-ammonium nitrate eutectic melt

International Nuclear Information System (INIS)

Dilimon, V.S.; Venkata Narayanan, N.S.; Sampath, S.

2010-01-01

The electrochemical reduction of oxygen has been studied on gold, boron-doped diamond (BDD) and glassy carbon (GC) electrodes in a ternary eutectic mixture of acetamide (CH 3 CONH 2 ), urea (NH 2 CONH 2 ) and ammonium nitrate (NH 4 NO 3 ). Cyclic voltammetry (CV), differential pulse voltammetry (DPV), chronoamperometry and rotating disk electrode (RDE) voltammetry techniques have been employed to follow oxygen reduction reaction (ORR). The mechanism for the electrochemical reduction of oxygen on polycrystalline gold involves 2-step, 2-electron pathways of O 2 to H 2 O 2 and further reduction of H 2 O 2 to H 2 O. The first 2-electron reduction of O 2 to H 2 O 2 passes through superoxide intermediate by 1-electron reduction of oxygen. Kinetic results suggest that the initial 1-electron reduction of oxygen to HO 2 is the rate-determining step of ORR on gold surfaces. The chronoamperometric and RDE studies show a potential dependent change in the number of electrons on gold electrode. The oxygen reduction reaction on boron-doped diamond (BDD) seems to proceed via a direct 4-electron process. The reduction of oxygen on the glassy carbon (GC) electrode is a single step, irreversible, diffusion limited 2-electron reduction process to peroxide.

Reduction of skin damage from transcutaneous oxygen electrodes using a spray on dressing.

OpenAIRE

Evans, N J; Rutter, N

1986-01-01

A spray on, copolymer acrylic dressing (Op-Site) was used to limit the skin damage caused by a transcutaneous oxygen electrode and its adhesive ring. Two identical electrodes were applied to the abdominal skin of 10 preterm infants, one on untreated skin, the other after application of Op-Site. It was found that Op-Site prevented the epidermal damage (as measured by transepidermal water loss) that occurs when the adhesive ring is removed from untreated skin. It did not interfere with transcut...

Polarographic investigation of complexing kinetics of polyacrylate anions with cadmium ions

International Nuclear Information System (INIS)

Avlyanov, Zh.K.; Kabanov, N.M.; Zezin, A.B.; Askarov, M.A.

1990-01-01

The processes which occur during the reduction of cadmium ions from polymer-metallic complexes (PMC) are studied for the purposes of polarographic investigation of complexing kinetics of polyacrylate anions (PAA) of different molecular masses with cadmium ions in KCl aqueous solutions. An expression is derived for establishing semiwave potential. PMC formation and dissociation reduction rate constants are calculated. It is shown that intramolecular reorderings required for the formation of a two-coordinate complex proceed much slower as compared to the diffusion of free ions

Improved Internal Reference Oxygen Sensors Using Composite Oxides as Electrodes

DEFF Research Database (Denmark)

Hu, Qiang

The thesis describes the research on and development of an internal reference oxygen sensor (IROS). The IROS is potentiometric and uses the equilibrium pO2of the binary mixture of Ni/NiO as the reference pO2. The sensing electrode of the IROS are made from metallic Pt or the composite of (La0.75S...... the application of IROSes are provided. Based on the concepts and fundamentals of the IROS, internal reference sensors that detect other gas species such as hydrogen, chlorine and bromine may be developed.......The thesis describes the research on and development of an internal reference oxygen sensor (IROS). The IROS is potentiometric and uses the equilibrium pO2of the binary mixture of Ni/NiO as the reference pO2. The sensing electrode of the IROS are made from metallic Pt or the composite of (La0.75Sr0...... from 8YSZ is evaluated quantitatively and figures that may be used to design the depletion period of an IROS due to the electronic leak of 8YSZ are provided. One dimensional numerical simulations are performed to study the variation in cell voltage during the process of gas mixing, and the asymmetric...

Stability and Performance of Oxygen Electrodes for Reversible Solid Oxide Cells

Science.gov (United States)

Railsback, Justin Gary

Worldwide, governments are beginning to take action to reduce anthropogenic CO2 emissions in order to mitigate the extent of global climate change. The largest fraction of global CO2 emission comes from electrical power generation, which is rapidly being converted to wind and solar installations. The intermittent nature of renewable resources requires that large scale energy storage be implemented to ensure grid stability. Pumped hydro storage is currently the only technology available for large scale energy storage; however, pumped hydro remains geographically confined and susceptible to seasonal fluctuations and offers limited discharge hours. Recent system level models predict that reversible solid oxide cells may be a competitive solution, but two key advancements are required to realize the technology: low cell resistance (cell resistance, and when a cell is operated in electrolysis the oxygen electrode is known to degrade quickly. This work focuses on both aspects of the oxygen electrode. A Pr2NiO4 based electrode is developed that has improved phase stability and good polarization resistance ( 0.1 O•cm2 at 650 °C). The electrode is prepared by wet chemical impregnation (infiltration) of Pr2NiO4 precursors into a La0.9Sr 0.1Ga0.8Mg0.2O3 scaffold. Electrochemical data for a number cells is presented and the number of infiltrations is optimized. Preliminary life tests and x-ray data are presented. Pressurization of the oxygen electrode is predicted to decrease its polarization resistance and pressurization of the reversible solid oxide cell system is desirable to achieve high round-trip efficiency. The electrochemical performance of mixed electronic-ionic conducting electrodes has not been reported above 1 atm. Four candidate electrodes are examined under pressurization up to 10 atm: Pr2NiO4 infiltrated La0.9Sr0.1 Ga0.8Mg0.2O3, Sm0.5Sr 0.5CoO3 infiltrated Ce0.9Gd0.1O 2, single phase La0.6Sr0.4Co0.2Fe 0.8O3, and single phase Nd2NiO4. The role of the ion

One-dimensional model of oxygen transport impedance accounting for convection perpendicular to the electrode

Energy Technology Data Exchange (ETDEWEB)

Mainka, J. [Laboratorio Nacional de Computacao Cientifica (LNCC), CMC 6097, Av. Getulio Vargas 333, 25651-075 Petropolis, RJ, Caixa Postal 95113 (Brazil); Maranzana, G.; Thomas, A.; Dillet, J.; Didierjean, S.; Lottin, O. [Laboratoire d' Energetique et de Mecanique Theorique et Appliquee (LEMTA), Universite de Lorraine, 2, avenue de la Foret de Haye, 54504 Vandoeuvre-les-Nancy (France); LEMTA, CNRS, 2, avenue de la Foret de Haye, 54504 Vandoeuvre-les-Nancy (France)

2012-10-15

A one-dimensional (1D) model of oxygen transport in the diffusion media of proton exchange membrane fuel cells (PEMFC) is presented, which considers convection perpendicular to the electrode in addition to diffusion. The resulting analytical expression of the convecto-diffusive impedance is obtained using a convection-diffusion equation instead of a diffusion equation in the case of classical Warburg impedance. The main hypothesis of the model is that the convective flux is generated by the evacuation of water produced at the cathode which flows through the porous media in vapor phase. This allows the expression of the convective flux velocity as a function of the current density and of the water transport coefficient {alpha} (the fraction of water being evacuated at the cathode outlet). The resulting 1D oxygen transport impedance neglects processes occurring in the direction parallel to the electrode that could have a significant impact on the cell impedance, like gas consumption or concentration oscillations induced by the measuring signal. However, it enables us to estimate the impact of convection perpendicular to the electrode on PEMFC impedance spectra and to determine in which conditions the approximation of a purely diffusive oxygen transport is valid. Experimental observations confirm the numerical results. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Improvement of Transparent Conducting Performance on Oxygen-Activated Fluorine-Doped Tin Oxide Electrodes Formed by Horizontal Ultrasonic Spray Pyrolysis Deposition.

Science.gov (United States)

Koo, Bon-Ryul; Oh, Dong-Hyeun; Riu, Doh-Hyung; Ahn, Hyo-Jin

2017-12-27

In this study, highly transparent conducting fluorine-doped tin oxide (FTO) electrodes were fabricated using the horizontal ultrasonic spray pyrolysis deposition. In order to improve their transparent conducting performances, we carried out oxygen activation by adjusting the ratio of O 2 /(O 2 +N 2 ) in the carrier gas (0%, 20%, and 50%) used during the deposition process. The oxygen activation on the FTO electrodes accelerated the substitution concentration of F (F O • ) into the oxygen sites in the FTO electrode while the oxygen vacancy (V O • • ) concentration was reduced. In addition, due to growth of pyramid-shaped crystallites with (200) preferred orientations, this oxygen activation caused the formation of a uniform surface structure. As a result, compared to others, the FTO electrode prepared at 50% O 2 showed excellent electrical and optical properties (sheet resistance of ∼4.0 ± 0.14 Ω/□, optical transmittance of ∼85.3%, and figure of merit of ∼5.09 ± 0.19 × 10 -2 Ω -1 ). This led to a superb photoconversion efficiency (∼7.03 ± 0.20%) as a result of the improved short-circuit current density. The photovoltaic performance improvement can be defined by the decreased sheet resistance of FTO used as a transparent conducting electrode in dye-sensitized solar cells (DSSCs), which is due to the combined effect of the high carrier concentration by the improved F O • concentration on the FTO electrodes and the fasted Hall mobility by the formation of a uniform FTO surface structure and distortion relaxation on the FTO lattices resulting from the reduced V O • • • concentration.

High performance cermet electrodes

Science.gov (United States)

Isenberg, Arnold O.; Zymboly, Gregory E.

1986-01-01

Disclosed is a method of increasing the operating cell voltage of a solid oxide electrochemical cell having metal electrode particles in contact with an oxygen-transporting ceramic electrolyte. The metal electrode is heated with the cell, and oxygen is passed through the oxygen-transporting ceramic electrolyte to the surface of the metal electrode particles so that the metal electrode particles are oxidized to form a metal oxide layer between the metal electrode particles and the electrolyte. The metal oxide layer is then reduced to form porous metal between the metal electrode particles and the ceramic electrolyte.

Enhanced Cyclability of Lithium-Oxygen Batteries with Electrodes Protected by Surface Films Induced via In-Situ Electrochemical Process

Energy Technology Data Exchange (ETDEWEB)

Liu, Bin; Xu, Wu; Tao, Jinhui; Yan, Pengfei; Zheng, Jianming; Engelhard, Mark H.; Lu, Dongping; Wang, Chongmin; Zhang, Jiguang

2018-04-16

Although the rechargeable lithium-oxygen (Li-O2) batteries have extremely high theoretical specific energy, the practical application of these batteries is still limited by the instability of their carbon-based air-electrode, Li metal anode, and electrolytes towards reduced oxygen species. Here we demonstrate a simple one-step in-situ electrochemical pre-charging strategy to generate thin protective films on both carbon nanotubes (CNTs) air-electrode and Li metal anode simultaneously under an inert atmosphere. Li-O2 cells after such pre-treatment demonstrate significantly extended cycle life of 110 and 180 cycles under the capacity-limited protocol of 1000 mAh g-1 and 500 mAh g-1, respectively, which is far more than those without pre-treatment. The thin-films formed from decomposition of electrolyte during in-situ electrochemical pre-charging process in an inert environment can protect both CNTs air-electrode and Li metal anode prior to conventional Li-O2 discharge/charge cycling where reactive reduced oxygen species are formed. This work provides a new approach for protections of carbon-based air-electrode and Li metal anode in practical Li-O2 batteries, and may also be applied to other battery systems.

Advances in interactive supported electro-catalysis for hydrogen and oxygen electrode reactions

Energy Technology Data Exchange (ETDEWEB)

Nedeljko V Krstajic; Ljiljana M Vracar; Jelena M Jaksic; Milan M Jaksic [Faculty of Technology and Metallurgy, University of Belgrade, Belgrade, Serbia and Montenegro (Yugoslavia); Stelios G Neophytides; Miranda Labou; Jelena M Jaksic; Milan M Jaksic [Institute of Chemical Engineering and High Temperature Chemical Processes FORTH, and Department of Chemistry, University of Patras, 26500 Patras, (Greece); Reidar Tunold [University of Trondheim, NTNU, Institute of Industrial Electrochemistry, Trondheim, (Norway); Polycarpos Falaras [Institute of Physical Chemistry, NCSR Demokritos, Attikis, Athens, (Greece)

2006-07-01

Magneli phases have been introduced as an unique electron conductive and interactive support for electro-catalysis both in hydrogen (HELR) and oxygen (OELR) electrode reactions in water electrolysis and Low Temperature PEM Fuel Cells (LT PEM FC). The Strong Metal-Support Interaction (SMSI) that imposes the former implies: (i) the hypo-hyper-d inter-bonding effect and its catalytic consequences, and (ii) the interactive primary oxide (M-OH) spillover from the hypo-d-oxide support as a dynamic electrocatalytic contribution. The stronger the bonding, the more strained appear d-orbitals, thereby the less strong the intermediate adsorptive strength in the rate determining step (RDS), and consequently, the faster the facilitated catalytic electrode reaction arises. At the same time the primary oxide spillover transferred from the hypo-d-oxide support directly interferes and reacts either individually and directly to contribute to finish the oxygen reduction, or with other interactive species, like CO to contribute to the CO tolerance. In such a respect, the conditions to provide Au to act as the reversible hydrogen electrode have been proved either by its potentiodynamic surface reconstruction in a heavy water solution, or by the nano-structured SMSI Au on anatase titania with characteristic strained d-orbitals in such a hypo-hyper-d-interactive bonding (Au/TiO{sub 2}). In the same context, the monoatomic network dispersion of Pt upon Magneli phases makes it possible to produce an advanced interactive supported electro-catalyst for cathodic oxygen reduction (ORR). The strained hypo-hyper-d-inter-electronic and inter-d-orbital metal/hypo-d-oxide support bonding relative to the strength of the latter, has been inferred to be the basis of the synergistic electrocatalytic effect both in the HELR and ORR. (authors)

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.

The contents of sesamol and related lignans in sesame, tahina and halva as determined by a newly developed polarographic and stripping voltammetric analysis

Energy Technology Data Exchange (ETDEWEB)

Tokusoglu, O.; Kocak, S.; Aycan, S.

2009-07-01

The contents of antioxidant lignans (Sesamol) in sesame, commercial formulations of tahina and halva, which are processed tahina foods, were determined by Differential Pulse Polarography (DPP) with a capillary hanging mercury drop electrode (HMDE). A platinum wire was used as the counter electrode and Ag/AgCl was the reference electrode. Samples have been analyzed by standard addition procedures and found to be quantitative (p<0.01). Due to the fact that sesamol is an oil-soluble phenolic compound , it was found in the oil levels of sesame, tahina and halvas. Sesame samples contained 51.05-56.46 % in oil whereas tahina samples contained 52.12-53.79 % in oil. The oil percentage of plain halva was found to be 28.79 - 30.13 % (p<0.01). Phenolic lignans sesamol in sesame was 0.26-0.32 mg/100g oil, whereas the sesamol in tahina was 10.98-12.33 mg/100g oil. The sesamol in commercial plain halva samples and the open marketed plain halva samples contained 8.24-9.12 mg/100g oil and 4.97 mg sesamol /100g oil, respectively (R{sup 2}=0.9999) (p<0.01). The proposed Differential Pulse Polarographic (DPP) method is a rapid, reproducible procedure for the simultaneous determination of phenolic lignans in sesame and food products with sesame. It provides an adequate, sensitive, quantitative detection of these nutraceuticals in the commercial food industry. (Author) 26 refs.

Uptake rate of cationic mitochondrial inhibitor MKT-077 determines cellular oxygen consumption change in carcinoma cells.

Directory of Open Access Journals (Sweden)

John L Chunta

Full Text Available OBJECTIVE: Since tumor radiation response is oxygen-dependent, radiosensitivity can be enhanced by increasing tumor oxygenation. Theoretically, inhibiting cellular oxygen consumption is the most efficient way to increase oxygen levels. The cationic, rhodacyanine dye-analog MKT-077 inhibits mitochondrial respiration and could be an effective metabolic inhibitor. However, the relationship between cellular MKT-077 uptake and metabolic inhibition is unknown. We hypothesized that rat and human mammary carcinoma cells would take up MKT-077, causing a decrease in oxygen metabolism related to drug uptake. METHODS: R3230Ac rat breast adenocarcinoma cells were exposed to MKT-077. Cellular MKT-077 concentration was quantified using spectroscopy, and oxygen consumption was measured using polarographic electrodes. MKT-077 uptake kinetics were modeled by accounting for uptake due to both the concentration and potential gradients across the plasma and mitochondrial membranes. These kinetic parameters were used to model the relationship between MKT-077 uptake and metabolic inhibition. MKT-077-induced changes in oxygen consumption were also characterized in MDA-MB231 human breast carcinoma cells. RESULTS: Cells took up MKT-077 with a time constant of ∼1 hr, and modeling showed that over 90% of intracellular MKT-077 was bound or sequestered, likely by the mitochondria. The uptake resulted in a rapid decrease in oxygen consumption, with a time constant of ∼30 minutes. Surprisingly the change in oxygen consumption was proportional to uptake rate, not cellular concentration. MKT-077 proved a potent metabolic inhibitor, with dose-dependent decreases of 45-73% (p = 0.003. CONCLUSIONS: MKT-077 caused an uptake rate-dependent decrease in cellular metabolism, suggesting potential efficacy for increasing tumor oxygen levels and radiosensitivity in vivo.

Effect of cathode porosity on the Lithium-air cell oxygen reduction reaction – A rotating ring-disk electrode investigation

International Nuclear Information System (INIS)

Seo, Jeongwook; Sankarasubramanian, Shrihari; Singh, Nikhilendra; Mizuno, Fuminori; Takechi, Kensuke; Prakash, Jai

2017-01-01

The kinetics of the oxygen reduction reaction (ORR) on the practical air cathode in a Lithium-air cell, which is conventionally composed of porous carbon with or without catalysts supported on it, was investigated. The mechanism and kinetics of the oxygen reduction reaction (ORR) was studied on a porous carbon electrode in an oxygen saturated solution of 0.1 M Lithium bis-trifluoromethanesulfonimide (LiTFSI) in Dimethoxyethane (DME) using cyclic voltammetery (CV) and the rotating ring-disk electrode (RRDE) technique. The oxygen reduction and evolution reactions were found to occur at similar potentials to those observed on a smooth, planar glassy carbon (GC) electrode. The effect of porosity and the resultant increase in surface area were readily observed in the increase in the transient time required for the intermediates to reach the ring and the much larger disk currents (compared to smooth, planar GC) recorded respectively. The RRDE data was analyzed using a kinetic model previously developed by us and the rate constants for the elementary reactions were calculated. The rates constant for the electrochemical reactions were found to be similar in magnitude to the rate constants calculated for smooth GC disks. The porosity of the electrode was found to decrease the rate of desorption of the intermediate and the product and delay their diffusion by shifting it from a Fickian regime in the electrolyte bulk to the Knudsen regime in the film pores. Thus, it is shown that the effect of the electrode porosity on the kinetics of the ORR is physical rather than electrochemical.

Analyzing the dependence of oxygen incorporation current density on overpotential and oxygen partial pressure in mixed conducting oxide electrodes.

Science.gov (United States)

Guan, Zixuan; Chen, Di; Chueh, William C

2017-08-30

The oxygen incorporation reaction, which involves the transformation of an oxygen gas molecule to two lattice oxygen ions in a mixed ionic and electronic conducting solid, is a ubiquitous and fundamental reaction in solid-state electrochemistry. To understand the reaction pathway and to identify the rate-determining step, near-equilibrium measurements have been employed to quantify the exchange coefficients as a function of oxygen partial pressure and temperature. However, because the exchange coefficient contains contributions from both forward and reverse reaction rate constants and depends on both oxygen partial pressure and oxygen fugacity in the solid, unique and definitive mechanistic assessment has been challenging. In this work, we derive a current density equation as a function of both oxygen partial pressure and overpotential, and consider both near and far from equilibrium limits. Rather than considering specific reaction pathways, we generalize the multi-step oxygen incorporation reaction into the rate-determining step, preceding and following quasi-equilibrium steps, and consider the number of oxygen ions and electrons involved in each. By evaluating the dependence of current density on oxygen partial pressure and overpotential separately, one obtains the reaction orders for oxygen gas molecules and for solid-state species in the electrode. We simulated the oxygen incorporation current density-overpotential curves for praseodymium-doped ceria for various candidate rate-determining steps. This work highlights a promising method for studying the exchange kinetics far away from equilibrium.

Polarographic determination of stability constants of Eu(III) complexes with acrylic and crotonic acid

Energy Technology Data Exchange (ETDEWEB)

Rao, A L.J.; Singh, Makhan [Punjabi Univ., Patiala (India). Dept. of Chemistry

1979-07-01

Compositions and formation constants of Eu(III) complexes with acrylic acid and crotonic acid have been studied polarographically. The reductions are reversible and diffusion-controlled. The plot of Esub(1/2) versus--log Csub(x) is linear in the case of Eu(III)-acrylic acid system. The change in number of ligands bound to europium during reduction was found to be approximately 1 and ratio of dissociation constants of Eu(III) and Eu(II) was found to be 40.76X10sup(-2). In the case of Eu(III)-crotonic acid system, composition and formation constants have been calculated by the method of Deford and Hume. Crotonic acid forms two complex species with europium (..beta../sub 1/,60; ..beta../sub 2/, 4.2x10sup(+2)). The percentage distribution of various complex species as a function of ligand concentration has been calculated in the case of Eu(III)-crotonic acid system. A polarographic method for the determination of micro amounts of Eu(III) in the presence of diverse ions has been developed. Under optimum conditions Eu(III) in the concentration range 4x19sup(-4)-2x10sup(-2)M can be successfully determined in various mixtures.

Roles of Bulk and Surface Chemistry in the Oxygen Exchange Kinetics and Related Properties of Mixed Conducting Perovskite Oxide Electrodes

Directory of Open Access Journals (Sweden)

Nicola H. Perry

2016-10-01

Full Text Available Mixed conducting perovskite oxides and related structures serving as electrodes for electrochemical oxygen incorporation and evolution in solid oxide fuel and electrolysis cells, respectively, play a significant role in determining the cell efficiency and lifetime. Desired improvements in catalytic activity for rapid surface oxygen exchange, fast bulk transport (electronic and ionic, and thermo-chemo-mechanical stability of oxygen electrodes will require increased understanding of the impact of both bulk and surface chemistry on these properties. This review highlights selected work at the International Institute for Carbon-Neutral Energy Research (I2CNER, Kyushu University, set in the context of work in the broader community, aiming to characterize and understand relationships between bulk and surface composition and oxygen electrode performance. Insights into aspects of bulk point defect chemistry, electronic structure, crystal structure, and cation choice that impact carrier concentrations and mobilities, surface exchange kinetics, and chemical expansion coefficients are emerging. At the same time, an understanding of the relationship between bulk and surface chemistry is being developed that may assist design of electrodes with more robust surface chemistries, e.g., impurity tolerance or limited surface segregation. Ion scattering techniques (e.g., secondary ion mass spectrometry, SIMS, or low energy ion scattering spectroscopy, LEIS with high surface sensitivity and increasing lateral resolution are proving useful for measuring surface exchange kinetics, diffusivity, and corresponding outer monolayer chemistry of electrodes exposed to typical operating conditions. Beyond consideration of chemical composition, the use of strain and/or a high density of active interfaces also show promise for enhancing performance.

The effects of high-Dk rigid contact lens center thickness, material permeability, and blinking on the oxygen uptake of the human cornea.

Science.gov (United States)

Gardner, Hope Patterson; Fink, Barbara A; Mitchell, Lynn G; Hill, Richard M

2005-06-01

The human corneal oxygen uptake responses associated with the static (nonblinking) and dynamic (blinking) wear of five rigid gas-permeable materials with high oxygen permeabilities were determined for three different center thicknesses and compared with the responses for the normal open eye and severe hypoxic stress (static wear of polymethylmethacrylate). Corneal oxygen uptake rates were measured with a Clark-type polarographic electrode during two sessions with each of 10 human subjects. Measurements were made on the right eye for the normal open eye (air) and after 5 minutes of static and dynamic wear of polymethylmethacrylate and five rigid gas-permeable contact lens materials: Fluoroperm 92 (paflufocon A, Dk = 92), Fluoroperm 151 (paflufocon D, Dk = 151), 1992 Menicon SF-P (melafocon A, Dk = 102), 1995 Menicon SF-P (melafocon A, Dk = 159), and Menicon Z (tisilfocon A, Dk = 163-250). Lenses were manufactured in three different center thicknesses (0.12, 0.16, and 0.20 mm), with all other parameters remaining constant. Repeated-measures analysis of variance was used and included lens material (five levels), blinking condition (two levels), and lens thickness (three levels) as within-subject effects. Significant differences were found in corneal oxygen responses to lens material (p Dk rigid lens materials studied here, moderate changes in lens thickness or material permeability may result in modest differences in corneal hypoxic relief, whereas blinking results in no significant improvement to corneal oxygenation.

Monitoring in microvascular tissue transfer by measurement of oxygen partial pressure: four years experience with 125 microsurgical transplants.

Science.gov (United States)

Jonas, René; Schaal, Thomas; Krimmel, Michael; Gülicher, Dirk; Reinert, Siegmar; Hoffmann, Jürgen

2013-06-01

In a prospective study, the characteristics and benefit of an invasive measurement of oxygen partial pressure (pO(2)) with the aid of a polarographic sensor were investigated in 125 microsurgical reconstructions of the head and neck area over a period of 45 months. Measurements were performed over 96 h in eight different types of microsurgically revascularized flaps for extra- and intraoral reconstructions and were evaluated separately for each flap type. Of 125 reconstructions the system indicated malperfusion in 18 cases. Salvage surgery was performed in 17 cases due to venous thrombosis (6 cases), arterial thrombosis (3 cases), a combination of arterial and venous thrombosis (2 cases), rheological problems (3 cases), venous insufficiency by hematoma (2 cases) and kinking of vessels (1 case). In 10 cases salvage surgery was successful, 7 flaps were lost despite salvage surgery. In all these cases, the polarographic probe indicated the necessity of salvage surgery correctly. After 96 h no malperfusion was seen. Postoperatively, a common and characteristic development of the oxygen partial pressure in different types of flaps was seen. Initially, a clear increase of pO(2) could be measured. During 96 h, a slow decrease of pO(2) was observed. In conclusion polarographic measurement of pO(2) can be an excellent apparative supplement for the postoperative clinical control of microsurgically revascularized transplants. In buried flaps, this technique represents the only reliable method for transplant monitoring. Copyright © 2012 European Association for Cranio-Maxillo-Facial Surgery. Published by Elsevier Ltd. All rights reserved.

Copper-substituted perovskite compositions for solid oxide fuel cell cathodes and oxygen reduction electrodes in other electrochemical devices

Science.gov (United States)

Rieke, Peter C [Pasco, WA; Coffey, Gregory W [Richland, WA; Pederson, Larry R [Kennewick, WA; Marina, Olga A [Richland, WA; Hardy, John S [Richland, WA; Singh, Prabhaker [Richland, WA; Thomsen, Edwin C [Richland, WA

2010-07-20

The present invention provides novel compositions that find advantageous use in making electrodes for electrochemical cells. Also provided are electrochemical devices that include active oxygen reduction electrodes, such as solid oxide fuel cells, sensors, pumps and the like. The compositions comprises a copper-substituted ferrite perovskite material. The invention also provides novel methods for making and using the electrode compositions and solid oxide fuel cells and solid oxide fuel cell assemblies having cathodes comprising the compositions.

Severe anemia is associated with poor tumor oxygenation in head and neck squamous cell carcinomas

International Nuclear Information System (INIS)

Becker, Axel; Stadler, Peter; Lavey, Robert S.; Haensgen, Gabriele; Kuhnt, Thomas; Lautenschlaeger, Christine; Feldmann, Horst Juergen; Molls, Michael; Dunst, Juergen

2000-01-01

Purpose: To investigate the relationship between tumor oxygenation and the blood hemoglobin (Hb) concentration in patients with squamous cell carcinoma of the head and neck (SCCHN). Methods and Materials: A total of 133 patients with SCCHN underwent pretreatment polarographic pO 2 measurements of their tumors. In 66 patients measurements were also made in sternocleidomastoid muscles. The patients were divided into three groups according to their Hb concentration--severe anemia (Hb 2 . Conclusion: Our data suggest that a low Hb concentration and cigarette smoking contribute to inadequate oxygenation of SCCHN and thus for increased radioresistance. Consequently, Hb correction and abstinence from smoking may significantly improve tumor oxygenation

Freestanding eggshell membrane-based electrodes for high-performance supercapacitors and oxygen evolution reaction

Science.gov (United States)

Geng, Jing; Wu, Hao; Al-Enizi, Abdullah M.; Elzatahry, Ahmed A.; Zheng, Gengfeng

2015-08-01

A type of freestanding, light-weight eggshell membrane-based electrode is demonstrated for supercapacitors and for oxygen evolution reaction (OER) catalysis. As a widely available daily waste, eggshell membranes have unique porous three-dimensional grid-like fibrous structures with relatively high surface area and abundant macropores, allowing for effective conjugation of carbon nanotubes and growth of NiCo2O4 nanowire arrays, an effective supercapacitor material and OER catalyst. The three-dimensional fibrous eggshell membrane frameworks with carbon nanotubes offer efficient pathways for charge transport, and the macropores between adjacent fibers are fully accessible for electrolytes and bubble evolution. As a supercapacitor, the eggshell membrane/carbon nanotube/NiCo2O4 electrode shows high specific capacitances at current densities from 1 to 20 A g-1, with excellent capacitance retention (>90%) at 10 A g-1 for over 10 000 cycles. When employed as an OER catalyst, this eggshell membrane-based electrode exhibits an OER onset potential of 1.53 V vs. the reversible hydrogen electrode (RHE), and a stable catalytic current density of 20 mA cm-2 at 1.65 V vs. the RHE.A type of freestanding, light-weight eggshell membrane-based electrode is demonstrated for supercapacitors and for oxygen evolution reaction (OER) catalysis. As a widely available daily waste, eggshell membranes have unique porous three-dimensional grid-like fibrous structures with relatively high surface area and abundant macropores, allowing for effective conjugation of carbon nanotubes and growth of NiCo2O4 nanowire arrays, an effective supercapacitor material and OER catalyst. The three-dimensional fibrous eggshell membrane frameworks with carbon nanotubes offer efficient pathways for charge transport, and the macropores between adjacent fibers are fully accessible for electrolytes and bubble evolution. As a supercapacitor, the eggshell membrane/carbon nanotube/NiCo2O4 electrode shows high specific

Sensor employing internal reference electrode

DEFF Research Database (Denmark)

2013-01-01

The present invention concerns a novel internal reference electrode as well as a novel sensing electrode for an improved internal reference oxygen sensor and the sensor employing same.......The present invention concerns a novel internal reference electrode as well as a novel sensing electrode for an improved internal reference oxygen sensor and the sensor employing same....

Free-standing, flexible β-Ni(OH)2/electrochemically-exfoliated graphene film electrode for efficient oxygen evolution

Science.gov (United States)

Wang, Lanlan; Zhang, Jian; Jiang, Weitao; Zhao, Hong; Liu, Hongzhong

2018-03-01

The oxidation of water into molecular oxygen (oxygen evolution reaction, OER) is a pivotal reaction in many energy conversion devices. The high cost of IrO2, however, seriously hinder its large-scale applications in water oxidation. Here, we have at first reported a free-standing and flexible film electrode consisting of 2D β-Ni(OH)2/electrochemically-exfoliated graphene hybrid nanosheets (NiG-2), which is synthesized by a solvothermal reaction and an assembly process. The as-obtained NiG-2 film electrode exhibited an excellent electrocatalytic OER activity with an extremely low OER onset overpotential of ∼250 mV in a 1 M KOH aqueous solution, which is lower than these of the commercial Ir/C (370 mV at 10 mA cm-2) catalyst.

In Situ-Grown ZnCo2O4 on Single-Walled Carbon Nanotubes as Air Electrode Materials for Rechargeable Lithium–Oxygen Batteries

Energy Technology Data Exchange (ETDEWEB)

Liu, Bin; Xu, Wu; Yan, Pengfei; Bhattacharya, Priyanka; Cao, Ruiguo; Bowden, Mark E.; Engelhard, Mark H.; Wang, Chong M.; Zhang, Jiguang

2015-10-12

Although lithium-oxygen (Li-O2) batteries have great potential to be used as one of the next generation energy storage systems due to their ultrahigh theoretical specific energy, there are still many significant barriers before their practical applications. These barriers include electrolyte and electrode instability, poor ORR/OER efficiency and cycling capability, etc. Development of a highly efficient catalyst will not only enhance ORR/OER efficiency, it may also improve the stability of electrolyte because the reduced charge voltage. Here we report the synthesis of nano-sheet-assembled ZnCo2O4 spheres/single walled carbon nanotubes (ZCO/SWCNTs) composites as high performance air electrode materials for Li-O2 batteries. The ZCO catalyzed SWCNTs electrodes delivered high discharge capacities, decreased the onset of oxygen evolution reaction by 0.9 V during charge processes, and led to more stable cycling stability. These results indicate that ZCO/SWCNTs composite can be used as highly efficient air electrode for oxygen reduction and evolution reactions. The highly enhanced catalytic activity by uniformly dispersed ZnCo2O4 catalyst on nanostructured electrodes is expected to inspire

Polarographic study of mixed-ligand complexes of cadmium(II) with L-amino acid and vitamin B5

International Nuclear Information System (INIS)

Jain, Alok K.; Khan, Farid

1998-01-01

A survey of literature shows that ternary complexes of Cd II with L-amino acids and vitamin B 5 have not been studied so far. The present communication reports the formation of mixed-ligand complexes of Cd II with L-amino acids as primary ligands and vitamin B 5 as secondary ligand, studied by polarographic technique. (author)

Polarographic and potentiometric studies on some binary and ternary complex systems of dioxouranium(VI)

International Nuclear Information System (INIS)

Janarthanam, M.; Sivasankar, B.; Rengaraj, K.; Nair, M.S.

1995-01-01

The relative coordinating abilities of donor sites in the potentially tridentate ligands viz., asparagine, glutamine, aspartic acid and glutamic acid towards uranyl ion have been investigated by polarographic and pH-metric techniques. The metal ion forms 1:2 complexes under polarographic conditions. However, only 1:1 complex is observed under pH-metric conditions, where 1:2 complexes do not proceed due to extensive hydrolysis of the metal ion. The relative variations of ΔE 1/2 with pH and ligand concentration supported by conductometric titration data indicate that the primary amino groups in the amino acids are not involved in coordination with uranyl ion. Further, the amide groups in asparagine and glutamine also do not participate in coordination thus rendering these ligands unidentate. In aspartic and glutamic acid complexes, seven- and eight- membered chelate rings are formed involving two terminal carboxyl groups. The mixed ligand complex equilibria of uranyl ion involving aspartic acid/glutamic acid as primary ligands (A) and maleic acid, malonic acid, succinic acid and lactic acid as secondary ligands (B) have also been studied by computer based numerical evaluation of pH titration data. The concentration profiles have indicated the favorability of the formation of ternary complexes in general as reflected in the Δlog K values. (author). 10 refs., 1 fig., 1 tab

Polarographic determination of stability constants of Eu(III) complexes with acrylic acid and crotonic acid

Energy Technology Data Exchange (ETDEWEB)

Rao, A L.J.; Makhan, S [Punjabi Univ., Patiala (India). Dept. of Chemistry

1979-07-01

Compositions and formation constants of Eu(III) complexes with acrylic acid and crotonic acid have been studied polarographically. The reductions are reversible and diffusion-controlled. The plot of Esub(1/2) versus -log Csub(x) is linear in the case of Eu(III)-acrylic acid system. The change in number of ligands bound to europium during reduction was found to be approximately equal to 1 and ratio of dissociation constants of Eu(III) and Eu(II) was found to be 40.76 x 10sup(-2). In the case of Eu(III)-crotonic acid system, composition and formation constants have been calculated by the method of Deford and Hume. Crotonic acid forms two complex species with europium (..beta../sub 1/, 60; ..beta../sub 2/, 4.2x10sup(+2)). The percentage distribution of various complex species as a function of ligand concentration has been calculated in the case of Eu(III)-crotonic acid system. A polarographic method for the determination of micro amounts of Eu(III) in the presence of diverse ions has been developed. Under optimum conditions Eu(III) in the concentration range 4x10sup(-4)-2x10sup(-3)M can be successfully determined in various mixtures.

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...

Freestanding eggshell membrane-based electrodes for high-performance supercapacitors and oxygen evolution reaction.

Science.gov (United States)

Geng, Jing; Wu, Hao; Al-Enizi, Abdullah M; Elzatahry, Ahmed A; Zheng, Gengfeng

2015-09-14

A type of freestanding, light-weight eggshell membrane-based electrode is demonstrated for supercapacitors and for oxygen evolution reaction (OER) catalysis. As a widely available daily waste, eggshell membranes have unique porous three-dimensional grid-like fibrous structures with relatively high surface area and abundant macropores, allowing for effective conjugation of carbon nanotubes and growth of NiCo2O4 nanowire arrays, an effective supercapacitor material and OER catalyst. The three-dimensional fibrous eggshell membrane frameworks with carbon nanotubes offer efficient pathways for charge transport, and the macropores between adjacent fibers are fully accessible for electrolytes and bubble evolution. As a supercapacitor, the eggshell membrane/carbon nanotube/NiCo2O4 electrode shows high specific capacitances at current densities from 1 to 20 A g(-1), with excellent capacitance retention (>90%) at 10 A g(-1) for over 10,000 cycles. When employed as an OER catalyst, this eggshell membrane-based electrode exhibits an OER onset potential of 1.53 V vs. the reversible hydrogen electrode (RHE), and a stable catalytic current density of 20 mA cm(-2) at 1.65 V vs. the RHE.

Oxygen-Vacancy Abundant Ultrafine Co3O4/Graphene Composites for High-Rate Supercapacitor Electrodes.

Science.gov (United States)

Yang, Shuhua; Liu, Yuanyue; Hao, Yufeng; Yang, Xiaopeng; Goddard, William A; Zhang, Xiao Li; Cao, Bingqiang

2018-04-01

The metal oxides/graphene composites are one of the most promising supercapacitors (SCs) electrode materials. However, rational synthesis of such electrode materials with controllable conductivity and electrochemical activity is the topical challenge for high-performance SCs. Here, the Co 3 O 4 /graphene composite is taken as a typical example and develops a novel/universal one-step laser irradiation method that overcomes all these challenges and obtains the oxygen-vacancy abundant ultrafine Co 3 O 4 nanoparticles/graphene (UCNG) composites with high SCs performance. First-principles calculations show that the surface oxygen vacancies can facilitate the electrochemical charge transfer by creating midgap electronic states. The specific capacitance of the UCNG electrode reaches 978.1 F g -1 (135.8 mA h g -1 ) at the current densities of 1 A g -1 and retains a high capacitance retention of 916.5 F g -1 (127.3 mA h g -1 ) even at current density up to 10 A g -1 , showing remarkable rate capability (more than 93.7% capacitance retention). Additionally, 99.3% of the initial capacitance is maintained after consecutive 20 000 cycles, demonstrating enhanced cycling stability. Moreover, this proposed laser-assisted growth strategy is demonstrated to be universal for other metal oxide/graphene composites with tuned electrical conductivity and electrochemical activity.

Influence of oxygen gas on characteristics of self-organized luminous pattern formation observed in an atmospheric dc glow discharge using a liquid electrode

International Nuclear Information System (INIS)

Shirai, Naoki; Uchida, Satoshi; Tochikubo, Fumiyoshi

2014-01-01

Self-organized luminous pattern formation is observed in the liquid surface of an atmospheric dc glow discharge using a liquid electrode with a miniature helium flow. The factors affecting pattern formation are the gap length, discharge current, helium mass flow rate and polarity. The pattern shape depends on the conductivity and temperature of the liquid electrode. A variety of patterns were observed by changing the conductivity and temperature of the liquid. We clarified that the self-organized pattern formation depends on the amount of electronegative gas, such as oxygen, in the gas in the electrode gap. When an oxygen gas flow was fed to the liquid surface from the outside in an obliquely downward direction, namely, the amount of oxygen gas on the liquid surface was increased locally, self-organized pattern formation was observed in the region with the increased amount of oxygen gas. When the amount of oxygen in the gas in the gap was changed by using a sheath flow system, the appearance of the pattern changed. The presence of oxygen gas strongly affected the self-organized pattern formation of the atmospheric dc discharge using a liquid anode. (paper)

SiC-Si as a support material for oxygen evolution electrode in PEM steam electrolysers

DEFF Research Database (Denmark)

Nikiforov, Aleksey; Tomás García, Antonio Luis; Petrushina, Irina

2011-01-01

The need of higher energy efficiency in hydrogen production has promoted the research on improved catalysts for water electrolysis. In this work, a novel supported catalyst for oxygen evolution electrodes was prepared and characterized with different techniques. IrO2 supported on a SiC/Si composite...

Electrocatalysis of oxygen electrode reactions by some perovskite oxides based on lanthanum manganate

International Nuclear Information System (INIS)

Raj, I.A.; Rao, K.V.; Venkatesan, V.K.

1984-01-01

In recent years, several electrocatalyst materials based on platinum, silver, tungsten bronzes, spinels, metal chelates, etc., have been studied for use as oxygen diffusion electrodes in alkaline fuel cells, secondary metal-air batteries, and water electrolyzers. However, virtually all catalysts of commercial importance are semiconducting transition metal oxides. The various oxide catalysts that have been studied can be grouped under mixed oxides, spinels, and perovskites

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

Development of a Novel Cu(II Complex Modified Electrode and a Portable Electrochemical Analyzer for the Determination of Dissolved Oxygen (DO in Water

Directory of Open Access Journals (Sweden)

Salvatore Gianluca Leonardi

2016-04-01

Full Text Available The development of an electrochemical dissolved oxygen (DO sensor based on a novel Cu(II complex-modified screen printed carbon electrode is reported. The voltammetric behavior of the modified electrode was investigated at different scan rates and oxygen concentrations in PBS (pH = 7. An increase of cathodic current (at about −0.4 vs. Ag/AgCl with the addition of oxygen was observed. The modified Cu(II complex electrode was demonstrated for the determination of DO in water using chronoamperometry. A small size and low power consumption home-made portable electrochemical analyzer based on custom electronics for sensor interfacing and operating in voltammetry and amperometry modes has been also designed and fabricated. Its performances in the monitoring of DO in water were compared with a commercial one.

Oxygen evolution reaction catalysis

Energy Technology Data Exchange (ETDEWEB)

Haber, Joel A.; Jin, Jian; Xiang, Chengxiang; Gregoire, John M.; Jones, Ryan J.; Guevarra, Dan W.; Shinde, Aniketa A.

2016-09-06

An Oxygen Evolution Reaction (OER) catalyst includes a metal oxide that includes oxygen, cerium, and one or more second metals. In some instances, the cerium is 10 to 80 molar % of the metals in the metal oxide and/or the catalyst includes two or more second metals. The OER catalyst can be included in or on an electrode. The electrode can be arranged in an oxygen evolution system such that the Oxygen Evolution Reaction occurs at the electrode.

The role of oxygen in porous molybdenum electrodes for the alkali metal thermoelectric converter

International Nuclear Information System (INIS)

Williams, R.M.; Nagasubramanian, G.; Khanna, S.K.; Bankston, C.P.; Thakoor, A.P.; Cole, T.

1986-01-01

The alkali metal thermoelectric converter is a direct energy conversion device, utilizing a high alkali metal activity gradient to generate electrical power. Its operation is based on the unique ion conductive properties of beta''-alumina solid electrolyte. The major barrier to application of this device is identification of an electrode which can maintain optimum power densities for operation times of >10,000h. Thin, porous molybdenum electrodes have shown the best performance characteristics, but show a variety of time dependent phenomena, including eventual degradation to power densities 3-5 times lower than initial values. Several Na-Mo-O compounds, including Na/sub 2/MoO/sub 4/ and Na/sub 2/Mo/sub 3/O/sub 6/, are formed during AMTEC operation. These compounds may be responsible for enhanced Na transport through Mo electrodes via sodium ion conduction, and eventual performance degradation due to their volatilization and decomposition. No decomposition of beta''-alumina has been observed under simulated AMTEC operating conditions up to 1373 K. In this paper, we present a model for chemical reactions occurring in porous molybdenum electrodes. The model is based on thermochemical and kinetic data, known sodium-molybdenum-oxygen chemistry, x-ray diffraction analysis of molybdenum and molybdenum oxide electrodes, and the electrochemical behavior of the cell

The oxygen sensitivity of a multipoint antimony electrode for tissue pH measurements. A study of the sensitivity for in vivo PO2 variations below 6 kPa.

Science.gov (United States)

Sjöberg, F; Edwall, G; Lund, N

1987-02-01

Monocrystalline micro antimony electrodes in a multipoint arrangement as described by Lund et al. were placed on the skeletal muscle surface of the rabbit. Tissue oxygen levels were measured simultaneously with the MDO (Mehrdraht Dortmund Oberfläche) oxygen electrode. The sensitivity for variations in tissue PO2 (PO2(t)) was evaluated for the antimony metal-metal oxide sensor. The sensitivity (delta E/delta log10 PO2)+/- SE was found to be 21.8 +/- 1.2 mV in the interval between 0.1 kPa and 1 kPa and 53 +/- 5 mV in the interval between 1 kPa and 6 kPa. These results are not consistent with the oxygen sensitivity of monocrystalline antimony described in vitro, but are in agreement with the findings of Nilsson & Edwall. A plausible explanation for the S-shaped oxygen sensitivity curve of antimony at oxygen levels below 10 kPa could be an interaction, at the electrode surface, between the dissolved oxygen and the oxygen bound to haemoglobin. If this is the case, the use of an antimony electrode would make possible the determination of the dissociation of oxyhaemoglobin in tissues.

Polarographic determination of selenium and tellurium in silver-gold alloys

International Nuclear Information System (INIS)

Gornostaeva, T.D.; Shmargun, S.V.

1986-01-01

The determination of selenium and tellurium is of importance in monitoring the composition of silver-gold alloys (SGA) since these elements are harmful impurities in the pure metals. Tellurium is determined in silver alloys by atomic absorption and atomic emmission methods; selenium determination is made by atomic absorption methods. This paper examines the polarographic determination of silver and tellurium in SGA containing platinum metals and copper. Copper and the bulk of the platinum and palladium were removed by precipitating selenium and tellurium with potassium hypophosphite in the elementary state from 6 M HC1. The results of an analysis of samples of SGA according to the proposed method were compared with the results obtained by the atomic absorption method. the relative deviation in the determination of 0.02-1.0% by weight selenium and tellurium does not exceed 0.12 (n = 5)

Report on the FY 1999 investigational survey on the activation of oxygen electrode by ion implantation; 1999 nendo ion chunyuho ni yoru sanso denkyoku no kasseika ni kansuru kenkyu chosa hokokusho

Energy Technology Data Exchange (ETDEWEB)

NONE

2000-03-01

The oxygen electrode is important as the base electrode for water electrolysis and fuel cell, but to move it, overvoltage (activated energy) in addition to equilibrium voltage is necessary, which leads to the lowering of energy efficiency. By forming the active spot by ion implantation, the lowering of overvoltage was studied. The implantation of Ru{sup +} ion in Ruthenium dioxide thin film electrode reduced the oxygen generating overvoltage by 15-20mV. Even in the oxygen reduction, activity was also increased. The chemical composition of thin film does not change by ion implantation. The increase in activity is based on a physical change which is called the surface defect formation. The layer of ion implantation is composed of microcrystals, which is thought to contribute to the formation of any active spot. Ions were implanted in Pt electrode as a practical use material, and even in the oxygen reduction of Pt, a possibility of heightening activity by ion implantation was admitted even in the oxygen reduction of Pt. The generation of high activity oxygen by ion plantation and development of oxygen reduction electrode were established as one method as a rule. (NEDO)

Electrochemical reduction of imazamethabenz methyl on mercury and carbon electrodes

International Nuclear Information System (INIS)

Ruiz Montoya, Mercedes; Pintado, Sara; Rodriguez Mellado, Jose Miguel

2010-01-01

This paper presents polarographic and voltammetric studies of the reduction of the herbicide imazamethabenz methyl (2/3-methyl-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)-p-toluate), on mercury and carbon electrodes. The electrochemical studies were performed in strongly acidic media (0.1-2.7 M H 2 SO 4 ) as well as in the pH range of 1-12. The overall reduction process involves the uptake of two electrons. The results obtained in polarography show that there is the reduction of two species, related via an acid-base equilibrium, and having very close reduction potentials. The voltammetric results obtained with a glassy carbon electrode were very similar to those observed on mercury electrodes. The reducible group in the molecule is the imidazolinone ring. In strongly acidic media (pH a ), the reaction mechanism proposed is the reduction of the protonated herbicide by an electrochemical-chemical-electrochemical (ECE) process, being the r.d.s. the second electron transfer. At pH > pK a the neutral form of the herbicide is reduced and the second electron transfer becomes reversible or quasi-reversible. In basic media, the species reduced is the deprotonated imazamethabenz methyl and the r.d.s. is the second electron transfer.

Electrochemical reduction of imazamethabenz methyl on mercury and carbon electrodes

Energy Technology Data Exchange (ETDEWEB)

Ruiz Montoya, Mercedes, E-mail: mmontoya@uhu.e [Departamento de Ingenieria Quimica, Quimica Fisica y Quimica Organica, Universidad de Huelva, Campus El Carmen, Facultad de Ciencias Experimentales, E-21071 Huelva (Spain); Pintado, Sara; Rodriguez Mellado, Jose Miguel [Departamento de Quimica Fisica y Termodinamica Aplicada, Universidad de Cordoba, Campus Universitario de Rabanales, edificio ' Marie Curie' , E-14014 Cordoba (Spain)

2010-03-30

This paper presents polarographic and voltammetric studies of the reduction of the herbicide imazamethabenz methyl (2/3-methyl-(4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl)-p-toluate), on mercury and carbon electrodes. The electrochemical studies were performed in strongly acidic media (0.1-2.7 M H{sub 2}SO{sub 4}) as well as in the pH range of 1-12. The overall reduction process involves the uptake of two electrons. The results obtained in polarography show that there is the reduction of two species, related via an acid-base equilibrium, and having very close reduction potentials. The voltammetric results obtained with a glassy carbon electrode were very similar to those observed on mercury electrodes. The reducible group in the molecule is the imidazolinone ring. In strongly acidic media (pH < pK{sub a}), the reaction mechanism proposed is the reduction of the protonated herbicide by an electrochemical-chemical-electrochemical (ECE) process, being the r.d.s. the second electron transfer. At pH > pK{sub a} the neutral form of the herbicide is reduced and the second electron transfer becomes reversible or quasi-reversible. In basic media, the species reduced is the deprotonated imazamethabenz methyl and the r.d.s. is the second electron transfer.

Author Details

African Journals Online (AJOL)

Subramanian, PA. Vol 5, No 1 (2013) - Articles DC Polarographic and Plane Polarographic investigation of the reduction of Thallium(I) - Aqueous systems at dropping mercury electrode. Abstract PDF. ISSN: 2073-073X. AJOL African Journals Online. HOW TO USE AJOL... for Researchers · for Librarians · for Authors · FAQ's ...

Oxygen Reduction Kinetics of La2-xSrxNiO 4+delta Electrodes for Solid Oxide Fuel Cells

Science.gov (United States)

Guan, Bo

In the development of intermediate temperature solid oxide fuel cell (IT-SOFC), mixed ionic-electronic conductors (MIEC) have drawn big interests due to their both ionic and electronic species transport which can enlarge the 3-dimension of the cathode network. This thesis presents an investigation of MIEC of Ruddlesden-popper (RP) phases like K2NiF4 type La2NiO4+delta (LNO)-based oxides which have interesting transport, catalytic properties and suitable thermal expansion coefficients. The motivation of this present work is to further understand the fundamental of the effect of Sr doing on the oxygen reduction reaction (ORR) kinetics of LNO cathode. Porous symmetrical cells of La2-xSrxNiO4+delta (0≤x≤0.4) were fabricated and characterized by electrochemical impedance spectroscopy (EIS) in different PO2 from temperature range of 600˜800°C. The spectra were analyzed based on the impedance model introduced by Adler et al. The rate determining steps (RDS) for ORR were proposed and the responsible reasons were discussed. The overall polarization resistances of doped samples increase with Sr level. Surface oxygen exchange and bulk ionic diffusion co-control the ORR kinetics. With high Sr content (x=0.3, 0.4), oxygen ion transfer resistance between nickelate/electrolyte is observed. However for porous symmetrical cells it is hard to associate the resistance from EIS directly to each ORR elementary processes because of the difficulty in describing the microstructure of the porous electrode. The dense electrode configuration was adopted in this thesis. By using the dense electrode, the surface area, the thickness of electrode, the interface between electrode and electrolyte and lastly the 3PB are theoretically well-defined. Through this method, there is a good chance to distinguish the contribution of surface exchange from other processes. Dense and thin electrode layers in thickness of ˜40 mum are fabricated by using a novel spray modified pressing method. Negligible

Luminescent sensing and imaging of oxygen: fierce competition to the Clark electrode.

Science.gov (United States)

Wolfbeis, Otto S

2015-08-01

Luminescence-based sensing schemes for oxygen have experienced a fast growth and are in the process of replacing the Clark electrode in many fields. Unlike electrodes, sensing is not limited to point measurements via fiber optic microsensors, but includes additional features such as planar sensing, imaging, and intracellular assays using nanosized sensor particles. In this essay, I review and discuss the essentials of (i) common solid-state sensor approaches based on the use of luminescent indicator dyes and host polymers; (ii) fiber optic and planar sensing schemes; (iii) nanoparticle-based intracellular sensing; and (iv) common spectroscopies. Optical sensors are also capable of multiple simultaneous sensing (such as O2 and temperature). Sensors for O2 are produced nowadays in large quantities in industry. Fields of application include sensing of O2 in plant and animal physiology, in clinical chemistry, in marine sciences, in the chemical industry and in process biotechnology. © 2015 The Author. Bioessays published by WILEY Periodicals, Inc.

Influence of oxygen on hydrogen storage and electrode properties for micro-designed V-based battery alloys

Energy Technology Data Exchange (ETDEWEB)

Tsukahara, M.; Takahashi, K.; Isomura, A. [Mater. R and D Co., Ltd., Aichi (Japan). IMRA; Sakai, T. [Osaka National Research Institute, Midorigaoka, Ikeda-shi, Osaka, 563 (Japan)

1998-01-30

The influence of oxygen on micro-structure, hydrogen storage and electrode properties were investigated for the alloy V{sub 3}TiNi{sub 0.56}Co{sub 0.14}Nb{sub 0.047}Ta{sub 0.047}. Since titanium in the alloy worked as a deoxidizer to form the oxide phase, the alloy preserved a large hydrogen capacity in the oxygen concentration range below 5000 mass ppm. More oxygen than 6000 mass ppm caused a remarkable contraction of the unit cell of the vanadium-based main phase and then a decrease in the hydrogen storage capacity. The contraction was accompanied by the precipitation of the Ti-based oxide phase. (orig.) 15 refs.

Polarographic determination of Sn (II) and total Sn in PYRO and MDP radiopharmaceutical kits

International Nuclear Information System (INIS)

Sebastian, Maria V.A.; Lugon, Marcelo Di M.V.; Silva, Jose L. da; Fukumori, Neuza T.O.; Pereira, Nilda P.S. de; Silva, Constancia P.G. da; Matsuda, Margareth M.N.

2007-01-01

A sensitive, alternative method to atom absorption spectrometry, fluorimetry or potentiometry for the evaluation of tin(II) ions (0.1- 10 mg) and total tin in radiopharmaceutical kits was investigated. Differential pulse polarography was chosen. The supporting electrolyte was H 2 SO 4 3 mol L -1 and HCl 3 mol L -1 solution. The potential was swept from -250 to -800 mV vs Ag/AgCl/saturated KCl, using a dropping mercury electrode with 1 s drop time, 50 mV s -1 scan rate, -50 mV pulse amplitude, 40 ms pulse time and 10 mV step amplitude. Pure nitrogen was used to deaerate the polarographic cell solution for 5 min, before and after each sample introduction. Oxidation of Sn(II) was made in the same sample vial by adding H 2 O 2 (hydrogen peroxide) 10 mol L -1 , at 37 deg C, in order to quantify the total Sn. The calibration curve for Sn(II) and Sn(IV) was obtained in the concentration range of 0-10 ppm from a 1000 ppm standard solution. The detection limit of Sn(II) is 0.5 ppm and for Sn(IV) is 0.6 ppm. Differential pulse polarography was performed in the pyrophosphate (PYRO) and methylenediphosphonic acid (MDP) radiopharmaceutical kits, containing 2 mg and 1 mg of SnCl 2 .2H 2 O per vial, respectively. The described method for determination of stannous ion (Sn(II)), is selective, reproducible and adequate to be used in the quality control of lyophilized reagents and it shall be performed for other cold kits produced at IPEN. (author)

Selenium and Trace Element Distribution in Astragalus Plants: Developing a Differential Pulse Polarographic Method for Their Determination

OpenAIRE

SOMER, Güler; ÇALIŞKAN, A. Cengiz

2007-01-01

Astragalus plants have a wide range of applications in pharmaceuticals (gum tragacanth), as thickening agents in foods, and may have applications in controlling cancer cells. They are used as feed for animals and they are indicator plants for selenium. Because of their use in health-related areas it is very important to determine their selenium and trace element content with high accuracy. A new differential pulse polarographic method was established for trace element determination (...

FY 1998 annual report on the development of novel, high-activity oxygen electrode by ion-implantation; 1998 nendo ion chunyuho ni yoru shinkina kokassei sanso denkyoku no kaihatsu chosa hokokusho

Energy Technology Data Exchange (ETDEWEB)

NONE

1999-03-01

An attempt has been made to develop an electrode material having high activity for oxygen generating reactions by ion-implantation, which is used to form the bulk defects (fine gaps at the atomic level) on the electrode surface, considered to serve as the active sites. It is found that implantation of the Co{sup +} or Zn{sup +} ion into a compound oxide electrode of Ti and Ru is accompanied by decreased overvoltage for oxygen generation by 50 to 100 mV. The Co{sup +} and Zn{sup +} ions, when implanted, cause damage of similar density in the thin film, decreasing its overvoltage to a similar extent, in spite of their different chemical properties, from which it is considered that the effect of ion implantation is not to change chemical properties of the film but to form a structural defect therein. A thin-film electrode of ruthenium dioxide, which is considered to be the oxygen generating electrode of the highest activity at present, is prepared and implanted with the Ru{sup +} ion, to observe the effect. The ion implantation also decreases the overvoltage by 50 to 70 mV, demonstrating its effect. The same principle is expected to be applicable to development of high-activity oxygen reducing electrode (electrode for fuel cell). (NEDO)

Iodine sorption of bentonite - radiometric and polarographic study

International Nuclear Information System (INIS)

Konirova, R.; Vinsova, H.; Koudelkova, M.; Ernestova, M.; Jedinakova-Krizova, V.

2003-01-01

The experiments focused on kinetics of iodine retardation on bentonite, influence of aqueous phase pH, buffering properties of bentonite, etc. were carried out by batch method. Distribution coefficient KD was the criterion applied for evaluation of iodine interaction with solid phase. High sorption potential of bentonite to cationic forms of various radionuclides, resulting from relatively high cation exchange capacity, is generally known. On the other hand the inorganic anions are not adsorbed strongly to mineral surface of clays thus uptake of iodine (occurring mainly at iodide (I - ) or iodate (IO 3 - ) form under oxoic conditions) is limited. The distribution coefficients of iodine anions' sorption on bentonite R reach order of magnitude 10 -1 mL/g. In order to increase the sorption capacity of the solid phase, several additives were added to bentonite. Most of them didn't provide satisfactory results except of the addition of activated carbon, which has high surface area. Electromigration and polarographic methods were used for investigation of the redox state of iodine in aqueous phase and determination of KD values as well. Acquired results were compared with data obtained by radiometric measurements. (authors)

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.

Electrochemical reduction of oxygen on small platinum particles supported on carbon in concentrated phosphoric acid. 2. Effects of teflon content in the catalyst layer and baking temperature of the electrode

Energy Technology Data Exchange (ETDEWEB)

Maoka, T.

1988-03-01

A relation between hydrophobicity (or wettability) of a porous gas diffusion electrode for use in a phosphoric acid fuel cell and its cathode performance (activity toward electrochemical oxygen reduction) was examined. The hydrophobicity of the gas diffusion electrode was regulated by changing either the amount of Teflon (PTFE) content in the catalyst layer or baking temperature of the electrode. The Tafel slope or electrochemical oxygen reduction became twice as high as that of the ordinary electrode when the wettability of electrode toward phosphoric acid was high. This fact supports a flooded agglomerate model as the mode of this type of porous gas diffusion electrode.

In Situ Characterization of Ni and Ni/Fe Thin Film Electrodes for Oxygen Evolution in Alkaline Media by a Raman-Coupled Scanning Electrochemical Microscope Setup.

Science.gov (United States)

Steimecke, Matthias; Seiffarth, Gerda; Bron, Michael

2017-10-17

We present a spectroelectrochemical setup, in which Raman microscopy is combined with scanning electrochemical microscopy (SECM) in order to provide both spectroscopic and electrochemical information on the very same location of an electrode at the same time. The setup is applied to a subject of high academic and practical interest, namely, the oxygen evolution reaction at Ni and Ni/Fe electrodes. It comprises a transparent substrate electrode, onto which Ni and Ni/Fe thin films are deposited. An ultramicroelectrode (UME) is placed closely above the substrate to obtain electrochemical information, while a Raman microscope probes the same sample spot from below. To obtain information on oxygen evolution activity and structural changes, increasingly positive potentials from 0.1 up to 0.7 V vs Hg|HgO|1 M KOH were applied to the Ni/Fe-electrodes in 0.1 M KOH solution. Evolved oxygen is detected by reduction at a Pt UME, allowing for the determination of onset potentials, while the substrate current, which is recorded in parallel, is due to both overlapping oxygen evolution and the oxidation of Ni(OH) 2 to NiOOH. An optimum of 15% Fe in Ni/Fe films with respect to oxygen evolution activity was determined. At the same time, the potential-dependent formation of γ-NiOOH characterized by the Raman double band at 475 and 557 cm -1 allows for the conclusion that a certain amount of disorder introduced by Fe atoms is necessary to obtain high oxygen evolution reaction (OER) activity.

Proton translocation stoichiometry of cytochrome oxidase: use of a fast-responding oxygen electrode.

Science.gov (United States)

Reynafarje, B; Alexandre, A; Davies, P; Lehninger, A L

1982-01-01

The mechanistic stoichiometry of vectorial H+ ejection coupled to electron transport from added ferrocytochrome c to oxygen by the cytochrome oxidase (EC 1.9.3.1) of rat liver mitoplasts was determined from measurements of the initial rates of electron flow and H+ ejection in the presence of K+ (with valinomycin). Three different methods of measuring electron flow were used: (a) dual-wavelength spectrophotometry of ferrocytochrome c oxidation, (b) uptake of scalar H+ for the reduction of O2 in the presence of a protonophore, and (c) a fast-responding membraneless oxygen electrode. The reliability of the rate measurements was first established against the known stoichiometry of the scalar reaction of cytochrome oxidase (2ferrocytochrome c + 2H+ + 1/2O2 leads to 2ferricytochrome c + H2O) in the presence of excess protonophore. With all three methods the directly observed vectorial H+/O ejection ratios in the presence of K+ + valinomycin significantly exceeded 3.0. However, because the rate of backflow of the ejected H+ into the mitoplasts is very high and increases with the increasing delta pH generated across the membrane, there is a very rapid decline in the observed H+/O ratio from the beginning of the reaction. Kinetic analysis of ferrocytochrome c oxidation by the mitoplasts, carried out with a fast-responding membraneless oxygen electrode, showed the reaction to be first order in O2 and allowed accurate extrapolation of the rates of O2 uptake and H+ ejection to zero time. At this point, at which there is zero delta pH across the membrane, the H+/O ejection ratio of the cytochrome oxidase reaction, obtained from the rates at zero time, is close to 4.0. PMID:6296824

A New Optic Technology for Measuring Oxygen Dissolved in Water: Luminescence Dissolved Oxygen (LDO); Nueva tecnologia optica para la medicion de oxigeno disuelto en agua: oxigeno disuelto por luminiscencia (LDO)

Energy Technology Data Exchange (ETDEWEB)

NONE

2003-07-01

Continual measurement of oxygen in the active sludge tank is a very important parameter is the biological treatment of waste waters. Traditional electrochemical sensors are based on polarographic or galvanic cells, a technique which produces electrolyte consumption and progressive deterioration of the anode. Both effects inevitable lead to a drift in the measurement signal, which requires periodical calibration. Lange has developed a completely new technique for its new LDO sensor for measuring oxygen concentration in waste waters. This technique is based on the luminescent radiation of a luminescent substance (luminophore) and reduces the determination to the purely physical measurement of time, so that, in theory it is free of drift and there is no need for the use to calibrate the sensor. (Author)

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)

Complete Decomposition of Li ₂ CO ₃ in Li–O ₂ Batteries Using Ir/B ₄ C as Noncarbon-Based Oxygen Electrode

Energy Technology Data Exchange (ETDEWEB)

Song, Shidong; Xu, Wu; Zheng, Jianming; Luo, Langli; Engelhard, Mark H.; Bowden, Mark E.; Liu, Bin; Wang, Chong-Min; Zhang, Ji-Guang

2017-02-10

Incomplete decomposition of Li2CO3 during charge process is a critical barrier for rechargeable Li-O2 batteries. Here we report complete decomposition of Li2CO3 in Li-O2 batteries using ultrafine iridium-decorated boron carbide (Ir/B4C) nanocomposite as oxygen electrode. The systematic investigation on charging the Li2CO3 preloaded Ir/B4C electrode in an ether-based electrolyte demonstrates that Ir/B4C electrode can decompose Li2CO3 with an efficiency close to 100% at below 4.37 V. In contrast, the bare B4C without Ir electrocatalyst can only decompose 4.7% of preloaded Li2CO3. The reaction mechanism of Li2CO3 decomposition in the presence of Ir/B4C electrocatalyst has been further investigated. A Li-O2 battery using Ir/B4C as oxygen electrode material shows highly enhanced cycling stability than that using bare B4C oxygen electrode. These results clearly demonstrate that Ir/B4C is an effecitive oxygen electrode amterial to completely decompose Li2CO3 at relatively low charge voltages and is of significant importance in improving the cycle performanc of aprotic Li-O2 batteries.

Interplay of tumor vascular oxygenation and tumor pO2 observed using near-infrared spectroscopy, an oxygen needle electrode, and 19F MR pO2 mapping.

Science.gov (United States)

Kim, Jae G; Zhao, Dawen; Song, Yulin; Constantinescu, Anca; Mason, Ralph P; Liu, Hanli

2003-01-01

This study investigates the correlation of tumor blood oxygenation and tumor pO(2) with respect to carbogen inhalation. After having refined and validated the algorithms for calculating hemoglobin concentrations, we used near-infrared spectroscopy (NIRS) to measure changes of oxygenated hemoglobin concentration (delta[HbO(2)]) and used an oxygen needle electrode and (19)F MRI for pO(2) measurements in tumors. The measurements were taken from Dunning prostate R3327 tumors implanted in rats, while the anesthetized rats breathed air or carbogen. The NIRS results from tumor measurements showed significant changes in tumor vascular oxygenation in response to carbogen inhalation, while the pO(2) electrode results showed an apparent heterogeneity for tumor pO(2) response to carbogen inhalation, which was also confirmed by (19)F MR pO(2) mapping. Furthermore, we developed algorithms to estimate hemoglobin oxygen saturation, sO(2), during gas intervention based on the measured values of delta[HbO(2)] and pO(2). The algorithms have been validated through a tissue-simulating phantom and used to estimate the values of sO(2) in the animal tumor measurement based on the NIRS and global mean pO(2) values. This study demonstrates that the NIRS technology can provide an efficient, real-time, noninvasive approach to monitoring tumor physiology and is complementary to other techniques, while it also demonstrates the need for an NIR imaging technique to study spatial heterogeneity of tumor vasculature under therapeutic interventions. Copyright 2003 Society of Photo-Optical Instrumentation Engineers

Ultrasound guided pO2 measurement of breast cancer reoxygenation after neoadjuvant chemotherapy and hyperthermia treatment.

Science.gov (United States)

Vujaskovic, Z; Rosen, E L; Blackwell, K L; Jones, E L; Brizel, D M; Prosnitz, L R; Samulski, T V; Dewhirst, M W

2003-01-01

The objective of this study was to determine whether neoadjuvant chemotherapy in combination with hyperthermia (HT) would improve oxygenation in locally advanced breast tumours. The study describes a new optimized ultrasound guided technique of pO2 measurement using Eppendorf polarographic oxygen probes in 18 stage IIB-III breast cancer patients. Prior to treatment, tumour hypoxia (median pO2pO2=3.2 mmHg). Seven patients had well oxygenated tumours (median pO2 of 48.3 mmHg). Eight patients with hypoxic tumours prior to treatment had a significant improvement (p=0.0008) in tumour pO2 after treatment (pO2 increased to 19.2 mmHg). In three patients, tumours remained hypoxic (average median pO2=4.5 mmHg). The advantages of the ultrasound guided pO2 probe are in the accuracy of the Eppendorf electrode placement in tumour tissue, the ability to monitor electrode movement through the tumour tissue during the measurement and the ability to avoid electrode placement near or in large blood vessels by using colour Doppler imaging. The results of this preliminary study suggest that the combination of neoadjuvant chemotherapy and hyperthermia improves oxygenation in locally advanced breast tumours that are initially hypoxic.

Polarographic behaviour and determination of selenite and tellurite in simple solutions or in a binary mixture

International Nuclear Information System (INIS)

Hassan, A.

1991-01-01

The polarographic behaviour of simple solutions of selenite and tellurite in 1 M ammonium salts of formate, acetate, tartrate, oxalate, and benzoate solutions in absence and in presence of Triton X-100 as a maximum suppressor and a temperature of 25 O C has been investigated. Schemes for the mechanism of reductions occuring at the DME have been deduced. A method for analytical determination of selenite and tellurite in simple solutions as well as in a binary mixture in the presence of 4-14 . 10 -3 % Triton X-100 is reported. (author)

Tailoring nanomaterial products through electrode material and oxygen partial pressure in a mini-arc plasma reactor

International Nuclear Information System (INIS)

Cui Shumao; Mattson, Eric C.; Lu, Ganhua; Hirschmugl, Carol; Gajdardziska-Josifovska, Marija; Chen Junhong

2012-01-01

Nanomaterials with controllable morphology and composition are synthesized by a simple one-step vapor condensation process using a mini-arc plasma source. Through systematic investigation of mini-arc reactor parameters, the roles of carrier gas, electrode material, and precursor on producing diverse nanomaterial products are revealed. Desired nanomaterial products, including tungsten oxide nanoparticles (NPs), tungsten oxide nanorods (NRs), tungsten oxide and tin oxide NP mixtures and pure tin dioxide NPs can thus be obtained by tailoring reaction conditions. The amount of oxygen in the reactor is critical to determining the final nanomaterial product. Without any precursor material present, a lower level of oxygen in the reactor favors the production of W 18 O 49 NRs with tungsten as cathode, while a high level of oxygen produces more round WO 3 NPs. With the presence of a precursor material, amorphous particles are favored with a high ratio of argon:oxygen. Oxygen is also found to affect tin oxide crystallization from its amorphous phase in the thermal annealing. Results from this study can be used for guiding gas phase nanomaterial synthesis in the future.

Electrochemical characterisation of solid oxide cell electrodes for hydrogen production

DEFF Research Database (Denmark)

Bernuy-Lopez, Carlos; Knibbe, Ruth; He, Zeming

2011-01-01

Oxygen electrodes and steam electrodes are designed and tested to develop improved solid oxide electrolysis cells for H2 production with the cell support on the oxygen electrode. The electrode performance is evaluated by impedance spectroscopy testing of symmetric cells at open circuit voltage (OCV...

Hydrogen Oxidation on Gas Diffusion Electrodes for Phosphoric Acid Fuel Cells in the Presence of Carbon Monoxide and Oxygen

DEFF Research Database (Denmark)

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

1995-01-01

Hydrogen oxidation has been studied on a carbon-supported platinum gas diffusion electrode in a phosphoric acidelectrolyte in the presence of carbon monoxide and oxygen in the feed gas. The poisoning effect of carbon monoxide presentin the feed gas was measured in the temperature range from 80...... to 150°C. It was found that throughout the temperaturerange, the potential loss due to the CO poisoning can be reduced to a great extent by the injection of small amounts ofgaseous oxygen into the hydrogen gas containing carbon monoxide. By adding 5 volume percent (v/o) oxygen, an almost...

Control of oxygen octahedral rotation in BiFeO3 films using modulation of SrRuO3 bottom electrode layer

Science.gov (United States)

Lee, Sungsu; Jo, Ji Young

2015-03-01

Oxygen octahedral rotation of multiferroic BiFeO3 (BFO) has attracted great attention due to changes of electrical and magnetic properties. Coupling of octahedral rotation in BFO-bottom electrode layer interface remains unexplored. Recently, there have been reported the control of octahedral rotation in SrRuO3 (SRO) film on SrTiO3 (001) substrate by coherently controlling the oxygen pressure during growth and interfacial coupling. Here we demonstrate that the octahedral rotation of BFO film is changed using tetragonal a0a0c- tilted-SRO bottom electrodes. In this work, BFO/SRO heterostructure is fabricated to SrTiO3 (001) single crystal substrates by pulsed laser deposition at different oxygen partial pressures. The rotation pattern of FeO6 and the structural symmetry are identified from half-integer reflections using high-resolution X-ray diffraction. The effects depending on octahedral tilting of BFO films on the magnetic and ferroelectric properties will be presented.

Bifunctional electrodes for unitised regenerative fuel cells

International Nuclear Information System (INIS)

Altmann, Sebastian; Kaz, Till; Friedrich, Kaspar Andreas

2011-01-01

Research highlights: → Different oxygen electrode configurations for the operation in a unitised reversible fuel cell were tested. → Polarisation curves and EIS measurements were recorded. → The mixture of catalysts performs best for the present stage of electrode development. → Potential improvements for the different compositions are discussed. - Abstract: The effects of different configurations and compositions of platinum and iridium oxide electrodes for the oxygen reaction of unitised regenerative fuel cells (URFC) are reported. Bifunctional oxygen electrodes are important for URFC development because favourable properties for the fuel cell and the electrolysis modes must be combined into a single electrode. The bifunctional electrodes were studied under different combinations of catalyst mixtures, multilayer arrangements and segmented configurations with single catalyst areas. Distinct electrochemical behaviour was observed for both modes and can be explained on the basis of impedance spectroscopy. The mixture of both catalysts performs best for the present stage of electrode development. Also, the multilayer electrodes yielded good results with the potential for optimisation. The influence of ionic and electronic resistances on the relative performance is demonstrated. However, penalties due to cross currents in the heterogeneous electrodes were identified and explained by comparing the performance curves with electrodes composed of a single catalyst. Potential improvements for the different compositions are discussed.

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)

Stability of a Cu0.7Co2.3O4 electrode during the oxygen evolution reaction for alkaline anion-exchange membrane water electrolysis

Science.gov (United States)

Kang, Kyoung Eun; Kim, Chi Ho; Lee, Myung Sup; Jung, Chang Wook; Kim, Yang Do; Lee, Jae Ho

2018-01-01

The electrode materials for oxygen evolution, especially non-platinum group metal oxides, have attracted increasing attention. Among the spinel-type transition metal oxides, Cu0.7Co2.3O4 powders were evaluated as a potential replacement for expensive dimensionally stabilized anode materials. Cu0.7Co2.3O4 powder for use as an electrode material for oxygen evolution in an alkaline anion-exchange membrane water electrolyzer was prepared using a thermal decomposition method. The Cu0.7Co2.3O4 powders heat-treated at 250 °C exhibited the same X-ray diffraction patterns without any secondary phases as the Co3O4 spinel structure did. The Cu0.7Co2.3O4 powders heat-treated at 250 °C for 30 minutes showed the smallest mean particle size of approximately 376 nm with the powders having a homogeneous shape and size distribution. The fine powders with a relatively homogeneous size distribution showed a higher current density during the oxygen evolution reaction. The lifetime of the Cu0.7Co2.3O4 electrode was relatively long at a low current density, but was quickly shortened due to physical detachment of the Cu0.7Co2.3O4 powders as the current density was increased. This study showed that the efficiency and the stability of Cu0.7Co2.3O4 powders during the oxygen evolution reaction were related directly to the active electrode area.

Regional perfusion and oxygenation of tumors upon methylxanthine derivative administration

International Nuclear Information System (INIS)

Kelleher, Debra K.; Thews, Oliver; Vaupel, Peter

1998-01-01

Purpose: The use of methylxanthine derivatives has been postulated as a means of increasing tumor perfusion and thus ameliorating tumor hypoxia. The aim of this study was to quantify and compare the effects of three methylxanthine derivatives: pentoxifylline (PX), torbafylline (TB), and HWA 138 (HW) on tumor perfusion and oxygenation. Methods and Materials: Anesthetized Sprague Dawley rats with DS-sarcomas implanted subcutaneously onto the hind foot dorsum were used in this study. Mean arterial blood pressure (MABP) was measured throughout experiments. Regional red blood cell (RBC) flux was monitored using a multichannel laser Doppler device and tumor oxygenation on a more global level was assessed polarographically using an O 2 -sensitive catheter electrode. The methylxanthine derivatives were administered as a single dose intraperitoneally (for PX 50 mg/kg; for TB and HW 75 mg/kg). Results: Following drug administration, initial decreases in MABP down to 75% of baseline values were observed for all three substances. PX, HW, and TB caused initial transient reductions in mean RBC flux followed by gradual increases to values of 137 ± 27 %, 139 ± 14 %, and 122 ± 14 % respectively at t = 60 min. Following a small initial decrease upon drug administration, O 2 partial pressure (pO 2 ) rose to 160 ± 31 %, 153 ± 34 %, and 121 ± 11 % for PX, HW, and TB, respectively at t = 60 min. At the end of the observation period (t = 90 min), increases in RBC flux and pO 2 were still evident. When individual tumors were considered, a variety of patterns (including opposing effects) for changes in RBC flux were seen, not necessarily reflected in the mean values. Thus, while the methylxanthine derivatives caused an increased average tumor perfusion, there is evidence suggesting that a redistribution of tumor blood flow occurs which may amplify preexisting heterogeneity. Conclusions: Substantial improvements in tumor oxygenation and perfusion were observed after administration of

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.

Fluctuations at electrode-YSZ interfaces

DEFF Research Database (Denmark)

Jacobsen, Torben; Hansen, Karin Vels; Skou, Eivind

2005-01-01

Current fluctuations at potentiostatically controlled point electrodes of Pt, La$_{0.85}$Sr$_{0.15}$MnO$_3$ and Ni on YSZ surfaces are determined at 1000$^\\circ$C. For the oxygen reduction process on Pt electrodes characteristic sawtooth shaped low frequency fluctuations are observed. At temperat......Current fluctuations at potentiostatically controlled point electrodes of Pt, La$_{0.85}$Sr$_{0.15}$MnO$_3$ and Ni on YSZ surfaces are determined at 1000$^\\circ$C. For the oxygen reduction process on Pt electrodes characteristic sawtooth shaped low frequency fluctuations are observed....../water atmosphere are presented for discussion. The origin of the observations is not known at present but it appears likely that they are related to the activation/deactivation mechanism of SOFCs....

Inkjet printing of nanoporous gold electrode arrays on cellulose membranes for high-sensitive paper-like electrochemical oxygen sensors using ionic liquid electrolytes.

Science.gov (United States)

Hu, Chengguo; Bai, Xiaoyun; Wang, Yingkai; Jin, Wei; Zhang, Xuan; Hu, Shengshui

2012-04-17

A simple approach to the mass production of nanoporous gold electrode arrays on cellulose membranes for electrochemical sensing of oxygen using ionic liquid (IL) electrolytes was established. The approach, combining the inkjet printing of gold nanoparticle (GNP) patterns with the self-catalytic growth of these patterns into conducting layers, can fabricate hundreds of self-designed gold arrays on cellulose membranes within several hours using an inexpensive inkjet printer. The resulting paper-based gold electrode arrays (PGEAs) had several unique properties as thin-film sensor platforms, including good conductivity, excellent flexibility, high integration, and low cost. The porous nature of PGEAs also allowed the addition of electrolytes from the back cellulose membrane side and controllably produced large three-phase electrolyte/electrode/gas interfaces at the front electrode side. A novel paper-based solid-state electrochemical oxygen (O(2)) sensor was therefore developed using an IL electrolyte, 1-butyl-3-methylimidazolium hexafluorophosphate (BMIMPF(6)). The sensor looked like a piece of paper but possessed high sensitivity for O(2) in a linear range from 0.054 to 0.177 v/v %, along with a low detection limit of 0.0075% and a short response time of less than 10 s, foreseeing its promising applications in developing cost-effective and environment-friendly paper-based electrochemical gas sensors.

New electrodes for hydrogen/oxygen solid polymer electrolyte fuel cell

Energy Technology Data Exchange (ETDEWEB)

Mosdale, R [CEA Centre d` Etudes de Grenoble, 38 (France). Dept. de Recherche Fondamentale sur la Matiere Condensee; Stevens, P [CEA Centre d` Etudes de Grenoble, 38 (France). Dept. de Thermohydraulique et de Physique

1993-12-31

A new method of preparation of Electrode/Membrane/Electrode (EME) assemblies for Proton Exchange Membrane Fuel Cells (PEMFC) has been developed. The electrodes are deposited directly onto a Nafion electrolyte membrane from a mixture of platinized carbon, Nafion solution, and PTFE by using a spray technique. By this technique, porous electrodes are obtained with an optimized gas/electrolyte/catalyst interface, and electrode/membrane interface.

Imprint and oxygen deficiency in (Pb,La)(Zr,Ti)O3 thin-film capacitors with La-Sr-Co-O electrodes

International Nuclear Information System (INIS)

Lee, J.; Ramesh, R.; Keramidas, V.G.; Warren, W.L.; Pike, G.E.; Evans, J.T. Jr.

1995-01-01

La-Sr-Co-O/Pb-La-Zr-Ti-O/La-Sr-Co-O thin-film capacitors have been grown in various oxygen ambients by pulsed laser deposition. As the oxygen ambient became more reducing, the capacitors developed more voltage asymmetry in hysteresis loops and a more preferred polarization state directed towards the top electrode. PLZT capacitors cooled in a fully oxidizing atmosphere (i.e., 1 atm oxygen pressure) exhibited nominally symmetric hysteresis loops and also showed little imprint both with and without fully saturating bias fields. We find that ambient oxygen pressure is an important process parameter and the imprint behavior is closely related with ambient oxygen induced effects such as oxygen vacancies, its related defect-dipole complexes and trapping of free charges. The different imprint behavior under negative and positive bias also suggests that the dipolar-defect complexes tend to cause imprint in PLZT capacitors

Discrepancies between measured changes of radiobiological hypoxic fraction and oxygen tension monitoring using two assay systems

International Nuclear Information System (INIS)

Sasai, K.; Brown, J.M.

1994-01-01

This study was conducted to assess the ability of computerized pO 2 histography to measure changes in tumor oxygenation produced by low oxygen breathing. Female syngeneic C3H/Km mice bearing SCC VII/St carcinomas were used in these experiments. Changes in tumor oxygenation produced by the mice breathing 10% oxygen were assessed with computerized pO2 histography, 3 H-misonidazole binding, and the paired survival curve assay of radiosensitivity. The hypoxic cell fraction of the tumors in mice breathing 10% oxygen was 3.1 times higher than that of tumors in mice breathing normal air determined by an in vivo-in vitro clonogenic assay. Binding of radiolabeled misonidazole to the tumors in mice breathing 10% oxygen was also significantly higher than that to tumors in mice breathing normal air (p 2 value for the tumor. The number of pO 2 readings lower than 5 mmHg in the tumor was not affected by the 10% oxygen breathing. These findings indicate that increases in radiobiological hypoxic fraction produced by lower blood oxygen levels may not correlate well with the results of polarographic measurements of tumor pO 2 levels. 29 refs., 4 figs., 1 tab

Persistent increase in oxygen consumption and impaired neurovascular coupling after spreading depression in rat neocortex

DEFF Research Database (Denmark)

Hansen, Henning Piilgaard; Lauritzen, Martin

2009-01-01

trauma. Here we tested the hypothesis that single episodes of CSD induced acute hypoxia, and prolonged impairment of neurovascular and neurometabolic coupling. Cortical spreading depression was induced in rat frontal cortex, whereas cortical electrical activity and local field potentials (LFPs) were......Cortical spreading depression (CSD) is associated with a dramatic failure of brain ion homeostasis and increased energy metabolism. There is strong clinical and experimental evidence to suggest that CSD is the mechanism of migraine, and involved in progressive neuronal injury in stroke and head...... recorded by glass microelectrodes, cerebral blood flow (CBF) by laser-Doppler flowmetry, and tissue oxygen tension (tpO(2)) with polarographic microelectrodes. Cortical spreading depression increased cerebral metabolic rate of oxygen (CMRO(2)) by 71%+/-6.7% and CBF by 238%+/-48.1% for 1 to 2 mins...

Preparation and Characterization of Nicke-iron Alloy Film as Freestanding Electrode for Oxygen Evolution Reaction

Directory of Open Access Journals (Sweden)

Yao Mengqi

2018-01-01

Full Text Available This work reports the porous nicke-iron alloy film supported on stainless steel mesh as freestanding electrode for enhanced oxygen evolution reaction (OER catalyst prepared from an one step electrodeposition method. Results indicated that the porous nickle-iron alloy film exhibits a low overpotential of 270 mV at 10 mA cm-2 and excellent electroconductibility. The superior OER properties can be attributed to its novel synthetic process, conductive substrate and porous structure. This work will provide a new strategy to fabricate alloy film for OER electrocatalyst.

Oxygen electrodes for energy conversion and storage. Annual report, 1 October 1977-30 September 1978

Energy Technology Data Exchange (ETDEWEB)

None

1980-01-15

Research on the development of high performance, long life O/sub 2/ cathodes for both alkaline and acid electrolytes for a spectrum of applications including industrial electrolysis, fuel cells, and metal-air batteries is described. Oxygen electrocatalysts studied include platinum, silver, underpotential deposited layers and alloy metal layers on noble metal substrates, intercalated graphite, transition metal macrocyclic complexes, and transition metal oxides. Research on gas fed electrodes is also described. Results are presented and discussed in detail. An appendix on the electrodeposition of platinum crystallites on graphite substrates is included. (WHK)

Comparative Photoelectrochemical Study of PEC Solar Cell Fabricated with n-TiO2 Photo-electrodes at Different Temperatures and under Different Oxygen Flow Rates

International Nuclear Information System (INIS)

Mishra, P.R.; Srivastava, O.N.; Shukla, P.K.

2006-01-01

Photoelectrochemical splitting of water induced by solar energy for hydrogen production has been studied in the present investigation. PEC solar cell was fabricated with n-TiO 2 photo-electrodes synthesized at different oxidation temperatures e.g. 700 C, 750 C, 800 C and 850 C under oxygen flow rate 200 ml/min, 350 ml/min and 500 ml/min. The optimum oxygen flow rate for all the temperatures was found to be 350 ml/min. This is therefore kept invariant for synthesis of electrodes at different temperatures. The photo-electrochemical characterization of the PEC cell was done in the three-electrode configuration, i.e Ti/n-TiO 2 /1M-NaOH/Pt. It has been observed that the optimum values of the PEC solar cell parameters are exhibited by the solar cell employing the photo-electrodes prepared at ∼7500 C. The XRD and SEM explorations revealed that the TiO 2 prepared at ∼7500 C is in the nano-metric range (∼100-150 nm). The TiO 2 films formed at this temperature has been found to exhibit optimum PEC solar cell parameters. The PEC parameters, like photocurrent density, photo-conversion efficiency and hydrogen production rate, with this photo-electrode correspond to 0.93 mA/cm 2 , 0.472% and 4.00 l/hm 2 respectively. (authors)

Effect of pH and Water Structure on the Oxygen Reduction Reaction on platinum electrodes

International Nuclear Information System (INIS)

Briega-Martos, Valentín; Herrero, Enrique; Feliu, Juan M.

2017-01-01

The oxygen reduction reaction (ORR) at different pH values has been studied at platinum single crystal electrodes using the hanging meniscus rotating disk electrode (HMRDE) configuration. The use of NaF/HClO 4 mixtures allows investigating the reaction up to pH = 6 in solutions with enough buffering capacity and in the absence of anion specific adsorption. The analysis of the currents shows that the kinetic current density measured at 0.85 V for the Pt(111) electrode follows a volcano curve with the maximum located around pH = 9. This maximum activity for pH = 9 can be related to the effects of the electrode charge and/or water structure in the ORR. On the other hand, the catalytic activity for the other basal planes shows a monotonic behavior with a small dependence of the activity with pH. For stepped surfaces with (111) terraces, the behavior with pH changes gets closer to that of the Pt(111) surface as the terrace length increases. Additionally, the ORR curves show a dependence of the limiting diffusion current with pH. It is observed that the limiting current density diminishes as the pH increases in a potential region where hydrogen peroxide is readily reduced. These results suggest the existence of a bifurcation point in the mechanism previous to peroxide formation, in which OOH • is proposed as the bifurcation intermediate. The reduction of OOH • requires proton addition and would be more difficult at neutral pH values, justifying the diminution of the limiting currents.

Polarographic study of the Cu(II)/Cu(I) system in the presence of 1-ascorbic acid and 0,1 M ClK

International Nuclear Information System (INIS)

Alonso Lopez, J.

1969-01-01

While studying the catalytic effect of Cu ↓ 2 ions on the oxidation process of 1-ascorbic acid, it has been observed that, in a 0,1 M solution of K1 at a pH 6 to 7, the above acid gives rise in the presence of Cu ↓ 2 ions to a polarographic wave of half-wave potential of -0,41 V (vs. S.C.E.). (Author) 14 refs

Suppressed Sr segregation and performance of directly assembled La0.6Sr0.4Co0.2Fe0.8O3-δ oxygen electrode on Y2O3-ZrO2 electrolyte of solid oxide electrolysis cells

Science.gov (United States)

Ai, Na; He, Shuai; Li, Na; Zhang, Qi; Rickard, William D. A.; Chen, Kongfa; Zhang, Teng; Jiang, San Ping

2018-04-01

Active and stable oxygen electrode is probably the most important in the development of solid oxide electrolysis cells (SOECs) technologies. Herein, we report the successful development of mixed ionic and electronic conducting (MIEC) La0.6Sr0.4Co0.2Fe0.8O3-δ (LSCF) perovskite oxides directly assembled on barrier-layer-free yttria-stabilized zirconia (YSZ) electrolyte as highly active and stable oxygen electrodes of SOECs. Electrolysis polarization effectively induces the formation of electrode/electrolyte interface, similar to that observed under solid oxide fuel cell (SOFC) operation conditions. However, in contrast to the significant performance decay under SOFC operation conditions, the cell with directly assembled LSCF oxygen electrodes shows excellent stability, tested for 300 h at 0.5 A cm-2 and 750 °C under SOEC operation conditions. Detailed microstructure and phase analysis reveal that Sr segregation is inevitable for LSCF electrode, but anodic polarization substantially suppresses Sr segregation and migration to the electrode/electrolyte interface, leading to the formation of stable and efficient electrode/electrolyte interface for water and CO2 electrolysis under SOECs operation conditions. The present study demonstrates the feasibility of using directly assembled MIEC cobaltite based oxygen electrodes on barrier-layer-free YSZ electrolyte of SOECs.

Oxygen status of cervical cancers prior and during definitive radiotherapy: possible impact of pretreatment with INF-α-2a/retinol acid on oxygenation

International Nuclear Information System (INIS)

Haensgen, Gabriele; Haensgen, Klaus; Dunst, Juergen

1996-01-01

Objective: Modern techniques have raised the possibility to measure intratumoral pO 2 with needle electrodes. We have investigated the oxygenation status of cervical cancers in patients undergoing definitive radiotherapy. Materials and Methods: From July 1995 through February 1996, 28 patients with squamous cell carcinoma of the cervix uteri FIGO II/III underwent polarographic measurement of tumor oxygenation prior to and during definitive radiotherapy. All received combined external irradiation and HDR-brachytherapy. 14 patients were enrolled in a phase II-protocol and received additional treatment with interferon-alpha-2a (INF-α-2a, daily dose 6x10 6 IU s.c. over 12 days) and cis-retinol acid (cRA, daily dose 1 mg/kg orally) starting 12 days before radiotherapy. During radiotherapy, INF-α-2a was given three times weekly in a dosage of 3x10 6 IU s.c. and cRA in daily doses of 0.5 mg/kg. Tumor oxygenation was measured with an Eppendorf-pO 2 -histograph prior to radiotherapy, after 20Gy and after completion of radiotherapy. Results: We found a broad range of pO 2 -values in the 28 patients. Significant hypoxic areas were detectable in about one third of the patients. The mean and median pO 2 -values did not correlate with tumor stage or tumor volume. At the beginning of radiotherapy, the patients with INF-α-2a/cRA-pretreatment had significant higher mean pO 2 -values as compared to patients without INF-α-2a/cRA-pretreatment: mean pO 2 34.7 ± 25.9 mmHg versus 18.0 ± 9.9 mmHg, p=0.03, median pO 2 28.6 versus 17.3 mmHg). Only two patients had pO 2 -measurements before and after INF-α-2a/cRA-pretreatment; in both the mean pO 2 increased threefold during INF-α-2a/cRA. During radiotherapy, the median pO 2 -value increased in both groups of patients. In patients with primary hypoxia, different patterns of oxygenation were detectable after 20Gy showing persistent hypoxia or an increase in the mean pO 2 . Persistent hypoxia without 'reoxygenation' was associated with

Cobalt phthalocyanine modified electrodes utilised in electroanalysis: nano-structured modified electrodes vs. bulk modified screen-printed electrodes.

Science.gov (United States)

Foster, Christopher W; Pillay, Jeseelan; Metters, Jonathan P; Banks, Craig E

2014-11-19

Cobalt phthalocyanine (CoPC) compounds have been reported to provide electrocatalytic performances towards a substantial number of analytes. In these configurations, electrodes are typically constructed via drop casting the CoPC onto a supporting electrode substrate, while in other cases the CoPC complex is incorporated within the ink of a screen-printed sensor, providing a one-shot economical and disposable electrode configuration. In this paper we critically compare CoPC modified electrodes prepared by drop casting CoPC nanoparticles (nano-CoPC) onto a range of carbon based electrode substrates with that of CoPC bulk modified screen-printed electrodes in the sensing of the model analytes L-ascorbic acid, oxygen and hydrazine. It is found that no "electrocatalysis" is observed towards L-ascorbic acid using either of these CoPC modified electrode configurations and that the bare underlying carbon electrode is the origin of the obtained voltammetric signal, which gives rise to useful electroanalytical signatures, providing new insights into literature reports where "electrocatalysis" has been reported with no clear control experiments undertaken. On the other hand true electrocatalysis is observed towards hydrazine, where no such voltammetric features are witnessed on the bare underlying electrode substrate.

High capacity V-based metal hydride electrodes for rechargeable batteries

OpenAIRE

Yang, Heng; Weadock, Nicholas J.; Tan, Hongjin; Fultz, Brent

2017-01-01

We report the successful development of Ti_(29)V_(62−x)Ni_9Cr_x (x = 0, 6, 12) body centered cubic metal hydride (MH) electrodes by addressing vanadium corrosion and dissolution in KOH solutions. By identifying oxygen as the primary source of corrosion and eliminating oxygen with an Ar-purged cell, the Cr-free Ti_(29)V_(62)Ni_9 alloy electrode achieved a maximum capacity of 594 mAh g^(-1), double the capacity of commercial AB_5 MH electrodes. With coin cells designed to minimize oxygen evolut...

Polarographic investigation of complexing kinetics of polyacrylate anions with cadmium ions. Polyarograficheskoe issledovanie kinetiki kompleksoobrazovaniya poliakrilat-anionov s ionami kadmiya

Energy Technology Data Exchange (ETDEWEB)

Avlyanov, Zh K; Kabanov, N M; Zezin, A B; Askarov, M A

1990-01-01

The processes which occur during the reduction of cadmium ions from polymer-metallic complexes (PMC) are studied for the purposes of polarographic investigation of complexing kinetics of polyacrylate anions (PAA) of different molecular masses with cadmium ions in KCl aqueous solutions. An expression is derived for establishing semiwave potential. PMC formation and dissociation reduction rate constants are calculated. It is shown that intramolecular reorderings required for the formation of a two-coordinate complex proceed much slower as compared to the diffusion of free ions.

Topotactic Consolidation of Monocrystalline CoZn Hydroxides for Advanced Oxygen Evolution Electrodes.

Science.gov (United States)

Wang, Jing; Tan, Chuan Fu; Zhu, Ting; Ho, Ghim Wei

2016-08-22

We present a room temperature topotactic consolidation of cobalt and zinc constituents into monocrystalline CoZn hydroxide nanosheets, by a localized corrosion of zinc foils with cobalt precursors. By virtue of similar lattice orientation and structure coordination, the hybrid hydroxides amalgamate atomically without phase separation. Importantly, this in situ growth strategy, in combination with configurable percolated nanosheets, renders a high areal density of catalytic sites, immobilized structures, and conductive pathways between the nanosheets and underlying foils-all of which allow monocrystalline CoZn hydroxide nanosheet materials to function as effective electrodes for electrochemical oxygen evolution reactions. This convenient and eco-friendly topotactical transformation approach facilitates high-quality single crystal growth with improved multiphase purity and homogeneity, which can be extended to other transition metals for the fabrication of advanced functional nanocomposites. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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 Electrode Kinetics and Surface Composition of Dense (La0.75Sr0.25)0.95MnO3 on YSZ

DEFF Research Database (Denmark)

Wu, Yuehua; Hansen, Karin Vels; Norrman, Kion

2013-01-01

in situ at temperatures from 660 to 860 C using a controlled atmosphere high temperature scanning probe microscope (CAHT-SPM) setup for measurements of impedance spectroscopy and potential sweep. The oxygen partial pressure, pO2, was varied. Further, ex situ surface analysis by time of flight secondary...... ion mass spectrometry (TOF-SIMS) and structure examination by scanning electron microscopy (SEM) were performed. Segregation of Sr and La oxides to LSM surfaces and Mn rich oxide to the three phase boundary (TPB) was observed. YSZ and LSM attract different oxides/impurities. The oxygen electrode...

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...

Cobalt Phthalocyanine Modified Electrodes Utilised in Electroanalysis: Nano-Structured Modified Electrodes vs. Bulk Modified Screen-Printed Electrodes

Directory of Open Access Journals (Sweden)

Christopher W. Foster

2014-11-01

Full Text Available Cobalt phthalocyanine (CoPC compounds have been reported to provide electrocatalytic performances towards a substantial number of analytes. In these configurations, electrodes are typically constructed via drop casting the CoPC onto a supporting electrode substrate, while in other cases the CoPC complex is incorporated within the ink of a screen-printed sensor, providing a one-shot economical and disposable electrode configuration. In this paper we critically compare CoPC modified electrodes prepared by drop casting CoPC nanoparticles (nano-CoPC onto a range of carbon based electrode substrates with that of CoPC bulk modified screen-printed electrodes in the sensing of the model analytes L-ascorbic acid, oxygen and hydrazine. It is found that no “electrocatalysis” is observed towards L-ascorbic acid using either of these CoPC modified electrode configurations and that the bare underlying carbon electrode is the origin of the obtained voltammetric signal, which gives rise to useful electroanalytical signatures, providing new insights into literature reports where “electrocatalysis” has been reported with no clear control experiments undertaken. On the other hand true electrocatalysis is observed towards hydrazine, where no such voltammetric features are witnessed on the bare underlying electrode substrate.

Use of a combined oxygen and carbon dioxide transcutaneous electrode in the estimation of gas exchange during exercise.

OpenAIRE

Sridhar, M K; Carter, R; Moran, F; Banham, S W

1993-01-01

BACKGROUND--Accurate and reliable measurement of gas exchange during exercise has traditionally involved arterial cannulation. Non-invasive devices to estimate arterial oxygen (O2) and carbon dioxide (CO2) tensions are now available. A method has been devised and evaluated for measuring gas exchange during exercise with a combined transcutaneous O2 and CO2 electrode. METHODS--Symptom limited exercise tests were carried out in 24 patients reporting effort intolerance and breathlessness. Exerci...

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

Relating surface chemistry and oxygen surface exchange in LnBaCo2O(5+δ) air electrodes.

Science.gov (United States)

Téllez, Helena; Druce, John; Kilner, John A; Ishihara, Tatsumi

2015-01-01

The surface and near-surface chemical composition of electroceramic materials often shows significant deviations from that of the bulk. In particular, layered materials, such as cation-ordered LnBaCo2O(5+δ) perovskites (Ln = lanthanide), undergo surface and sub-surface restructuring due to the segregation of the divalent alkaline-earth cation. These processes can take place during synthesis and processing steps (e.g. deposition, sintering or annealing), as well as at temperatures relevant for the operation of these materials as air electrodes in solid oxide fuel cells and electrolysers. Furthermore, the surface segregation in these double perovskites shows fast kinetics, starting at temperatures as low as 400 °C over short periods of time and leading to a decrease in the transition metal surface coverage exposed to the gas phase. In this work, we use a combination of stable isotope tracer labeling and surface-sensitive ion beam techniques to study the oxygen transport properties and their relationship with the surface chemistry in ordered LnBaCo2O(5+δ) perovskites. Time-of-Flight Secondary-Ion Mass Spectrometry (ToF-SIMS) combined with (18)O isotope exchange was used to determine the oxygen tracer diffusion (D*) and surface exchange (k*) coefficients. Furthermore, Low Energy Ion Scattering (LEIS) was used for the analysis of the surface and near surface chemistry as it provides information from the first mono-atomic layer of the materials. In this way, we could relate the compositional modifications (e.g. cation segregation) taking place at the electrochemically-active surface during the exchange at high temperatures and the oxygen transport properties in double perovskite electrode materials to further our understanding of the mechanism of the surface exchange process.

Novel nanostructured oxygen sensor

Science.gov (United States)

Boardman, Alan James

New government regulations and industry requirements for medical oxygen sensors require the development of alternate materials and process optimization of primary sensor components. Current oxygen sensors are not compliant with the Restriction of Hazardous Substances (RoHS) Directive. This work focused on two areas. First, was finding suitable readily available materials for the sensor anodes. Second was optimizing the processing of the sensor cathode membrane for reduced delamination. Oxygen sensors were made using tin (Sn) and bismuth (Bi) electrodes, potassium hydroxide (KOH) and acetic acid (CH3COOH) electrolytes with platinum (Pt) and gold (Au) reference electrodes. Bi electrodes were fabricated by casting and pressing processes. Electrochemical characterization of the Sn and Bi electrodes was performed by Cyclic Voltammetry (CV), Electrochemical Impedance Spectroscopy (EIS) and sensing characterization per BSEN ISO 21647:2009 at various oxygen percentages, 0%, 20.9% and 100% oxygen levels with an automated test apparatus. The Sn anode with both electrolyte solutions showed good oxygen sensing properties and performance in a sensor. This system shows promise for replacement of Pb electrodes as required by the RoHS Directive. The Bi anode with Au cathode in both KOH and CH3COOH electrolytes showed acceptable performance and oxygen sensing properties. The Bi anodes fabricated by separate manufacturing methods demonstrated effectiveness for use in medical oxygen sensors. Gold thin films were prepared by magnetron sputtering on Flouroethylene Polymer (FEP) films. The FEP substrate temperature ranged from -77°C to 50°C. X-Ray Diffraction (XRD) and 4-point resistivity characterized the effects of substrate temperature to Au thin film particle size. XRD peak broadening and resistivity measurements showed a strong correlation of particle size to FEP substrate temperature. Particle size at 50°C was 594A and the -77°C particle size was 2.4 x 103A. Substrate

Investigation of a Spinel-forming Cu-Mn Foam as an Oxygen Electrode Contact Material in a Solid Oxide Cell Single Repeating Unit

DEFF Research Database (Denmark)

Zielke, Philipp; Wulff, Anders Christian; Sun, Xiufu

2017-01-01

A critical issue in state-of-the-art solid oxide cell stacks is the contacting of the oxygen electrode. The commonly used ceramic contact layers are applied in a green state and cannot be sintered properly, due to compliance limitations arising from other stack components like sealing glasses...

Screen-Printed Graphite Electrodes as Low-Cost Devices for Oxygen Gas Detection in Room-Temperature Ionic Liquids.

Science.gov (United States)

Lee, Junqiao; Hussain, Ghulam; Banks, Craig E; Silvester, Debbie S

2017-11-26

Screen-printed graphite electrodes (SPGEs) have been used for the first time as platforms to detect oxygen gas in room-temperature ionic liquids (RTILs). Up until now, carbon-based SPEs have shown inferior behaviour compared to platinum and gold SPEs for gas sensing with RTIL solvents. The electrochemical reduction of oxygen (O₂) in a range of RTILs has therefore been explored on home-made SPGEs, and is compared to the behaviour on commercially-available carbon SPEs (C-SPEs). Six common RTILs are initially employed for O₂ detection using cyclic voltammetry (CV), and two RTILs ([C₂mim][NTf₂] and [C₄mim][PF₆]) chosen for further detailed analytical studies. Long-term chronoamperometry (LTCA) was also performed to test the ability of the sensor surface for real-time gas monitoring. Both CV and LTCA gave linear calibration graphs-for CV in the 10-100% vol. range, and for LTCA in the 0.1-20% vol. range-on the SPGE. The responses on the SPGE were far superior to the commercial C-SPEs; more instability in the electrochemical responses were observed on the C-SPEs, together with some breaking-up or dissolution of the electrode surface materials. This study highlights that not all screen-printed ink formulations are compatible with RTIL solvents for longer-term electrochemical experiments, and that the choice of RTIL is also important. Overall, the low-cost SPGEs appear to be promising platforms for the detection of O₂, particularly in [C₄mim][PF₆].

Enhancement of oxygen diffusion process on a rotating disk electrode for the electro-Fenton degradation of tetracycline

International Nuclear Information System (INIS)

Zhang, Yan; Gao, Ming-Ming; Wang, Xin-Hua; Wang, Shu-Guang; Liu, Rui-Ting

2015-01-01

An electro-Fenton process was developed for wastewater treatment in which hydrogen peroxide was generated in situ with a rotating graphite disk electrode as cathode. The maximum H 2 O 2 generation rate for the RDE reached 0.90 mg/L/h/cm 2 under the rotation speed of 400 rpm at pH 3, and −0.8 V vs SCE. The performance of this electro-Fenton reactor was assessed by tetracycline degradation in an aqueous solution. Experimental results showed the rotation of disk cathode resulted in the efficient production of H 2 O 2 without oxygen aeration, and excellent ability for degrading organic pollutants compared to the electro-Fenton system with fixed cathode. Tetracycline of 50 mg/L was degraded completely within 2 h with the addition of ferrous ion (1.0 mM). The chronoamperometry analysis was employed to investigate the oxygen diffusion on the rotating cathode. The results demonstrated that the diffusion coefficients of dissolved oxygen is 19.45 × 10 −5 cm 2 /s, which is greater than that reported in the literature. Further calculation indicated that oxygen is able to diffuse through the film on the rotating cathode within the contact time in each circle. This study proves that enhancement of oxygen diffusion on RDE is benefit for H 2 O 2 generation, thus provides a promising method for organic pollutants degradation by the combination of RDE with electro-Fenton reactor and offers a new insight on the oxygen transform process in this new system.

New highly active oxygen reduction electrode for PEM fuel cell and Zn/air battery applications (NORA). Final report

Energy Technology Data Exchange (ETDEWEB)

Thiele, D.; Zuettel, A.

2008-04-15

This illustrated final report for the Swiss Federal Office of Energy (SFOE) presents the results of a project concerning a new, highly active oxygen reduction electrode for PEM fuel cell and zinc/air battery applications. The goal of this project was, according to the authors, to increase the efficiency of the oxygen reduction reaction by lowering the activation polarisation through the right choice of catalyst and by lowering the concentration polarisation. In this work, carbon nanotubes are used as support material. The use of these nanotubes grown on perovskites is discussed. Theoretical considerations regarding activation polarisation are discussed and alternatives to the use of platinum are examined. The results of experiments carried out are presented in graphical and tabular form. The paper is completed with a comprehensive list of references.

Low temperature formation of electrode having electrically conductive metal oxide surface

Science.gov (United States)

Anders, Simone; Anders, Andre; Brown, Ian G.; McLarnon, Frank R.; Kong, Fanping

1998-01-01

A low temperature process is disclosed for forming metal suboxides on substrates by cathodic arc deposition by either controlling the pressure of the oxygen present in the deposition chamber, or by controlling the density of the metal flux, or by a combination of such adjustments, to thereby control the ratio of oxide to metal in the deposited metal suboxide coating. The density of the metal flux may, in turn, be adjusted by controlling the discharge current of the arc, by adjusting the pulse length (duration of on cycle) of the arc, and by adjusting the frequency of the arc, or any combination of these parameters. In a preferred embodiment, a low temperature process is disclosed for forming an electrically conductive metal suboxide, such as, for example, an electrically conductive suboxide of titanium, on an electrode surface, such as the surface of a nickel oxide electrode, by such cathodic arc deposition and control of the deposition parameters. In the preferred embodiment, the process results in a titanium suboxide-coated nickel oxide electrode exhibiting reduced parasitic evolution of oxygen during charging of a cell made using such an electrode as the positive electrode, as well as exhibiting high oxygen overpotential, resulting in suppression of oxygen evolution at the electrode at full charge of the cell.

Mathematical modeling of oxygen transport in solid oxide fuel cells

Energy Technology Data Exchange (ETDEWEB)

Svensson, Ann Mari

1997-12-31

This thesis develops mathematical models to describe the electrochemical performance of a solid oxide fuel cell cathode based on electrochemical kinetics and mass transfer. The individual effects of various coupled processes are investigated. A one-dimensional model is developed based on porous electrode theory. Two different mechanisms are investigated for the charge transfer reaction. One of these assumes that intermediately adsorbed oxygen atoms are reduced at the electrode/electrolyte interface, similar to the models proposed for metal electrodes. Simulated polarization curves exhibit limited currents due to depletion of oxygen adsorbates at high cathodic overvoltages. An empirical correlation is confirmed to exist between the limiting current an the oxygen partial pressure, however, a similar correlation often assumed to exist between the measured polarization resistance and the oxygen partial pressure could not be justified. For the other model, oxygen vacancies are assumed to be exchanged directly at the electrode/electrolyte interface. The electrochemical behaviour is improved by reducing the oxygen partial pressure, due to increased vacancy concentration of the electrode material. Simulated polarization curves exhibit Tafel-like slopes in the cathodic direction, which are due to polarization concentration, and not activation polarization in the conventional sense. Anodic limiting currents are predicted due to lack of available free sites for vacancy exchange at the cathode side. The thesis also presents a theoretical treatment of current and potential distributions in simple two-dimensional cell geometries, and a two-dimensional model for a porous electrode-electrolyte system for investigation of the effect of interfacial diffusion of adsorbates along the electrode/electrolyte interface. 172 refs., 60 figs., 11 tabs.

Use of lanthanide catalysts in air electrodes

International Nuclear Information System (INIS)

Souza Parente, L.T. de

1982-01-01

A review on the lanthanide catalysts suitable for the reduction catalysis of oxygen in air electrodes is presented. The kinds of lanthanide indicated to be used as catalysts of oxygen reduction are shown. (A.R.H.) [pt

Influence of zirconium doping in ceria lattice as an active electrode in amperometric electrochemical ammonia gas sensor using oxygen pumping current

International Nuclear Information System (INIS)

Sharan, R.; Dutta, Atanu; Roy, Mainak

2016-01-01

An amperometric electrochemical sensor using Ce-Zr system as ammonia gas detecting electrode is reported. Using lanthanum gallate based electrolyte La_0_._8Sr_0_._2Ga_0_._8Mg_0_._1Ni_0_._1O_3 (LSGMN) and lanthanum strontium cobaltite La_0_._5Sr_0_._5CoO_3 (LSC) as oxygen reduction electrode, the sensor was found to be highly sensitive to NH_3 gas down to few ppm level, when operated in the temperature range 300-450°C. Keeping LSC electrodecomposition same, when sensing properties were studied with the variation of Zr concentration in ceria for active electrode, sensor with 30 mol % Zr doped ceria showed highest sensitivity of 28μA/ decade at 400°C. For all active electrodecompositions Ce_1_-_xZr_xO_2 (x = 0 to 0.7) highest sensitivity was observed at 400°C. All the sensors performed reproducibly with time response and recovery time 40 and 120 seconds respectively. (author)

Electrochemical monitoring of native catalase activity in skin using skin covered oxygen electrode.

Science.gov (United States)

Nocchi, Sarah; Björklund, Sebastian; Svensson, Birgitta; Engblom, Johan; Ruzgas, Tautgirdas

2017-07-15

A skin covered oxygen electrode, SCOE, was constructed with the aim to study the enzyme catalase, which is part of the biological antioxidative system present in skin. The electrode was exposed to different concentrations of H 2 O 2 and the amperometric current response was recorded. The observed current is due to H 2 O 2 penetration through the outermost skin barrier (referred to as the stratum corneum, SC) and subsequent catalytic generation of O 2 by catalase present in the underlying viable epidermis and dermis. By tape-stripping the outermost skin layers we demonstrate that SC is a considerable diffusion barrier for H 2 O 2 penetration. Our experiments also indicate that skin contains a substantial amount of catalase, which is sufficient to detoxify H 2 O 2 that reaches the viable epidermis after exposure of skin to high concentrations of peroxide (0.5-1mM H 2 O 2 ). Further, we demonstrate that the catalase activity is reduced at acidic pH, as compared with the activity at pH 7.4. Finally, experiments with often used penetration enhancer thymol shows that this compound interferes with the catalase reaction. Health aspect of this is briefly discussed. Summarizing, the results of this work show that the SCOE can be utilized to study a broad spectrum of issues involving the function of skin catalase in particular, and the native biological antioxidative system in skin in general. Copyright © 2017 Elsevier B.V. All rights reserved.

Graphene-based battery electrodes having continuous flow paths

Science.gov (United States)

Zhang, Jiguang; Xiao, Jie; Liu, Jun; Xu, Wu; Li, Xiaolin; Wang, Deyu

2014-05-24

Some batteries can exhibit greatly improved performance by utilizing electrodes having randomly arranged graphene nanosheets forming a network of channels defining continuous flow paths through the electrode. The network of channels can provide a diffusion pathway for the liquid electrolyte and/or for reactant gases. Metal-air batteries can benefit from such electrodes. In particular Li-air batteries show extremely high capacities, wherein the network of channels allow oxygen to diffuse through the electrode and mesopores in the electrode can store discharge products.

Dual mode antimony electrode for simultaneous measurements of PO2 and pH.

Science.gov (United States)

Sjöberg, F; Nilsson, G

2000-01-01

In biomedical research and clinical medicine there is a demand for potent sensors to measure the components that make up blood gas analyses. Today, as when the electrochemical PO2, PCO2 and pH electrodes were first introduced, these measurements are usually made with the same type of sensor technology. The aims of the present study were, firstly, to find out whether the platinum cathode in the Clark electrode can be replaced by antimony for oxygen measurements (amperometry (A)); secondly, whether, during oxygen measurements, the inherent corrosion potential of the antimony metal can be used for measurement of pH in the same measurement area (potentiometry (P)). An electrode of purified, crystallographically orientated monocrystalline antimony (COMA) connected to a reference electrode (silver-silver chloride) was used for the P measurements. Measurements of A (at -900 mV) and P were made in an aqueous environment regulated for oxygen, pH, and temperature. Reproducible oxygen sensitivities of 0.925 nA/% oxygen (2% CV (coefficient of variation)) (A), 10.7 mV/% (P), and 0.7 mV/% (P) were found in the oxygen range: 0-21%, <5%, and above 5%, respectively. The pH sensitivity was 57 mV/pH unit (P). Oxygen and pH measurements were less accurate at oxygen concentrations close to 0%. Both the oxygen and pH part of the composite electrode signal can be identified by this dual mode technique (A and P). The sensor seems to be promising as it provides measurements of two separate variables (oxygen and pH) and also has the desirable characteristics of a solid state sensor.

Screen-Printed Graphite Electrodes as Low-Cost Devices for Oxygen Gas Detection in Room-Temperature Ionic Liquids

Directory of Open Access Journals (Sweden)

Junqiao Lee

2017-11-01

Full Text Available Screen-printed graphite electrodes (SPGEs have been used for the first time as platforms to detect oxygen gas in room-temperature ionic liquids (RTILs. Up until now, carbon-based SPEs have shown inferior behaviour compared to platinum and gold SPEs for gas sensing with RTIL solvents. The electrochemical reduction of oxygen (O2 in a range of RTILs has therefore been explored on home-made SPGEs, and is compared to the behaviour on commercially-available carbon SPEs (C-SPEs. Six common RTILs are initially employed for O2 detection using cyclic voltammetry (CV, and two RTILs ([C2mim][NTf2] and [C4mim][PF6] chosen for further detailed analytical studies. Long-term chronoamperometry (LTCA was also performed to test the ability of the sensor surface for real-time gas monitoring. Both CV and LTCA gave linear calibration graphs—for CV in the 10–100% vol. range, and for LTCA in the 0.1–20% vol. range—on the SPGE. The responses on the SPGE were far superior to the commercial C-SPEs; more instability in the electrochemical responses were observed on the C-SPEs, together with some breaking-up or dissolution of the electrode surface materials. This study highlights that not all screen-printed ink formulations are compatible with RTIL solvents for longer-term electrochemical experiments, and that the choice of RTIL is also important. Overall, the low-cost SPGEs appear to be promising platforms for the detection of O2, particularly in [C4mim][PF6].

Perovskite electrodes and method of making the same

Science.gov (United States)

Seabaugh, Matthew M.; Swartz, Scott L.

2005-09-20

The invention relates to perovskite oxide electrode materials in which one or more of the elements Mg, Ni, Cu, and Zn are present as minority components that enhance electrochemical performance, as well as electrode products with these compositions and methods of making the electrode materials. Such electrodes are useful in electrochemical system applications such as solid oxide fuel cells, ceramic oxygen generation systems, gas sensors, ceramic membrane reactors, and ceramic electrochemical gas separation systems.

Long life lithium batteries with stabilized electrodes

Science.gov (United States)

Amine, Khalil [Downers Grove, IL; Liu, Jun [Naperville, IL; Vissers, Donald R [Naperville, IL; Lu, Wenquan [Darien, IL

2009-03-24

The present invention relates to non-aqueous electrolytes having electrode stabilizing additives, stabilized electrodes, and electrochemical devices containing the same. Thus the present invention provides electrolytes containing an alkali metal salt, a polar aprotic solvent, and an electrode stabilizing additive. In some embodiments the additives include a substituted or unsubstituted cyclic or spirocyclic hydrocarbon containing at least one oxygen atom and at least one alkenyl or alkynyl group. When used in electrochemical devices with, e.g., lithium manganese oxide spinel electrodes or olivine or carbon-coated olivine electrodes, the new electrolytes provide batteries with improved calendar and cycle life.

Pt Electrodes Enable the Formation of μ4-O Centers in MOF-5 from Multiple Oxygen Sources.

Science.gov (United States)

Li, Minyuan M; Dincă, Mircea

2017-10-04

The μ 4 -O 2- ions in the Zn 4 O(O 2 C-) 6 secondary building units of Zn 4 O(1,4-benzenedicarboxylate) 3 (MOF-5) electrodeposited under cathodic bias can be sourced from nitrate, water, and molecular oxygen when using platinum gauze as working electrodes. The use of Zn(ClO 4 ) 2 ·6H 2 O, anhydrous Zn(NO 3 ) 2 , or anhydrous Zn(CF 3 SO 3 ) 2 as Zn 2+ sources under rigorous control of other sources of oxygen, including water and O 2 , confirm that the source of the μ 4 -O 2- ions can be promiscuous. Although this finding reveals a relatively complicated manifold of electrochemical processes responsible for the crystallization of MOF-5 under cathodic bias, it further highlights the importance of hydroxide intermediates in the formation of the Zn 4 O(O 2 C-R) secondary building units in this iconic material and is illustrative of the complicated crystallization mechanisms of metal-organic frameworks in general.

Low-temperature behavior of ZrO2 oxygen sensors

International Nuclear Information System (INIS)

Badwal, S.P.S.; Bannister, M.J.

1983-01-01

The relative importance of the solid electrolyte and the electrodes in determining the low-temperature behavior of stabilized zirconia oxygen sensors is considered. Contrary to general belief, the electrodes play the more important role at low temperatures. The performance may be greatly improved by using, instead of porous platinum, oxide electrodes comprising solid solutions based on UO 2 . Laboratory tests and plant trials show that ideal behavior in oxygen-excess gases can be achieved below 400 0 C

Tumor oxygenation in a transplanted rat rhabdomyosarcoma during fractionated irradiation

International Nuclear Information System (INIS)

Zywietz, Friedrich; Reeker, Wolfram; Kochs, Eberhard

1995-01-01

Purpose: To quantify the changes in tumor oxygenation in the course of a fractionated radiation treatment extending over 4 weeks. Methods and Materials: Rhabdomyosarcomas R1H of the rat were irradiated with 60 Co-γ-rays with a total dose of 60 Gy, given in 20 fractions over 4 weeks. Oxygen partial pressure (pO 2 ) in tumors was measured at weekly intervals using polarographic needle probes in combination with a microprocessor-controlled device (pO 2 -Histograph/KIMOC). The pO 2 measurements were carried out in anesthetized animals under mechanical ventilation and in respiratory and hemodynamic steady state. Tumor pO 2 values were correlated to the arterial oxygen pressure p a O 2 , arterial pCO 2 , and pH determined with a blood gas analyzer. Results: Tumor oxygenation did not change significantly during the 3 weeks of irradiation (up to 45 Gy), from a median pO 2 of 23 ± 2 mmHg in untreated controls to 19 ± 4 mmHg after the third week. The decrease of the number of pO 2 values between 0 and 5 mmHg indicated that an improved oxygenation in the tumors occurred. However, with increasing radiation dose (fourth week, 60 Gy) a significant decrease in tumor oxygenation to a median pO 2 of 8 ± 2 mmHg and a rapid increase in the frequency of pO 2 values (35 ± 4%) between 0 and 5 mmHg was found. Conclusion: Improved oxygenation in rhabdomyosarcomas R1H was only present in the early phase of the fractionated irradiation. Radiation doses above 45 Gy led to a considerable decrease of tumor oxygenation in the later phase of irradiation

The oxygen-binding properties of hemocyanin from the mollusk Concholepas concholepas.

Science.gov (United States)

González, Andrea; Nova, Esteban; Del Campo, Miguel; Manubens, Augusto; De Ioannes, Alfredo; Ferreira, Jorge; Becker, María Inés

2017-12-01

Hemocyanins have highly conserved copper-containing active sites that bind oxygen. However, structural differences among the hemocyanins of various mollusks may affect their physicochemical properties. Here, we studied the oxygen-binding cooperativity and affinity of Concholepas concholepas hemocyanin (CCH) and its two isolated subunits over a wide range of temperatures and pH values. Considering the differences in the quaternary structures of CCH and keyhole limpet hemocyanin (KLH), we hypothesized that the heterodidecameric CCH has different oxygen-binding parameters than the homodidecameric KLH. A novel modification of the polarographic method was applied in which rat liver submitochondrial particles containing cytochrome c oxidase were introduced to totally deplete oxygen of the test solution using ascorbate as the electron donor. This method was both sensitive and reproducible. The results showed that CCH, like other hemocyanins, exhibits cooperativity, showing an inverse relationship between the oxygen-binding parameters and temperature. According to their Hill coefficients, KLH has greater cooperativity than CCH at physiological pH; however, CCH is less sensitive to pH changes than KLH. Appreciable differences in binding behavior were found between the CCH subunits: the cooperativity of CCH-A was not only almost double that of CCH-B, but it was also slightly superior to that of CCH, thus suggesting that the oxygen-binding domains of the CCH subunits are different in their primary structure. Collectively, these data suggest that CCH-A is the main oxygen-binding domain in CCH; CCH-B may play a more structural role, perhaps utilizing its surprising predisposition to form tubular polymers, unlike CCH-A, as demonstrated here using electron microscopy. Copyright © 2017 Elsevier B.V. All rights reserved.

Importance of Electrode Material in the Electrochemical Treatment of Wastewater Containing Organic Pollutants

Science.gov (United States)

Panizza, Marco

Electrochemical oxidation is a promising method for the treatment of wastewaters containing organic compounds. As a general rule, the electrochemical incineration of organics at a given electrode can take place at satisfactory rates and without electrode deactivation only at high anodic potentials in the region of the water discharge due to the participation of the intermediates of oxygen evolution. The nature of the electrode material strongly influences both the selectivity and the efficiency of the process. In particular, anodes with low oxygen evolution overpotential (i.e., good catalysts for oxygen evolution reactions), such as graphite, IrO2, RuO2, and Pt only permit the partial oxidation of organics, while anodes with high oxygen evolution overpotential (i.e., anodes that are poor catalysts for oxygen evolution reactions), such as SnO2, PbO2, and boron-doped diamond (BDD) favor the complete oxidation of organics to CO2 and so are ideal electrodes for wastewater treatment.However, the application of SnO2 and PbO2 anodes may be limited by their short service life and the risk of lead contamination, while BDD electrodes exhibit good chemical and electrochemical stability, a long life, and a wide potential window for water discharge, and are thus promising anodes for industrial-scale wastewater treatment.

Bias polarization study of steam electrolysis by composite oxygen electrode Ba0.5Sr0.5Co0.8Fe0.2O3-δ/BaCe0.4Zr0.4Y0.2O3-δ

Science.gov (United States)

Yang, Tao; Shaula, Aliaksandr; Pukazhselvan, D.; Ramasamy, Devaraj; Deng, Jiguang; da Silva, E. L.; Duarte, Ricardo; Saraiva, Jorge A.

2017-12-01

The polarization behavior of Ba0.5Sr0.5Co0.8Fe0.2O3-δ-BaCe0.4Zr0.4Y0.2O3-δ (BSCF-BCZY) electrode under steam electrolysis conditions was studied in detail. The composite oxygen electrode supported by BCZY electrolyzer has been assessed as a function of temperature (T), water vapor partial pressures (pH2O), and bias polarization voltage for electrodes of comparable microstructure. The Electrochemical impedance spectra show two depressed arcs in general without bias polarization. And the electrode resistance became smaller with the increase of the bias polarization under the same water vapor partial pressures. The total resistance of the electrode was shown to be significantly affected by temperature, with the same level of pH2O and bias polarization voltage. This result highlights BSCF-BCZY as an effective oxygen electrode under moderate polarization and pH2O conditions.

Study on oxidization of Ru and its application as electrode of PZT capacitor for FeRAM

International Nuclear Information System (INIS)

Jia Ze; Ren Tianling; Liu Tianzhi; Hu Hong; Zhang Zhigang; Xie Dan; Liu Litian

2007-01-01

Oxidization for Ru through anneal with plenteous oxygen atmosphere and its application as the top electrode of sol-gel PZT capacitor are investigated in this study. PZT capacitor with RuO 2 or oxygen-doped Ru as top electrode can be obtained from Ru/PZT/Pt capacitor through slow-rate anneal at 650 deg. C for 20 min in cannulation furnace. It has larger remanent polarization, better rectangle shape, better fatigue properties and lower leakage current than the other capacitors with PZT film prepared by the same process and different top electrodes in this study. Plenteous oxygen atmosphere and 650 deg. C in cannulation furnace are important conditions for the oxidation of Ru and renewed crystallization of PZT in this capacitor. Plenteous oxygen at interface can compensate the oxygen vacancies at PZT/electrode interface, which results in the above good characteristics

Nitrogen and oxygen co-doped carbon nanofibers with rich sub-nanoscale pores as self-supported electrode material of high-performance supercapacitors

International Nuclear Information System (INIS)

Li, Qun; Xie, Wenhe; Liu, Dequan; Wang, Qi; He, Deyan

2016-01-01

Self-supported porous carbon nanofibers (CNFs) network has been prepared by electrospinning technology assisted with template method. The as-prepared material is rich in sub-nanoscale pores and nitrogen and oxygen functional groups, which can serve as a fast conductive network with abundant electrochemical active sites and greatly facilitates the transport of electrons and ions. When the porous CNFs network is used as an electrode for supercapacitor in a three electrode system, it displays a high capacitance of 233.1 F/g at 0.2 A/g, and a capacitance of 130.2 F/g even at 14 A/g. It maintains a capacitance of 154.0 F/g with 90.17% retention after 4000 cycles at 2 A/g. Moreover, the assembled symmetric supercapacitor not only exhibits excellent rate capability and cycle performance, but also delivers an energy density of 4.17 Wh/kg and a power density of 2500 W/kg. The experimental results demonstrate that the prepared N, O co-doped carbon nanofibers with rich sub-nanoscale pores are a promising electrode material for high-performance supercapacitors.

Catalyst Stability Benchmarking for the Oxygen Evolution Reaction: The Importance of Backing Electrode Material and Dissolution in Accelerated Aging Studies.

Science.gov (United States)

Geiger, Simon; Kasian, Olga; Mingers, Andrea M; Nicley, Shannon S; Haenen, Ken; Mayrhofer, Karl J J; Cherevko, Serhiy

2017-09-18

In searching for alternative oxygen evolution reaction (OER) catalysts for acidic water splitting, fast screening of the material intrinsic activity and stability in half-cell tests is of vital importance. The screening process significantly accelerates the discovery of new promising materials without the need of time-consuming real-cell analysis. In commonly employed tests, a conclusion on the catalyst stability is drawn solely on the basis of electrochemical data, for example, by evaluating potential-versus-time profiles. Herein important limitations of such approaches, which are related to the degradation of the backing electrode material, are demonstrated. State-of-the-art Ir-black powder is investigated for OER activity and for dissolution as a function of the backing electrode material. Even at very short time intervals materials like glassy carbon passivate, increasing the contact resistance and concealing the degradation phenomena of the electrocatalyst itself. Alternative backing electrodes like gold and boron-doped diamond show better stability and are thus recommended for short accelerated aging investigations. Moreover, parallel quantification of dissolution products in the electrolyte is shown to be of great importance for comparing OER catalyst feasibility. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

pO polarography, contrast enhanced color duplex sonography (CDS), [18F] fluoromisonidazole and [18F] fluorodeoxyglucose positron emission tomography: validated methods for the evaluation of therapy-relevant tumor oxygenation or only bricks in the puzzle of tumor hypoxia?

International Nuclear Information System (INIS)

Gagel, Bernd; Hamacher, Kurt; Coenen, Heinz H; Scholbach, Thomas; Maneschi, Payam; DiMartino, Ercole; Eble, Michael J; Piroth, Marc; Pinkawa, Michael; Reinartz, Patrick; Zimny, Michael; Kaiser, Hans J; Stanzel, Sven; Asadpour, Branka; Demirel, Cengiz

2007-01-01

The present study was conducted to analyze the value of ([ 18 F] fluoromisonidazole (FMISO) and [ 18 F]-2-fluoro-2'-deoxyglucose (FDG) PET as well as color pixel density (CPD) and tumor perfusion (TP) assessed by color duplex sonography (CDS) for determination of therapeutic relevant hypoxia. As a standard for measuring tissue oxygenation in human tumors, the invasive, computerized polarographic needle electrode system (pO 2 histography) was used for comparing the different non invasive measurements. Until now a total of 38 Patients with malignancies of the head and neck were examined. Tumor tissue pO 2 was measured using a pO 2 -histograph. The needle electrode was placed CT-controlled in the tumor without general or local anesthesia. To assess the biological and clinical relevance of oxygenation measurement, the relative frequency of pO 2 readings, with values ≤ 2.5, ≤ 5.0 and ≤ 10.0 mmHg, as well as mean and median pO 2 were stated. FMISO PET consisted of one static scan of the relevant region, performed 120 min after intravenous administration. FMISO tumor to muscle ratios (FMISO T/M ) and tumor to blood ratios (FMISO T/B ) were calculated. FDG PET of the lymph node metastases was performed 71 ± 17 min after intravenous administration. To visualize as many vessels as possible by CDS, a contrast enhancer (Levovist ® , Schering Corp., Germany) was administered. Color pixel density (CPD) was defined as the ratio of colored to grey pixels in a region of interest. From CDS signals two parameters were extracted: color hue – defining velocity (v) and color area – defining perfused area (A). Signal intensity as a measure of tissue perfusion (TP) was quantified as follows: TP = v mean × A mean . In order to investigate the degree of linear association, we calculated the Pearson correlation coefficient. Slight (|r| > 0.4) to moderate (|r| > 0.6) correlation was found between the parameters of pO 2 polarography (pO 2 readings with values ≤ 2.5, ≤ 5

Oxygen tension in transplanted mouse osteosarcomas during fractionated high-LET- and low-LET radiotherapy - predictive aspects for choosing beam quality?

International Nuclear Information System (INIS)

Auberger, T.; Thuerriegel, B.; Freude, T.; Weissfloch, L.; Kneschaurek, P.; Molls, M.; Senekowitsch-Schmidtke, R.; Wagner, F.M.

1999-01-01

Murine OTS64 - osteosarcomas were tranplanted in 102 balb-C mice and irradiated by 36 Gy of photons in fractions of 3 Gy five times a week (group P-36/3) or by 12 Gy of reactor fission neutrons in fractions of 2 Gy two times a week (group N-12/2). Irradiations started at a tumor volume of 500 to 600 mm 3 . A third group received no radiotherapy, but all investigations (group CG). Tumor volume and tumor oxygenation were measured once a week under therapy and during three weeks after therapy. For in vivo-evaluation of oxygen status a computerized polarographic needle electrode system (KIMOC pO 2 histograph, Eppendorf) was used. The median pO 2 and the hypoxic fraction (pO 2 values 2 decreased from 20 mm to 8 mm Hg and the hypoxic fraction increased from 7% to 31%. After fractionated photon therapy a growth delay of three weeks was observed. Six weeks after beginning of the irradiation the median tumor volume had been doubled again. After fission neutron therapy growth delay continued until the end of the follow-up period. In both of the irradiated groups a significant decrease of median pO 2 values and an increase of the hypoxic fraction were observed under radiotherapy. Hypoxia was more intensive after neutrons with a decrease of the median pO 2 from 20 mm Hg to 1 mm Hg vs. 10 mm Hg after photon therapy and with an increase of the hypoxic fraction from 7% to 78% vs. 36% respectively. Two weeks after the end of therapy the median pO 2 and the hypoxic fraction of both treated groups reached the levels prior to irradiation indicating a complete reoxygenation. (orig.)

Oxygen transport through soft contact lens and cornea: Lens characterization and metabolic modeling

Science.gov (United States)

Chhabra, Mahendra

The human cornea requires oxygen to sustain metabolic processes critical for its normal functioning. Any restriction to corneal oxygen supply from the external environment (e.g., by wearing a low oxygen-permeability contact lens) can lead to hypoxia, which may cause corneal edema (swelling), limbal hyperemia, neovascularization, and corneal acidosis. The need for adequate oxygen to the cornea is a major driving force for research and development of hypertransmissible soft contact lenses (SCLs). Currently, there is no standard technique for measuring oxygen permeability (Dk) of hypertransmissible silicone-hydrogel SCLs. In this work, an electrochemistry-based polarographic apparatus was designed, built, and operated to measure oxygen permeability in hypertransmissible SCLs. Unlike conventional methods where a range of lens thickness is needed for determining oxygen permeabilities of SCLs, this apparatus requires only a single lens thickness. The single-lens permeameter provides a reliable, efficient, and economic tool for measuring oxygen permeabilities of commercial hypertransmissible SCLs. The single-lens permeameter measures not only the product Dk, but, following modification, it measures separately diffusivity, D, and solubility, k, of oxygen in hypertransmissible SCLs. These properties are critical for designing better lens materials that ensure sufficient oxygen supply to the cornea. Metabolism of oxygen in the cornea is influenced by contact-lens-induced hypoxia, diseases such as diabetes, surgery, and drug treatment, Thus, estimation of the in-vivo corneal oxygen consumption rate is essential for gauging adequate oxygen supply to the cornea. Therefore, we have developed an unsteady-state reactive-diffusion model for the cornea-contact-lens system to determine in-vivo human corneal oxygen-consumption rate. Finally, a metabolic model was developed to determine the relation between contact-lens oxygen transmissibility (Dk/L) and corneal oxygen deficiency. A

Domestic wastewater treatment using multi-electrode continuous flow MFCs with a separator electrode assembly design

KAUST Repository

Ahn, Yongtae; Logan, Bruce E.

2012-01-01

Treatment of domestic wastewater using microbial fuel cells (MFCs) will require reactors with multiple electrodes, but this presents unique challenges under continuous flow conditions due to large changes in the chemical oxygen demand (COD

Limiting Current of Oxygen Reduction on Gas-Diffusion Electrodes for Phosphoric Acid Fuel Cells

DEFF Research Database (Denmark)

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

1994-01-01

on polytetrafluorine-ethyl bonded gas-diffusion electordes in phosphoric acid with and without fluorinated additives. This provides an alternative to estimate the film thickness by combining it with the acid-adsorption measurements and the porosity analysis of the catalyst layer. It was noticed that the limiting......Various models have been devoted to the operation mechanism of porous diffusion electrodes. They are, however, suffering from the lack of accuracy concerning the acid-film thickness on which they are based. In the present paper the limiting current density has been measured for oxygen reduction...... current density can be accomplished either by gas-phase diffusion or liquid-phase diffusion, and it is the latter that can be used in the film-thickness estimation. It is also important to mention that at such a limiting condition, both the thin-film model and the filmed agglomerate model reach the same...

Modulating indium doped tin oxide electrode properties for laccase electron transfer enhancement

Energy Technology Data Exchange (ETDEWEB)

Diaconu, Mirela [National Institute for Biological Sciences, Centre of Bioanalysis, 296 Spl. Independentei, Bucharest 060031 (Romania); Chira, Ana [National Institute for Biological Sciences, Centre of Bioanalysis, 296 Spl. Independentei, Bucharest 060031 (Romania); Politehnica University of Bucharest, Faculty of Applied Chemistry and Materials Science, 1-7 Polizu Str., 011061 (Romania); Radu, Lucian, E-mail: gl_radu@chim.upb.ro [Politehnica University of Bucharest, Faculty of Applied Chemistry and Materials Science, 1-7 Polizu Str., 011061 (Romania)

2014-08-28

Indium doped tin oxide (ITO) electrodes were functionalized with gold nanoparticles (GNPs) and cysteamine monolayer to enhance the heterogeneous electron transfer process of laccase from Trametes versicolor. The assembly of GNP on ITO support was performed through generation of H{sup +} species at the electrode surface by hydroquinone electrooxidation at 0.9 V vs Ag/AgCl. Uniform distribution of gold nanoparticle aggregates on electrode surfaces was confirmed by atomic force microscopy. The size of GNP aggregates was in the range of 200–500 nm. The enhanced charge transfer at the GNP functionalized ITO electrodes was observed by cyclic voltammetry (CV) and electrochemical impedance spectroscopy. Electrocatalytic behavior of laccase immobilized on ITO modified electrode toward oxygen reduction reaction was evaluated using CV in the presence of 2,2′-azino-bis 3-ethylbenzothiazoline-6-sulfuric acid (ABTS). The obtained sigmoidal-shaped voltammograms for ABTS reduction in oxygen saturated buffer solution are characteristic for a catalytic process. The intensity of catalytic current increased linearly with mediator concentration up to 6.2 × 10{sup −4} M. The registered voltammogram in the absence of ABTS mediator clearly showed a significant faradaic current which is the evidence of the interfacial oxygen reduction. - Highlights: • Assembly of gold nanoparticles on indium tin oxide support at positive potentials • Electrochemical and morphological evaluation of the gold nanoparticle layer assembly • Bioelectrocatalytic oxygen reduction on laccase modified electrode.

Polarographic determination of Iodide and Iodate, in Solutions Coming from Aerosols in Fission Products Containment Studies in Nuclear Power Stations

International Nuclear Information System (INIS)

Sanchez, M.; Ballesteros, O.; Fernandez, M.; Clavero, M.A.; Gonzalez, A.M.

2000-01-01

A polarographic method is described for the iodine species determination, iodide and iodate in water solutions. the iodate can be determined by differential pulse polarography. Calibration curves and the detection and determination limits have been obtained. Iodides is oxidized to iodate with sodium hypochlorite and the excess of oxidizing agent is destroyed with sodium sulphide. The concentration of iodide is calculated as the difference between the concentration of iodate in the sample before and after the oxidation. As an application, species of iodine in samples coming from the experimental plants GIRS (Gaseous Iodine Removal by Sprays) of Nuclear Fission Department of the CIEMAT, dedicated to fission products containment studies in nuclear power station, were determined. (Author) 10 refs

Nickel-hydrogen battery with oxygen and electrolyte management features

Science.gov (United States)

Sindorf, John F.

1991-10-22

A nickel-hydrogen battery or cell having one or more pressure vessels containing hydrogen gas and a plurality of cell-modules therein. Each cell-module includes a configuration of cooperatively associated oxygen and electrolyte mangement and component alignment features. A cell-module having electrolyte includes a negative electrode, a positive electrode adapted to facilitate oxygen diffusion, a separator disposed between the positive and negative electrodes for separating them and holding electrolyte for ionic conductivity, an absorber engaging the surface of the positive electrode facing away from the separator for providing electrolyte to the positive electrode, and a pair of surface-channeled diffusion screens for enclosing the positive and negative electrodes, absorber, and separator and for maintaining proper alignment of these components. The screens, formed in the shape of a pocket by intermittently sealing the edges together along as many as three sides, permit hydrogen gas to diffuse therethrough to the negative electrodes, and prevent the edges of the separator from swelling. Electrolyte is contained in the cell-module, absorbhed by the electrodes, the separator and the absorber.

Real-time monitoring of nitric oxide (NO) and pO2 levels under ischemic conditions associated with small bowel ischemia/reperfusion injury using selective electrodes for NO and oxygen molecules.

Science.gov (United States)

Watanabe, T; Owada, S; Kobayashi, H; Ishiuchi, A; Nakano, H; Asakuta, T; Shimamura, T; Asano, T; Koizumi, S; Jinnouchi, Y; Katayama, M; Kamibayasi, M; Murakami, E; Otsubo, T

2007-12-01

The present study demonstrated the feasibility of monitoring nitric oxide (NO) and pO2 levels under ischemic conditions associated with small bowel ischemia/reperfusion (I/R) injury through the use of selective electrodes for NO and oxygen molecules. NO levels gradually increased during ischemia. When reperfusion was started, the NO level decreased suddenly and returned to pre-ischemia values within 10 minutes. After clamping, pO2 decreased rapidly. When reperfusion was started, pO2 increased suddenly, returning to pre-ischemia values within 10 minutes. We concluded that it is feasible to monitor NO and pO2 levels under ischemic conditions of small bowel I/R injury through the use of electrodes selective for NO and oxygen molecules.

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.

Microbial electrode sensor for alcohols

Energy Technology Data Exchange (ETDEWEB)

Hikuma, M [Ajinomoto Co., Inc., Kawasaki, Japan; Kubo, T; Yasuda, T; Karube, I; Suzuki, S

1979-10-01

A microbial electrode consisting of immobilized microorganisms, a gas permeable Teflon membrane, and an oxygen electrode was prepared for the continuous determination of methyl and ethyl alcohols. Immobilized Trichosporon brassicae was employed for a microbial electrode sensor for ethyl alcohol. When a sample solution containing ethyl alcohol was injected into a microbial electrode system, the current of the electrode decreased markedly with time until a steady state was reached. The response time was within 10 min by the steady state method and within 6 min by the pulse method. A linear relationship was observed between the current decrease and the concentration of ethyl alcohol below 22.5 mg/liter. The current was reproducible within +- 6% of the relative error when a sample solution containing 16.5 mg/liter ethyl alcohol. The standard deviation was 0.5 mg/liter in 40 experiments. The selectivity of the microbial electrode sensor for ethyl alcohol was satisfactory. The microbial electrode sensor was applied to a fermentation broth of yeasts and satisfactory comparative results were obtained (correlation coefficient 0.98). The current output of the microbial electrode sensor was almost constant for more than three weeks and 2100 assays. A microbial electrode sensor using immobilized bacteria for methyl alcohol was also described.

An atomic oxygen device based on PIG oxygen negative ion source

International Nuclear Information System (INIS)

Yu Jinxiang; Cai Minghui; Han Jianwei

2008-01-01

It is an important research subject for the spaceflight countries to conduct equivalent simulation of 5 eV atomic oxygen effects for the spaceflight material in low earth orbit. This paper introduces an apparatus used for producing atomic oxygen, which consists of a PIG ion source with permanent magnet, two electrodes extraction system, an electron deflector, an einzel lens, an ion decelerating electrode and a sample bracket. At present it has been used on the small debris accelerator in the Center for Space Science and Applied Research, Chinese Academy of Sciences, and the producing experiments of O - are carried out. 200-300μA of O - ions are extracted at the extraction voltage of 2-3 kV. The experiments for decelerating of O - ions and erosion of kapton foil are carried out also. Because of the target room used for both the atomic oxygen device and the small debris accelerator, the facility can be used for small debris impinging and atomic erosion for spaceflight materials simultaneously. (authors)

Carbon aerogel electrodes for direct energy conversion

Science.gov (United States)

Mayer, Steven T.; Kaschmitter, James L.; Pekala, Richard W.

1997-01-01

A direct energy conversion device, such as a fuel cell, using carbon aerogel electrodes, wherein the carbon aerogel is loaded with a noble catalyst, such as platinum or rhodium and soaked with phosphoric acid, for example. A separator is located between the electrodes, which are placed in a cylinder having plate current collectors positioned adjacent the electrodes and connected to a power supply, and a pair of gas manifolds, containing hydrogen and oxygen positioned adjacent the current collectors. Due to the high surface area and excellent electrical conductivity of carbon aerogels, the problems relative to high polarization resistance of carbon composite electrodes conventionally used in fuel cells are overcome.

Graphite-graphite oxide composite electrode for vanadium redox flow battery

International Nuclear Information System (INIS)

Li Wenyue; Liu Jianguo; Yan Chuanwei

2011-01-01

Highlights: → A new composite electrode is designed for vanadium redox flow battery (VRB). → The graphite oxide (GO) is used as electrode reactions catalyst. → The excellent electrode activity is attributed to the oxygen-containing groups attached on the GO surface. → A catalytic mechanism of the GO towards the redox reactions is presumed. - Abstract: A graphite/graphite oxide (GO) composite electrode for vanadium redox battery (VRB) was prepared successfully in this paper. The materials were characterized with X-ray diffraction, X-ray photoelectron spectroscopy and scanning electron microscopy. The specific surface area was measured by the Brunauer-Emmett-Teller method. The redox reactions of [VO 2 ] + /[VO] 2+ and V 3+ /V 2+ were studied with cyclic voltammetry and electrochemical impedance spectroscopy. The results indicated that the electrochemical performances of the electrode were improved greatly when 3 wt% GO was added into graphite electrode. The redox peak currents of [VO 2 ] + /[VO] 2+ and V 3+ /V 2+ couples on the composite electrode were increased nearly twice as large as that on the graphite electrode, and the charge transfer resistances of the redox pairs on the composite electrode are also reduced. The enhanced electrochemical activity could be ascribed to the presence of plentiful oxygen functional groups on the basal planes and sheet edges of the GO and large specific surface areas introduced by the GO.

Ultramicroelectrode studies of oxygen reduction 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

A study on the oxygen reduction reaction in a solid state electrochemical cell was presented. The oxygen reduction reaction is a rate limiting reaction in the operation of solid polymer electrolyte fuel cells which use H{sub 2} and O{sub 2}. Interest in the oxygen reduction reaction of platinum electrodes in contact with Nafion electrolytes stems from its role in fuel cell technology. The kinetics of the oxygen reduction reaction in different polyelectrolyte membranes, such as Nafion and non-Nafion membranes, were compared. The electrode kinetics and mass transport parameters of the oxygen reduction reaction in polyelectrolyte membranes were measured by ultramicroelectrode techniques. The major difference found between these two classes of membrane was the percentage of water, which is suggestive of superior electrochemical mass transport properties of the non-Nafion membranes. 2 refs. 1 fig.

Determination of Sn in 99mTc Radiopharmaceutical Kits by Polarographic Methods

International Nuclear Information System (INIS)

Castro, M.; Cruz, J.; Sanchez, M.

2009-01-01

Kits of 99 m Tc radiopharmaceuticals are used in nuclear medicine for diagnosis of different diseases. Sn (II) is one of the essential components in their formulations, which is used for reduction 99 m Tc-pertechnetate in cold kits for on-site preparation 99 m Tc-pertechnetate radiopharmaceuticals. Usually, these cold kits contain different additives (complexing agents, antioxidants, buffers, etc.) and the amount of Sn (II) varies from kit to kit. The determination of Sn in these products is essential in assessing their quality. We report here the development of a new polarographic method for the determination of Sn (II) and total Sn in representative radiopharmaceuticals kits (for the content of Sn and chemical composition) produced at the Center of Isotopes of Cuba (CENTIS). These methods were validated by analysis of variance and recovery techniques. From the results of the validation, the characteristic functions of uncertainties and fits are considered for the established methods, which give the necessary evidences to demonstrate the usefulness of these methods according to the current trends in Analytical Chemistry. This work provides practical results of great importance for CENTIS. After the speciation of Sn in the MAG3 radiopharmaceuticals kit is inferred that the production process is affected by uncontrolled factors that influence in the product stability, which demonstrates the necessity for analytical tools for the characterization of products and processes. (Author) 57 refs.

Copper separation using modified active carbon before the polarographic determination of Pb, Cd, Ni, Zn and Fe in wastes

International Nuclear Information System (INIS)

Rubel, S.; Lada, Z.M.; Golimowski, J.

1977-01-01

The investigations on the selective separation of Pb 2+ , Cd 2+ , Ni 2+ , Zn 2+ and Fe 3+ ions from the excess of copper were carried out. For this purpose active carbon modified by Na-diethyldithiocarbamate was used. The manner of DDTK-Na deposition on active carbon has been elaborated. The influence of pH was investigated and it was found that at pH 1(HNO 3 ) copper ions are quantitavely bound on modified carbon whereas other ions (Pb 2+ , Cd 2+ , Ni 2+ , Zn 2+ and Fe 3+ ) remain in the solution and can be determined polarographically. The elaborated method was applied to the determination of mentioned ions in the samples of wastes containing even 100-fold excess of copper. The concentration of copper can not exceed 100 mg/dm 3 . (author)

Strategies for enhancing electrochemical activity of carbon-based electrodes for all-vanadium redox flow batteries

International Nuclear Information System (INIS)

Flox, Cristina; Skoumal, Marcel; Rubio-Garcia, Javier; Andreu, Teresa; Morante, Juan Ramón

2013-01-01

Highlights: ► Improved reactions at the positive electrode in all-vanadium redox flow batteries. ► Graphene-derived and PAN-modified electrodes have been successfully prepared. ► Modification with bimetallic CuPt 3 nanocubes yielded the best catalytic behavior. ► N and O-containing groups enhances the vanadium flow battery performance. - Abstract: Two strategies for improving the electroactivity towards VO 2+ /VO 2 + redox pair, the limiting process in all-vanadium redox flow batteries (VFBs), were presented. CuPt 3 nanoparticles supported onto graphene substrate and nitrogen and oxygen polyacrylonitrile (PAN)-functionalized electrodes materials have been evaluated. The morphology, composition, electrochemical properties of all electrodes prepared was characterized with field emission-scanning electrode microscopy, X-ray photoelectron spectroscopy, cyclic voltammetry, electrochemical impedance spectroscopy and cell charge–discharge test. The presence of the CuPt 3 nanocubes and nitrogen and oxygen functionalities enhance the electrocatalytic activity of the electrodes materials accelerating the oxygen and electron transfer processes. The battery performance was also evaluated using PAN-functionalized electrodes exhibiting a high of energy efficiency of 84% (at current density 20 mA cm −2 ) up to 30th cycle, indicating a promising alternative for improving the VFB

Development of oxygen sensing technology in an irradiated fuel rod. Characteristic test of oxygen sensor

International Nuclear Information System (INIS)

Saito, Junichi; Hoshiya, Taiji; Sakurai, Fumio; Sakai, Haruyuki

1996-03-01

At the Department of JMTR (Japan Materials Test Reactor), the re-instrumentation technologies to a high burnup fuel rod irradiated in an LWR have been developed to study irradiation behavior of the fuel during power transient. It has been progressed developing a chemical sensor as one of the re-instrumentation technologies. This report summarizes the results of characteristic tests of an oxygen sensor made of Yttria Stabilized Zirconia (YSZ) as a solid electrolyte. Several kinds of experiments were carried out to evaluate the electromotive force (emf) performance, stability and lifetime of the oxygen sensor with Ni/NiO, Cr/Cr 2 O 3 and Fe/FeO, respectively as a reference electrode. From the experimental data, it is suggested that the reference electrode of Ni/NiO reveals the most appropriate characteristic of the sensor to measure the partial oxygen pressure in a fuel rod. It is the final goal of this development to clarify the change of oxygen chemical potential in a fuel rod during power transient. (author)

Altering Anode Thickness To Improve Power Production in Microbial Fuel Cells with Different Electrode Distances

KAUST Repository

Ahn, Yongtae

2013-01-17

A better understanding of how anode and separator physical properties affect power production is needed to improve energy and power production by microbial fuel cells (MFCs). Oxygen crossover from the cathode can limit power production by bacteria on the anode when using closely spaced electrodes [separator electrode assembly (SEA)]. Thick graphite fiber brush anodes, as opposed to thin carbon cloth, and separators have previously been examined as methods to reduce the impact of oxygen crossover on power generation. We examined here whether the thickness of the anode could be an important factor in reducing the effect of oxygen crossover on power production, because bacteria deep in the electrode could better maintain anaerobic conditions. Carbon felt anodes with three different thicknesses were examined to see the effects of thicker anodes in two configurations: widely spaced electrodes and SEA. Power increased with anode thickness, with maximum power densities (604 mW/m 2, 0.32 cm; 764 mW/m2, 0.64 cm; and 1048 mW/m2, 1.27 cm), when widely spaced electrodes (4 cm) were used, where oxygen crossover does not affect power generation. Performance improved slightly using thicker anodes in the SEA configuration, but power was lower (maximum of 689 mW/m2) than with widely spaced electrodes, despite a reduction in ohmic resistance to 10 Ω (SEA) from 51-62 Ω (widely spaced electrodes). These results show that thicker anodes can work better than thinner anodes but only when the anodes are not adversely affected by proximity to the cathode. This suggests that reducing oxygen crossover and improving SEA MFC performance will require better separators. © 2012 American Chemical Society.

Altering Anode Thickness To Improve Power Production in Microbial Fuel Cells with Different Electrode Distances

KAUST Repository

Ahn, Yongtae; Logan, Bruce E.

2013-01-01

A better understanding of how anode and separator physical properties affect power production is needed to improve energy and power production by microbial fuel cells (MFCs). Oxygen crossover from the cathode can limit power production by bacteria on the anode when using closely spaced electrodes [separator electrode assembly (SEA)]. Thick graphite fiber brush anodes, as opposed to thin carbon cloth, and separators have previously been examined as methods to reduce the impact of oxygen crossover on power generation. We examined here whether the thickness of the anode could be an important factor in reducing the effect of oxygen crossover on power production, because bacteria deep in the electrode could better maintain anaerobic conditions. Carbon felt anodes with three different thicknesses were examined to see the effects of thicker anodes in two configurations: widely spaced electrodes and SEA. Power increased with anode thickness, with maximum power densities (604 mW/m 2, 0.32 cm; 764 mW/m2, 0.64 cm; and 1048 mW/m2, 1.27 cm), when widely spaced electrodes (4 cm) were used, where oxygen crossover does not affect power generation. Performance improved slightly using thicker anodes in the SEA configuration, but power was lower (maximum of 689 mW/m2) than with widely spaced electrodes, despite a reduction in ohmic resistance to 10 Ω (SEA) from 51-62 Ω (widely spaced electrodes). These results show that thicker anodes can work better than thinner anodes but only when the anodes are not adversely affected by proximity to the cathode. This suggests that reducing oxygen crossover and improving SEA MFC performance will require better separators. © 2012 American Chemical Society.

Erosion on spark plug electrodes; Funkenerosion an Zuendkerzenelektroden

Energy Technology Data Exchange (ETDEWEB)

Rager, J.

2006-07-01

Durability of spark plugs is mainly determined by spark gap widening, caused by electrode wear. Knowledge about the erosion mechanisms of spark plug materials is of fundamental interest for the development of materials with a high resistance against electrode erosion. It is therefore crucial to identify those parameters which significantly influence the erosion behaviour of a material. In this work, a reliable and reproducible testing method is presented which produces and characterizes electrode wear under well-defined conditions and which is capable of altering parameters specifically. Endurance tests were carried out to study the dependence of the wear behaviour of pure nickel and platinum on the electrode temperature, gas, electrode gap, electrode diameter, atmospheric pressure, and partial pressure of oxygen. It was shown that erosion under nitrogen is negligible, irrespective of the material. This disproves all common mechanism discussed in the literature explaining material loss of spark plug electrodes. Based on this observation and the variation of the mentioned parameters a new erosion model was deduced. This relies on an oxidation of the electrode material and describes the erosion of nickel and platinum separately. For nickel, electrode wear is caused by the removal of an oxide layer by the spark. In the case of platinum, material loss occurs due to the plasma-assisted formation and subsequent evaporation of volatile oxides in the cathode spot. On the basis of this mechanism a new composite material was developed whose erosion resistance is superior to pure platinum. Oxidation resistant metal oxide particles were added to a platinum matrix, thus leading to a higher erosion resistance of the composite. However, this can be decreased by a side reaction, the separation of oxygen from the metal oxides, which effectively assists the oxidation of the matrix. This reaction can be suppressed by using highly stable oxides, characterized by a large negative Gibbs

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 ...

Redox switching and oxygen evolution at oxidized metal and metal oxide electrodes: iron in base.

Science.gov (United States)

Lyons, Michael E G; Doyle, Richard L; Brandon, Michael P

2011-12-28

Outstanding issues regarding the film formation, redox switching characteristics and the oxygen evolution reaction (OER) electrocatalytic behaviour of multicycled iron oxyhydroxide films in aqueous alkaline solution have been revisited. The oxide is grown using a repetitive potential multicycling technique, and the mechanism of the latter hydrous oxide formation process has been discussed. A duplex layer model of the oxide/solution interphase region is proposed. The acid/base behaviour of the hydrous oxide and the microdispersed nature of the latter material has been emphasised. The hydrous oxide is considered as a porous assembly of interlinked octahedrally coordinated anionic metal oxyhydroxide surfaquo complexes which form an open network structure. The latter contains considerable quantities of water molecules which facilitate hydroxide ion discharge at the metal site during active oxygen evolution, and also charge compensating cations. The dynamics of redox switching has been quantified via analysis of the cyclic voltammetry response as a function of potential sweep rate using the Laviron-Aoki electron hopping diffusion model by analogy with redox polymer modified electrodes. Steady state Tafel plot analysis has been used to elucidate the kinetics and mechanism of oxygen evolution. Tafel slope values of ca. 60 mV dec(-1) and ca. 120 mV dec(-1) are found at low and high overpotentials respectively, whereas the reaction order with respect to hydroxide ion activity changes from ca. 3/2 to ca. 1 as the potential is increased. These observations are rationalised in terms of a kinetic scheme involving Temkin adsorption and the rate determining formation of a physisorbed hydrogen peroxide intermediate on the oxide surface. The dual Tafel slope behaviour is ascribed to the potential dependence of the surface coverage of adsorbed intermediates.

Characteristics of Honeycomb-Type Oxygen Generator with Electrolyte Based on Doped Bismuth Oxide

Science.gov (United States)

Chen, Yu-Wen; Liu, Yi-Xin; Wang, Sea-Fue; Devasenathipathy, Rajkumar

2018-03-01

An oxygen generator using Y-doped Bi2O3 as electrolyte to transport oxygen ions has been developed, having honeycomb-type structure with dimensions of 40 mm × 35 mm × 30 mm and consisting of 13 × 12 channels. External wire circuitry for the channels arrayed using parallel, series, and hybrid connection was evaluated to achieve the best oxygen separation efficiency. It was observed that the oxygen generator with hybrid connection facilitated evolution of oxygen at maximum of 117 sccm and high purity > 99.9% at 550°C under current flow of 14 A. Addition of 5 wt.% silane and 3 wt.% glass-ceramic powder to the Ag slurry used at both electrodes not only increased the coverage of the metal electrode on the ceramic substrate during dip coating but also prevented cracking at the electrode layer of the module under stress from the electric field and temperature during high-temperature operation, thus reducing the decay rate of the oxygen generator in durability testing.

Surface effects of electrode-dependent switching behavior of resistive random-access memory

KAUST Repository

Ke, Jr Jian; Wei, Tzu Chiao; Tsai, Dung Sheng; Lin, Chun-Ho; He, Jr-Hau

2016-01-01

of the oxygen chemisorption process was proposed to explain this electrode-dependent switching behavior. The temperature-dependent switching voltage demonstrates that the ReRAM devices fabricated with Pt electrodes have a lower activation energy

Microcomputer-based system for registration of oxygen tension in peripheral muscle.

Science.gov (United States)

Odman, S; Bratt, H; Erlandsson, I; Sjögren, L

1986-01-01

For registration of oxygen tension fields in peripheral muscle a microcomputer based system was designed on the M6800 microprocessor. The system was designed to record the signals from a multiwire oxygen electrode, MDO, which is a multiwire electrode for measuring oxygen on the surface of an organ. The system contained patient safety isolation unit built on optocopplers and the upper frequency limit was 0.64 Hz. Collected data were corrected for drift and temperature changes during the measurement by using pre- and after calibrations and a linear compensation technique. Measure drift of the electrodes were proved to be linear and thus the drift could be compensated for. The system was tested in an experiment on pig. To study the distribution of oxygen statistically mean, standard deviation, skewness and curtosis were calculated. To see changes or differences between histograms a Kolmogorv-Smirnov test was used.

Rhodium nanoparticle-modified screen-printed graphite electrodes for the determination of hydrogen peroxide in tea extracts in the presence of oxygen.

Science.gov (United States)

Gatselou, Vasiliki A; Giokas, Dimothenis L; Vlessidis, Athanasios G; Prodromidis, Mamas I

2015-03-01

In this work we describe the fabrication of nanostructured electrocatalytic surfaces based on polyethyleneimine (PEI)-supported rhodium nanoparticles (Rh-NP) over graphite screen-printed electrodes (SPEs) for the determination of hydrogen peroxide in the presence of oxygen. Rh-NP, electrostatically stabilized by citrate anions, were immobilized over graphite SPEs, through coulombic attraction on a thin film of positively charged PEI. The functionalized sensors, polarized at 0.0 V vs. Ag/AgCl/3 M KCl, exhibited a linear response to H2O2 over the concentration range from 5 to 600 μmol L(-1) H2O2 in the presence of oxygen. The 3σ limit of detection was 2 μmol L(-1) H2O2, while the reproducibility of the method at the concentration level of 10 μmol L(-1) H2O2 (n=10) and between different sensors (n=4) was lower than 3 and 5%, respectively. Most importantly, the sensors showed an excellent working and storage stability at ambient conditions and they were successfully applied to the determination of H2O2 produced by autooxidation of polylphenols in tea extracts with ageing. Recovery rates ranged between 97 and 104% suggesting that the as-prepared electrodes can be used for the development of small-scale, low-cost chemical sensors for use in on-site applications. Copyright © 2014 Elsevier B.V. All rights reserved.

Novel solid oxide cells with SrCo0.8Fe0.1Ga0.1O3-δ oxygen electrode for flexible power generation and hydrogen production

Science.gov (United States)

Meng, Xiuxia; Shen, Yichi; Xie, Menghan; Yin, Yimei; Yang, Naitao; Ma, Zi-Feng; Diniz da Costa, João C.; Liu, Shaomin

2016-02-01

This work investigates the performance of solid oxide cells as fuel cells (SOFCs) for power production and also as electrolysis cells (SOECs) for hydrogen production. In order to deliver this dual mode flexible operation system, a novel perovskite oxide based on Ga3+ doped SrCo0.8Fe0.1Ga0.1O3-δ (SCFG) is synthesized via a sol-gel method. Its performance for oxygen electrode catalyst was then evaluated. Single solid oxide cell in the configuration of Ni-YSZ|YSZ|GDC|SCFG is assembled and tested in SOFC or SOEC modes from 550 to 850 °C with hydrogen as the fuel or as the product, respectively. GDC is used to avoid the reaction between the electrolyte YSZ and the cobalt-based electrode. Under SOFC mode, a maximum power density of 1044 mW cm-2 is obtained at 750 °C. Further, the cell delivers a stable power output of 650 mW cm-2 up to 125 h at 0.7 V. In the electrolysis mode, when the applied voltage is controlled at 2 V, the electrolysis current density reaches 3.33 A cm-2 at 850 °C with the hydrogen production rate up to 22.9 mL min-1 cm-2 (STP). These results reveal that SCFG is a very promising oxygen electrode material for application in both SOFC and SOEC.

In situ formation of a 3D core-shell and triple-conducting oxygen reduction reaction electrode for proton-conducting SOFCs

Science.gov (United States)

Zhang, Zhenbao; Wang, Jian; Chen, Yubo; Tan, Shaozao; Shao, Zongping; Chen, Dengjie

2018-05-01

BaZrxCeyY1-x-yO3-δ are recognized proton-conducting electrolyte materials for proton-conducting solid oxide fuel cells (H+-SOFCs) below 650 °C. Here Co cations are incorporated into the BaZr0.4Ce0.4Y0.2O3-δ (BZCY) scaffold to generate a 3D core-shell and triple-conducting (H+/O2-/e-) electrode in situ via infiltrating and reactive sintering. The core is the bulk BZCY scaffold, while the shell is composed of the cubic Ba(Zr0.4Ce0.4Y0.2)1-xCoxO3-δ, cubic spinel Co3O4 and cubic fluorite (Ce, Zr, Y)O2. The obtained electrode exhibits an excellent compatibility with the BZCY electrolyte, and performs well in yielding a low and stable polarization resistance for oxygen reduction reaction for intermediate-temperature H+-SOFCs. In particular, it achieves polarization resistances as low as 0.094 and 0.198 Ω cm2 at 650 and 600 °C in wet air (3% H2O) when the sintering temperature for the electrode is 900 °C. In addition, a symmetrical cell also exhibits operation stability of 70 h at 650 °C. Furthermore, a fuel cell assembled with the 3D core-shell and triple-conducting electrode delivers a peak power density of ∼330 mW cm-2 at 650 °C. The substantially improved electrochemical performance and high stability are ascribed to the unique core-shell structure and the formation of Ba(Zr0.4Ce0.4Y0.2)1-xCoxO3-δ in the shell.

Tailoring properties of reduced graphene oxide by oxygen plasma treatment

Science.gov (United States)

Kondratowicz, Izabela; Nadolska, Małgorzata; Şahin, Samet; Łapiński, Marcin; Prześniak-Welenc, Marta; Sawczak, Mirosław; Yu, Eileen H.; Sadowski, Wojciech; Żelechowska, Kamila

2018-05-01

We report an easily controllable, eco-friendly method for tailoring the properties of reduced graphene oxide (rGO) by means of oxygen plasma. The effect of oxygen plasma treatment time (1, 5 and 10 min) on the surface properties of rGO was evaluated. Physicochemical characterization using microscopic, spectroscopic and thermal techniques was performed. The results revealed that different oxygen-containing groups (e.g. carboxyl, hydroxyl) were introduced on the rGO surface enhancing its wettability. Furthermore, upon longer treatment time, other functionalities were created (e.g. quinones, lactones). Moreover, external surface of rGO was partially etched resulting in an increase of the material surface area and porosity. Finally, the oxygen plasma-treated rGO electrodes with bilirubin oxidase were tested for oxygen reduction reaction. The study showed that rGO treated for 10 min exhibited twofold higher current density than untreated rGO. The oxygen plasma treatment may improve the enzyme adsorption on rGO electrodes by introduction of oxygen moieties and increasing the porosity.

Assay of Aliphatic Phthalates in Polymer Products by Sensitive Polarographic Method: Health and Environmental Issue

Directory of Open Access Journals (Sweden)

Munawar Saeed

2010-06-01

Full Text Available A faster, simpler and sensitive method was developed for determination of aliphatic phthalates using differential pulse polarography (DPP as standard technique. The choice and concentration of base electrolyte, solvent, initial potential, effect of water addition and interference by other phthalates were the main parameters to optimize for enhancement of peak current and to obtain well-defined polarogram with lower background current using 1.3 x 10-4 M di-butyl phthalate (DBP solution. Best results were obtained in the presence of tetra methyl ammonium bromide (TMAB as electrolyte in methanol solvent with initial potential, -1.4 V. A linear calibration plot was observed in the range of 3 x 10-7 – 1.6 x 10-4 M DBP solution as aliphatic phthalates with lower detection limit of 5.9 x 10-8 M and linear regression coefficient of 0.9987. The developed polarographic method was successfully applied for analysis of aliphtaic phthalates in various samples of locally available polymer products such as baby toys, nipples, teethers, infusion blood bags and shopping bags. The results of the current method were compared with those obtained by a reported method and good agreement was found between them.

Microwave exposure as a fast and cost-effective alternative of oxygen plasma treatment of indium-tin oxide electrode for application in organic solar cells

Science.gov (United States)

Soultati, Anastasia; Kostis, Ioannis; Papadimitropoulos, Giorgos; Zeniou, Angelos; Gogolides, Evangelos; Alexandropoulos, Dimitris; Vainos, Nikos; Davazoglou, Dimitris; Speliotis, Thanassis; Stathopoulos, Nikolaos A.; Argitis, Panagiotis; Vasilopoulou, Maria

2017-12-01

Pre-treatment methods are commonly employed to clean as well as to modify electrode surfaces. Many previous reports suggest that modifying the surface properties of indium tin oxide (ITO) by oxygen plasma treatment is a crucial step for the fabrication of high performance organic solar cells. In this work, we propose a fast and cost-effective microwave exposure step for the modification of the surface properties of ITO anode electrodes used in organic solar cells. It is demonstrated that a short microwave exposure improves the hydrophilicity and reduces the roughness of the ITO surface, as revealed by contact angle and atomic force microscopy (AFM) measurements, respectively, leading to a better quality of the PEDOT:PSS film coated on top of it. Similar results were obtained with the commonly used oxygen plasma treatment of ITO suggesting that microwave exposure is an effective process for modifying the surface properties of ITO with the benefits of low-cost, easy and fast processing. In addition, the influence of the microwave exposure of ITO anode electrode on the performance of an organic solar cell based on the poly(3-hexylthiophene):[6,6]-phenyl C70 butyric acid methyl ester (P3HT:PC70BM) blend is investigated. The 71% efficiency enhancement obtained in the microwave annealed-ITO based device as compared to the device with the as-received ITO was mainly attributed to the improvement in the short circuit current (J sc) and decreased leakage current caused by the reduced series and the increased shunt resistances and also by the higher charge generation efficiency, and the reduced recombination losses.

Estudo polarográfico sobre a determinação de Fe(III utilizando-se a técnica da polarografia de pulso diferencial Polarographic study about the determination of Fe(III using the technique of differencial pulse polarography

Directory of Open Access Journals (Sweden)

Luiz Manoel Aleixo

2001-12-01

Full Text Available A differential pulse polarographic study with the objective to determine iron (III in presense of copper (II in a supporting electrolyte based on citrate - EDTA was made. The best experimental conditions found were a supporting electrolyte of citrate 0.25 mol L-1, EDTA 0.050 mol L-1 and KNO3 0.50 mol L-1, pH 5.00. In this media iron (III showed a polarographic peak in -0.08 V and the copper (II in -0.34 V, both vs. Ag/AgCl (saturated KCl. Thus, a analytical method was developed and applied to determine iron (III in brass alloy, a matrix were copper is in large excess over iron. The results obtained showed no interference of copper in the iron determination. The value of 0.21% of iron in the sample alloy composition was obtained and the method was validated by atomic absortion and recovery test, and the results exhibited a good agreement with the proposed method.

Reversible Decomposition of Secondary Phases in BaO Infiltrated LSM Electrodes-Polarization Effects

DEFF Research Database (Denmark)

Traulsen, Marie Lund; McIntyre, Melissa D.; Norrman, Kion

2016-01-01

and Raman spectroscopy reveal the formation of a secondary phase, Ba3Mn2O8, on the electrode. During the in operando Raman investigation of the BaO-infiltrated La0.85Sr0.15MnO3±δ electrodes, experiments are performed at 300 and 500 °C with oxygen partial pressure 0.1 atm and with −1 or +1 V Applied...... for the reduced polarization resistance observed at open Circuit voltage (OCV) in an oxygen containing atmosphere. Furthermore, the results illustrate the dramatic differences between the electrode surface composition at OCV and during cathodic polarization. Overall, the results highlight the dynamic interactions...... between minor secondary phases and applied potential, a general effect that may be important for the high-performance frequently observed with ceramic electrodes prepared by infiltration....

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

African Journals Online (AJOL)

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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 ...

Limitations of potentiometric oxygen sensors operating at low oxygen levels

DEFF Research Database (Denmark)

Lund, Anders; Jacobsen, Torben; Hansen, Karin Vels

2011-01-01

The electrochemical processes that limit the range of oxygen partial pressures in which potentiometric oxygen sensors can be used, were analysed using a theoretical and an experimental approach. Electrochemical impedance spectroscopy was performed on porous Pt/yttria stabilised zirconia (YSZ......) electrodes between 10−6 and 0.2 bar and at temperatures between 500 and 950 °C. The flow of oxide ions and electron holes through a sensor cell, with a YSZ electrolyte, were calculated under similar conditions. The oxygen permeation of the sensor cell was insignificant at an oxygen partial pressure of 10......−6 bar for an inlet flow rate higher than 2 L h−1 between 600 and 800 °C. The polarisation resistance measured between 10−6 and 10−4 bar was found to be inversely proportional to the oxygen partial pressure, nearly temperature independent and inversely proportional to the inlet gas flow rate, which shows...

Advanced Architectures and Relatives of Air Electrodes in Zn–Air Batteries

Science.gov (United States)

Pan, Jing; Xu, Yang Yang; Yang, Huan; Dong, Zehua; Liu, Hongfang

2018-01-01

Abstract Zn–air batteries are becoming the promising power sources for portable and wearable electronic devices and hybrid/electric vehicles because of their high specific energy density and the low cost for next‐generation green and sustainable energy technologies. An air electrode integrated with an oxygen electrocatalyst is the most important component and inevitably determines the performance and cost of a Zn–air battery. This article presents exciting advances and challenges related to air electrodes and their relatives. After a brief introduction of the Zn–air battery, the architectures and oxygen electrocatalysts of air electrodes and relevant electrolytes are highlighted in primary and rechargeable types with different configurations, respectively. Moreover, the individual components and major issues of flexible Zn–air batteries are also highlighted, along with the strategies to enhance the battery performance. Finally, a perspective for design, preparation, and assembly of air electrodes is proposed for the future innovations of Zn–air batteries with high performance. PMID:29721418

Antibacterial validation of electrogenerated hypochlorite using carbon-based electrodes.

Science.gov (United States)

Locker, J; Fitzgerald, P; Sharp, D

2014-12-01

This proof-of-concept study explores the novel use of carbon-based electrodes for the electrochemical generation of hypochlorite and compares the antimicrobial efficacy against commercial hypochlorite solution. Antimicrobial concentrations of hypochlorite were generated using pad-printed carbon and carbon fibre electrodes, yielding up to 0·027% hypochlorite in 60 min and 0·1% hypochlorite in 15 min, respectively, in a nondivided assembly. The minimum inhibitory concentration (MIC) of the electrogenerated hypochlorite produced using carbon fibre electrodes was established for four medically important bacteria (Pseudomonas aeruginosa and Staphylococcus aureus approx. 0·025%, Escherichia coli and Enterococcus faecalis approx. 0·012%) and found to be in agreement with those determined using commercial hypochlorite solution. Therefore, carbon-based electrodes, particularly carbon fibre, have proven effective for the generation of antimicrobial concentrations of hypochlorite. The similarity of the MIC values to commercial hypochlorite solutions suggests that the antimicrobial efficacy is derived from the quantified hypochlorite generated and not due to marked cogeneration of reactive oxygen species, as identified for other assemblies. As such, the application of carbon electrodes may be suitable for the local production of hypochlorite for healthcare antisepsis. Carbon fibre electrodes can rapidly generate antimicrobial concentrations of hypochlorite; as such, these cheap and commercially available electrodes are proposed for the local production of hypochlorite for healthcare antisepsis. Importantly, the antimicrobial properties of the electrochemically generated hypochlorite mirror those of commercial hypochlorite, suggesting this is not enhanced by the cogeneration of reactive oxygen species. This illustrates the potential use of disposable carbon electrodes for localized small-volume production of hypochlorite for surface and skin cleansing, and opens a broader

Electrochemistry of technetium

International Nuclear Information System (INIS)

Russell, C.D.; Alabama Univ., Birmingham

1982-01-01

Recent work on the electrochemistry of technetium is reviewed, covering the period 1973-1980. Topics include polarographic studies of aqueous pertechnetate, coulometric studies of aqueous pertechnetate at mercury cathodes, and electrochemistry of pertechnetate at solid electrodes. A review is also given of electrochemistry of other technetium compounds, non-aqueous systems, chemical redox reactions, and substitution reactions. Consideration is also given to studies of electrochemistry at tracer concentrations, electrolytic syntheses, standard electrode potentials, and electroanalytical methods. (author)

Mass-Producible 2D-MoS2-Impregnated Screen-Printed Electrodes That Demonstrate Efficient Electrocatalysis toward the Oxygen Reduction Reaction.

Science.gov (United States)

Rowley-Neale, Samuel J; Smith, Graham C; Banks, Craig E

2017-07-12

Two-dimensional molybdenum disulfide (2D-MoS 2 ) screen-printed electrodes (2D-MoS 2 -SPEs) have been designed, fabricated, and evaluated toward the electrochemical oxygen reduction reaction (ORR) within acidic aqueous media. A screen-printable ink has been developed that allows for the tailoring of the 2D-MoS 2 content/mass used in the fabrication of the 2D-MoS 2 -SPEs, which critically affects the observed ORR performance. In comparison to the graphite SPEs (G-SPEs), the 2D-MoS 2 -SPEs are shown to exhibit an electrocatalytic behavior toward the ORR which is found, critically, to be reliant upon the percentage mass incorporation of 2D-MoS 2 in the 2D-MoS 2 -SPEs; a greater percentage mass of 2D-MoS 2 incorporated into the 2D-MoS 2 -SPEs results in a significantly less electronegative ORR onset potential and a greater signal output (current density). Using optimally fabricated 2D-MoS 2 -SPEs, an ORR onset and a peak current of approximately +0.16 V [vs saturated calomel electrode (SCE)] and -1.62 mA cm -2 , respectively, are observed, which exceeds the -0.53 V (vs SCE) and -635 μA cm -2 performance of unmodified G-SPEs, indicating an electrocatalytic response toward the ORR utilizing the 2D-MoS 2 -SPEs. An investigation of the underlying electrochemical reaction mechanism of the ORR within acidic aqueous solutions reveals that the reaction proceeds via a direct four-electron process for all of the 2D-MoS 2 -SPE variants studied herein, where oxygen is electrochemically favorably reduced to water. The fabricated 2D-MoS 2 -SPEs are found to exhibit no degradation in the observed achievable current over the course of 1000 repeat scans. The production of such inks and the resultant mass-producible 2D-MoS 2 -SPEs mitigates the need to modify post hoc an electrode via the drop-casting technique that has been previously shown to result in a loss of achievable current over the course of 1000 repeat scans. The 2D-MoS 2 -SPEs designed, fabricated, and tested herein could

Response behaviour of oxygen sensing solid electrolytes

NARCIS (Netherlands)

Winnubst, Aloysius J.A.; Scharenborg, A.H.A.; Burggraaf, A.J.

1985-01-01

The response time (t r) after a step change in oxygen partial pressure was investigated for some solid electrolytes used in Nernst type oxygen sensors. The electrolyte as well as the (porous) electrode material affect the value oft r. Stabilized Bi2O3 materials exhibit slower response rates (largert

Micro-Membrane Electrode Assembly Design to Precisely Measure the in Situ Activity of Oxygen Reduction Reaction Electrocatalysts for PEMFC.

Science.gov (United States)

Long, Zhi; Li, Yankai; Deng, Guangrong; Liu, Changpeng; Ge, Junjie; Ma, Shuhua; Xing, Wei

2017-06-20

An in situ micro-MEA technique, which could precisely measure the performance of ORR electrocatalyst using Nafion as electrolyte, was designed and compared with regular thin-film rotating-disk electrode (TFRDE) (0.1 M HClO 4 ) and normal in situ membrane electrode assembly (MEA) tests. Compared to the traditional TFRDE method, the micro-MEA technique makes the acquisition of catalysts' behavior at low potential values easily achieved without being limited by the solubility of O 2 in water. At the same time, it successfully mimics the structure of regular MEAs and obtains similar results to a regular MEA, thus providing a new technique to simply measure the electrode activity without being bothered by complicated fabrication of regular MEA. In order to further understand the importance of in situ measurement, Fe-N-C as a typical oxygen reduction reaction (ORR) free-Pt catalyst was evaluated by TFRDE and micro-MEA. The results show that the half wave potential of Fe-N-C only shifted negatively by -135 mV in comparison with state-of-the-art Pt/C catalysts from TFRDE tests. However, the active site density, mass transfer of O 2 , and the proton transfer conductivity are found to strongly influence the catalyst activity in the micro-MEA, thereby resulting in a much lower limiting current density than Pt/C (8.7 times lower). Hence, it is suggested that the micro-MEA is better in evaluating the in situ ORR performance, where the catalysts are characterized more thoroughly in terms of intrinsic activity, active site density, proton transfer, and mass transfer properties.

Phenomena and significance of intermediate spillover in electrocatalysis of oxygen and hydrogen electrode reactions

Directory of Open Access Journals (Sweden)

Jakšić Jelena M.

2012-01-01

Full Text Available Altervalent hypo-d-oxides of transition metal series impose spontaneous dissociative adsorption of water molecules and pronounced membrane spillover transferring properties instantaneously resulting with corresponding bronze type (Pt/HxWO3 under cathodic, and/or its hydrated state (Pt/W(OH6 responsible for the primary oxide (Pt-OH effusion, under anodic polarization, this way establishing instantaneous reversibly revertible alterpolar bronze features (Pt/H0.35WO3 Pt/W(OH6, and substantially advanced electrocatalytic properties of these composite interactive electrocatalysts. As the consequence, the new striking and unpredictable prospects both in law and medium temperature proton exchange membrane fuell cell (L&MT PEMFC and water electrolysis (WE have been opened by the interactive supported individual (Pt, Pd, Ni or prevailing hyper-d-electronic nanostructured intermetallic phase clusters (WPt3, NbPt3, HfPd3, ZrNi3, grafted upon and within high altervalent capacity hypo-d-oxides (WO3, Nb2O5, Ta2O5, TiO2 and their proper mixed valence compounds, to create a novel type of alterpolar interchangeable composite electrocatalysts for hydrogen and oxygen electrode reactions. Whereas in aqueous media Pt (Pt/C features either chemisorbed catalytic surface properties of H-adatoms (Pt-H, or surface oxide (Pt=O, missing any effusion of other interacting species, new generation and selection of composite and interactive strong metal-support interaction (SMSI electrocatalysts in condensed wet state primarily characterizes interchangeable extremely fast reversible spillover of either H-adatoms, or the primary oxides (Pt-OH, Au-OH, or the invertible bronze type behavior of these significant interactive electrocatalytic ingredients. Such nanostructured type electrocatalysts, even of mixed hypo-d-oxide structure (Pt/H0.35WO3/TiO2/C, Pt/HxNbO3/TiO2/C, have for the first time been synthesized by the sol-gel methods and shown rather high stability, electron

Mn valence state and electrode performance of perovskite-type ...

Indian Academy of Sciences (India)

increase in the oxidation state of Mn ions was due to the formation of Mn4+ ions and oxygen vacancies. The addition of Cu ions to LSM systems could lead to enhanced electrode performance for oxygen reduction reactions originating from the change in valence of Mn ions. Keywords. Cu-doped LSM; electrical conductivity; ...

Characterization and Electrocatalytic Properties of Titanium-Based Ru0.3Co0.7−xCex Mixed Oxide Electrodes for Oxygen Evolution in Alkaline Solution

Directory of Open Access Journals (Sweden)

Hongjun Wu

2011-01-01

Full Text Available Ti-supported RuO2-Co3O4-CeO2 (Ru0.3Co0.7−xCex oxide, 0≤x≤0.7 electrodes were prepared by sol-gel process. The phase structure, surface morphology, and microstructure of the oxide layer were characterized by X-ray diffraction (XRD and scanning electron microscopy (SEM. Electrocatalytic activity and oxygen evolution reaction (OER kinetics on these electrodes in 1.0 mol⋅dm−3 KOH solution were studied by recording open-circuit potential, cyclic voltammetry, and polarisation curves. The results showed that the appropriate content of CeO2 could reduce the grain size and increase active surface area. The electrocatalytic activity shows a strong dependence on the CeO2 content in the film. Catalytic performance of mixed oxide electrodes with 40 mol % CeO2 was the best, with the greatest voltammetric charge, 86.23 mC⋅cm−2, and the smallest apparent activation energy for OER at 0.60 V was 22.76 kJ⋅mol−1.

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)

Methods and systems for in-situ electroplating of electrodes

Science.gov (United States)

Zappi, Guillermo Daniel; Zarnoch, Kenneth Paul; Huntley, Christian Andrew; Swalla, Dana Ray

2015-06-02

The present techniques provide electrochemical devices having enhanced electrodes with surfaces that facilitate operation, such as by formation of a porous nickel layer on an operative surface, particularly of the cathode. The porous metal layer increases the surface area of the electrode, which may result in increasing the efficiency of the electrochemical devices. The formation of the porous metal layer is performed in situ, that is, after the assembly of the electrodes into an electrochemical device. The in situ process offers a number of advantages, including the ability to protect the porous metal layer on the electrode surface from damage during assembly of the electrochemical device. The enhanced electrode and the method for its processing may be used in any number of electrochemical devices, and is particularly well suited for electrodes in an electrolyzer useful for splitting water into hydrogen and oxygen.

An electrochemical sensor for monitoring oxygen or hydrogen in water

International Nuclear Information System (INIS)

Leitai Yang; Morris, D.R.; Lister, D.H.

1997-01-01

Preliminary studies have been done on a simple electrochemical sensor which shows promise as a cheap, robust instrument for measuring dissolved oxygen or hydrogen in water. The sensor is based upon the solid-state electrolyte ''Nafion'' (trade name of perfluorinated sulphonic acid, manufactured by DuPont Inc.). The Nafion was dissolved in a mixture of aliphatic alcohols, made into a slurry with platinum black, and applied to a ∼1 cm-square electrode made of stainless steel gauze. The potential of the electrode was measured relative to a standard calomel electrode (SCE) in acid solutions at room temperature through which mixtures of oxygen and nitrogen or hydrogen and nitrogen were bubbled. The sensor was responsive to the equilibrating gas with good reproducibility. A similar sensor without the Nafion was not at all sensitive to changes in oxygen concentration. The voltage response of the sensor showed non-Nernstian behaviour, which suggests that the electrochemical reactions at the electrode surface are complex. Further testing of the sensor is required to verify its sensitivity and responsiveness in typical reactor coolant chemistries and to demonstrate its durability over a range of temperatures. (author). 4 refs, 4 figs, 1 tab

An electrochemical sensor for monitoring oxygen or hydrogen in water

Energy Technology Data Exchange (ETDEWEB)

Yang, Leitai; Morris, D R; Lister, D H [University of New Brunswick, Fredericton (Canada). Dept. of Chemical Engineering

1997-02-01

Preliminary studies have been done on a simple electrochemical sensor which shows promise as a cheap, robust instrument for measuring dissolved oxygen or hydrogen in water. The sensor is based upon the solid-state electrolyte ``Nafion`` (trade name of perfluorinated sulphonic acid, manufactured by DuPont Inc.). The Nafion was dissolved in a mixture of aliphatic alcohols, made into a slurry with platinum black, and applied to a {approx}1 cm-square electrode made of stainless steel gauze. The potential of the electrode was measured relative to a standard calomel electrode (SCE) in acid solutions at room temperature through which mixtures of oxygen and nitrogen or hydrogen and nitrogen were bubbled. The sensor was responsive to the equilibrating gas with good reproducibility. A similar sensor without the Nafion was not at all sensitive to changes in oxygen concentration. The voltage response of the sensor showed non-Nernstian behaviour, which suggests that the electrochemical reactions at the electrode surface are complex. Further testing of the sensor is required to verify its sensitivity and responsiveness in typical reactor coolant chemistries and to demonstrate its durability over a range of temperatures. (author). 4 refs, 4 figs, 1 tab.

Metabolic Prosthesis for Oxygenation of Ischemic Tissue

Energy Technology Data Exchange (ETDEWEB)

Greenbaum, Elias [ORNL

2009-01-01

This communication discloses new ideas and preliminary results on the development of a "metabolic prosthesis" for local oxygenation of ischemic tissue under physiological neutral conditions. We report for the first time the selective electrolysis of physiological saline by repetitively pulsed charge-limited electrolysis for the production of oxygen and suppression of free chlorine. For example, using 800 A amplitude current pulses and <200 sec pulse durations, we demonstrated prompt oxygen production and delayed chlorine production at the surface of a shiny 0.85 mm diameter spherical platinum electrode. The data, interpreted in terms of the ionic structure of the electric double layer, suggest a strategy for in situ production of metabolic oxygen via a new class of "smart" prosthetic implants for dealing with ischemic disease such as diabetic retinopathy. We also present data indicating that drift of the local pH of the oxygenated environment can be held constant using a feedback-controlled three electrode electrolysis system that chooses anode and cathode pair based on pH data provided by local microsensors. The work is discussed in the context of diabetic retinopathy since surgical techniques for multielectrode prosthetic implants aimed at retinal degenerative diseases have been developed.

Singular Sheet Etching of Graphene with Oxygen Plasma

Institute of Scientific and Technical Information of China (English)

Haider Al-Mumen; Fubo Rao; Wen Li; Lixin Dong

2014-01-01

This paper reports a simple and controllable post-synthesis method for engineering the number of graphene layers based on oxygen plasma etching. Singular sheet etching(SSE) of graphene was achieved with the optimum process duration of 38 seconds. As a demonstration of this SSE process, monolayer graphene films were produced from bilayer graphenes. Experimental investigations verified that the oxygen plasma etching removes a single layer graphene sheet in an anisotropic fashion rather than anisotropic mode. In addition,etching via the oxygen plasma at the ground electrodes introduced fewer defects to the bottom graphene layer compared with the conventional oxygen reactive ion etching using the powered electrodes. Such defects can further be reduced with an effective annealing treatment in an argon environment at 900-1000?C. These results demonstrate that our developed SSE method has enabled a microelectronics manufacturing compatible way for single sheet precision subtraction of graphene layers and a potential technique for producing large size graphenes with high yield from multilayer graphite materials.

Singular Sheet Etching of Graphene with Oxygen Plasma

Institute of Scientific and Technical Information of China (English)

Haider Al-Mumen; Fubo Rao; Wen Li; Lixin Dong

2014-01-01

This paper reports a simple and controllable post-synthesis method for engineering the number of graphene layers based on oxygen plasma etching. Singular sheet etching (SSE) of graphene was achieved with the optimum process duration of 38 seconds. As a demonstration of this SSE process, monolayer graphene films were produced from bilayer graphenes. Experimental investigations verified that the oxygen plasma etching removes a single layer graphene sheet in an anisotropic fashion rather than anisotropic mode. In addition, etching via the oxygen plasma at the ground electrodes introduced fewer defects to the bottom graphene layer compared with the conventional oxygen reactive ion etching using the powered electrodes. Such defects can further be reduced with an effective annealing treatment in an argon environment at 900-1000◦C. These results demonstrate that our developed SSE method has enabled a microelectronics manufacturing compatible way for single sheet precision subtraction of graphene layers and a potential technique for producing large size graphenes with high yield from multilayer graphite materials.

Meso-pores carbon nano-tubes (CNTs) tissues-perfluorocarbons (PFCs) hybrid air-electrodes for Li-O2 battery

Science.gov (United States)

Balaish, Moran; Ein-Eli, Yair

2018-03-01

Adding immiscible perfluorocarbons (PFCs), possessing superior oxygen solubility and diffusivity, to a free-standing (metal-free and binder-free) CNTs air-electrode tissues with a meso-pore structure, fully maximized the advantages of PFCs as oxygenated-species' channels-providers. The discharge behavior of hybrid PFCs-CNT Li-O2 systems demonstrated a drastic increase in cell capacity at high current density (0.2 mA cm-2), where oxygen transport limitations are best illustrated. The results of this research revealed several key factors affecting PFCs-Li-O2 systems. The incorporation of PFCs with higher superoxide solubility and oxygen diffusivity, but more importantly higher PFCs/electrolyte miscibility, in a meso-pore air-electrode enabled better exploitation of PFCs potential. Consequently, the utilization of the air-electrode' surface area was enhanced via the formation of artificial three phase reaction zones with additional oxygen transportation routes, leading to uniform and intimate Li2O2 deposit at areas further away from the oxygen reservoir. Associated mechanisms are discussed along with insights into an improved Li-O2 battery system.

Analysis of gases by a pulsed voltammetric sensor and the electrochemistry of high T[sub c] superconductors

Energy Technology Data Exchange (ETDEWEB)

Rochani, S.

1991-01-01

This thesis is presented in two parts: Studies of gas sensing probes and the electrochemistry of superconductors. A Clark type polarographic oxygen sensor was used to analyze oxygen, hydrogen, chlorine, sulphur dioxide and nitrogen dioxide. A pulsed potential was applied driven by an IBM/XT compatible microcomputer with a 12 bit A-D/D-A card. In a series of experiments for each gas singly, and then mixtures, the probe was calibrated at different concentrations of gas dissolved in water at different times during the pulse to observe the optimum measurement. In the case of oxygen for a 20 s pulse at [minus]0.65 V between a platinum and silver/silver chloride, the optimum calibration was obtained between 2 and 4 s with a detection limit of 0.27 ppm oxygen. Hydrogen was determined at +0.60 V with a 50 s pulse and optimum range 3 to 4 s and detection limit 0.02 ppm. Chlorine was reduced at 0 V and optimally detected after 2 s of a 20 s pulse with a detection limit of 3 ppm. A mixture of hydrogen and oxygen was analyzed without mutual interference by a train of pulses at [minus]0.65, 0, +0.60 V or [minus]0.65, +0.60 V. For sulphur dioxide, a new probe was constructed with a separate reference, working and auxillary electrodes to overcome the formation of silver sulphide at the auxillary electrode. A preliminary study of nitrogen dioxide was done by observing the oxidation and reduction current at different applied voltages. Samples of each of the room temperature superconductors YBa[sub 2]Cu[sub 3]O[sub 7[minus][sigma

Voltammetric and impedance behaviours of surface-treated nano-crystalline diamond film electrodes

International Nuclear Information System (INIS)

Liu, F. B.; Jing, B.; Cui, Y.; Di, J. J.; Qu, M.

2015-01-01

The electrochemical performances of hydrogen- and oxygen-terminated nano-crystalline diamond film electrodes were investigated by cyclic voltammetry and AC impedance spectroscopy. In addition, the surface morphologies, phase structures, and chemical states of the two diamond films were analysed by scanning probe microscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy, respectively. The results indicated that the potential window is narrower for the hydrogen-terminated nano-crystalline diamond film than for the oxygen-terminated one. The diamond film resistance and capacitance of oxygen-terminated diamond film are much larger than those of the hydrogen-terminated diamond film, and the polarization resistances and double-layer capacitance corresponding to oxygen-terminated diamond film are both one order of magnitude larger than those corresponding to the hydrogen-terminated diamond film. The electrochemical behaviours of the two diamond film electrodes are discussed

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

Molecule-Level g-C3N4 Coordinated Transition Metals as a New Class of Electrocatalysts for Oxygen Electrode Reactions

KAUST Repository

Zheng, Yao

2017-02-21

Organometallic complexes with metal-nitrogen/carbon (M-N/C) coordination are the most important alternatives to precious metal catalysts for oxygen reduction and evolution reactions (ORR and OER) in energy conversion devices. Here, we designed and developed a range of molecule-level graphitic carbon nitride (g-C3N4) coordinated transition metals (M-C3N4) as a new generation of M-N/C catalysts for these oxygen electrode reactions. As a proof-of-concept example, we conducted theoretical evaluation and experimental validation on a cobalt-C3N4 catalyst with a desired molecular configuration, which possesses comparable electrocatalytic activity to that of precious metal benchmarks for the ORR and OER in alkaline media. The correlation of experimental and computational results confirms that this high activity originates from the precise M-N2 coordination in the g-C3N4 matrix. Moreover, the reversible ORR/OER activity trend for a wide variety of M-C3N4 complexes has been constructed to provide guidance for the molecular design of this promising class of catalysts.

Direct detection of ammonium ion by means of oxygen electrocatalysis at a copper-polyaniline composite on a screen-printed electrode

International Nuclear Information System (INIS)

Zhybak, Mykhailo T.; Vagin, Mikhail Yu.; Beni, Valerio; Liu, Xianjie; Turner, Anthony P. F.; Dempsey, Eithne; Korpan, Yaroslav I.

2016-01-01

We describe a composite material for use in electrochemical oxygen reduction. A screen-printed electrode (SPE) was consecutively modified with electrodeposited copper, a Nafion membrane and electropolymerized polyaniline (PANi) to give an electrocatalytic composite of type PANi/Nafion/Cu_2O/SPE that displays good electrical conductivity at neutral pH values. It is found that the presence of ammonia causes complex formation with Cu(I), and this causes electroreduction of oxygen to result in an increased cathodic current. The finding was applied to the quantification of ammonium ions in the 1 to 1000 μM concentration range by amperometry at −0.45 V (vs. Ag/AgCl). This Faradaic phenomenon offers the advantage of direct voltammetric detection, one of the lowest known limits of detection (0.5 μM), and high sensitivity (250 mA∙M"−"1∙cm"−"2). It was applied to the determination of ammonium ion in human serum where it compared well with the photometric routine approach for clinical analysis using glutamate dehydrogenase. (author)

Voltammetric studies on composition and stabilities of complexes of tetracycline and oxytetracycline with some metal ions in aqueous medium

International Nuclear Information System (INIS)

Ghandour, M.A.; Azab, H.A.; Hassan, A.; Ali, A.M.

1992-01-01

The composition and stability of complexes of tetracycline and oxytetracycline with Cu(II), Cd(II), Pb(II) and UO 2 (II) have been studied polarographically (direct current and differential pulse polarographic techniques) at 25±0.1 deg C. Differential pulse polarographic studies have been particularly helpful in deciding the nature of metal-drug interactions at low concentrations. The reduction of Cu(II)-tetracycline has been found to be irreversible and diffusion controlled with the presence of an adsorption component. In the system uranyl(II)-tetracycline the complex formed has a stoichiometry of 1:1 and log K ox = 4.04 which is very close to that obtained by potentiometric measurements. The peak half width W 1/2 of the Pb(II)-OTC system is 60-70 mV indicating that the process is reversible and two electrons are consumed. The log β' is 10.30 in 0.1 mol dm -3 NaClO 4 . In the Cu(II)-OTC system two complexes were formed with log β 1 ' = 8.50 and log β 2 ' = 14.10. Cyclic voltammograms were recorded using a hanging dropping mercury electrode for the systems Cu(II), Cd(II), Pb(II) and UO 2 (II)-OTC to examine the irregularities in both peak potentials and peak currents during the polarographic investigations. (authors)

Voltammetric studies on composition and stabilities of complexes of tetracycline and oxytetracycline with some metal ions in aqueous medium. Voltammetrische Untersuchungen zur Zusammensetzung und Stabilitaet von Komplexen von Tetracyclin und Oxytetracyclin mit einigen Metallionen in waessrigem Medium

Energy Technology Data Exchange (ETDEWEB)

Ghandour, M A; Azab, H A; Hassan, A; Ali, A M [Dept. of Chemistry, Faculty of Science, Assiut Univ., Assiut (Egypt)

1992-01-01

The composition and stability of complexes of tetracycline and oxytetracycline with Cu(II), Cd(II), Pb(II) and UO[sub 2](II) have been studied polarographically (direct current and differential pulse polarographic techniques) at 25[+-]0.1 deg C. Differential pulse polarographic studies have been particularly helpful in deciding the nature of metal-drug interactions at low concentrations. The reduction of Cu(II)-tetracycline has been found to be irreversible and diffusion controlled with the presence of an adsorption component. In the system uranyl(II)-tetracycline the complex formed has a stoichiometry of 1:1 and log K[sub ox] = 4.04 which is very close to that obtained by potentiometric measurements. The peak half width W[sub 1/2] of the Pb(II)-OTC system is 60-70 mV indicating that the process is reversible and two electrons are consumed. The log [beta]' is 10.30 in 0.1 mol dm[sup -3] NaClO[sub 4]. In the Cu(II)-OTC system two complexes were formed with log [beta][sub 1]' = 8.50 and log [beta][sub 2]' = 14.10. Cyclic voltammograms were recorded using a hanging dropping mercury electrode for the systems Cu(II), Cd(II), Pb(II) and UO[sub 2](II)-OTC to examine the irregularities in both peak potentials and peak currents during the polarographic investigations. (authors).

Treating refinery wastewaters in microbial fuel cells using separator electrode assembly or spaced electrode configurations

KAUST Repository

Zhang, Fang

2014-01-01

The effectiveness of refinery wastewater (RW) treatment using air-cathode, microbial fuel cells (MFCs) was examined relative to previous tests based on completely anaerobic microbial electrolysis cells (MECs). MFCs were configured with separator electrode assembly (SEA) or spaced electrode (SPA) configurations to measure power production and relative impacts of oxygen crossover on organics removal. The SEA configuration produced a higher maximum power density (280±6mW/m2; 16.3±0.4W/m3) than the SPA arrangement (255±2mW/m2) due to lower internal resistance. Power production in both configurations was lower than that obtained with the domestic wastewater (positive control) due to less favorable (more positive) anode potentials, indicating poorer biodegradability of the RW. MFCs with RW achieved up to 84% total COD removal, 73% soluble COD removal and 92% HBOD removal. These removals were higher than those previously obtained in mini-MEC tests, as oxygen crossover from the cathode enhanced degradation in MFCs compared to MECs. © 2013 Elsevier Ltd.

Migration of interfacial oxygen ions modulated resistive switching in oxide-based memory devices

Science.gov (United States)

Chen, C.; Gao, S.; Zeng, F.; Tang, G. S.; Li, S. Z.; Song, C.; Fu, H. D.; Pan, F.

2013-07-01

Oxides-based resistive switching memory induced by oxygen ions migration is attractive for future nonvolatile memories. Numerous works had focused their attentions on the sandwiched oxide materials for depressing the characteristic variations, but the comprehensive studies of the dependence of electrodes on the migration behavior of oxygen ions are overshadowed. Here, we investigated the interaction of various metals (Ni, Co, Al, Ti, Zr, and Hf) with oxygen atoms at the metal/Ta2O5 interface under electric stress and explored the effect of top electrode on the characteristic variations of Ta2O5-based memory device. It is demonstrated that chemically inert electrodes (Ni and Co) lead to the scattering switching characteristics and destructive gas bubbles, while the highly chemically active metals (Hf and Zr) formed a thick and dense interfacial intermediate oxide layer at the metal/Ta2O5 interface, which also degraded the resistive switching behavior. The relatively chemically active metals (Al and Ti) can absorb oxygen ions from the Ta2O5 film and avoid forming the problematic interfacial layer, which is benefit to the formation of oxygen vacancies composed conduction filaments in Ta2O5 film thus exhibit the minimum variations of switching characteristics. The clarification of oxygen ions migration behavior at the interface can lead further optimization of resistive switching performance in Ta2O5-based memory device and guide the rule of electrode selection for other oxide-based resistive switching memories.

Sulfur tolerant composite cermet electrodes for solid oxide electrochemical cells

Science.gov (United States)

Isenberg, Arnold O.

1987-01-01

An electrochemical apparatus is made containing an exterior electrode bonded to the exterior of a tubular, solid, oxygen ion conducting electrolyte where the electrolyte is also in contact with an interior electrode, said exterior electrode comprising particles of an electronic conductor contacting the electrolyte, where a ceramic metal oxide coating partially surrounds the particles and is bonded to the electrolyte, and where a coating of an ionic-electronic conductive material is attached to the ceramic metal oxide coating and to the exposed portions of the particles.

Efficient oxidative dissolution of V2O3 by the in situ electro-generated reactive oxygen species on N-doped carbon felt electrodes

International Nuclear Information System (INIS)

Xue, Yudong; Wang, Yunting; Zheng, Shili; Sun, Zhi; Zhang, Yi; Jin, Wei

2017-01-01

Highlights: • Novel alkaline electro-Fenton-like was applied for V 2 O 3 oxidative dissolution. • N-doped carbon felt electrode was fabricated for the two-electron ORR. • ROS including ·OH and HO 2 − was in-situ generated from the electrochemical system. • A significant enhancement of V 2 O 3 dissolution was achieved due to the ROS. - Abstract: Oxidative dissolution is a critical step for the efficient remediation of heavy metal oxides in large-scale solid wastes. In the present study, a novel electro-oxidative dissolution process of V 2 O 3 to VO 4 3− is achieved by the in-situ generated reactive oxygen species on the N-doped carbon felt cathode in alkaline media. The electro-catalytic HO 2 − generation and hydrophilic behavior were significantly enhanced by the introduction of nitrogen-containing functional groups. Besides, the mechanism of electrochemical vanadium conversion is systematically illustrated, and a vanadium self-induced electro-Fenton-like reaction is proposed. By employing the radical quenching and ESR measurements, the contributions for V(III) dissolution is determined to be 43.5% by HO 2 − and 56.5% by hydroxyl radicals, respectively. It should be noted that the V 2 O 3 solid particles can be efficiently dissolved via adsorption-reaction scheme on the carbon felt electrode. This novel electrochemical strategy provides a promising solution for the heavy metal oxide treatment and further understanding for the in situ reactive oxygen species.

Hierarchically Designed 3D Holey C2N Aerogels as Bifunctional Oxygen Electrodes for Flexible and Rechargeable Zn-Air Batteries.

Science.gov (United States)

Shinde, Sambhaji S; Lee, Chi Ho; Yu, Jin-Young; Kim, Dong-Hyung; Lee, Sang Uck; Lee, Jung-Ho

2018-01-23

The future of electrochemical energy storage spotlights on the designed formation of highly efficient and robust bifunctional oxygen electrocatalysts that facilitate advanced rechargeable metal-air batteries. We introduce a scalable facile strategy for the construction of a hierarchical three-dimensional sulfur-modulated holey C 2 N aerogels (S-C 2 NA) as bifunctional catalysts for Zn-air and Li-O 2 batteries. The S-C 2 NA exhibited ultrahigh surface area (∼1943 m 2 g -1 ) and superb electrocatalytic activities with lowest reversible oxygen electrode index ∼0.65 V, outperforms the highly active bifunctional and commercial (Pt/C and RuO 2 ) catalysts. Density functional theory and experimental results reveal that the favorable electronic structure and atomic coordination of holey C-N skeleton enable the reversible oxygen reactions. The resulting Zn-air batteries with liquid electrolytes and the solid-state batteries with S-C 2 NA air cathodes exhibit superb energy densities (958 and 862 Wh kg -1 ), low charge-discharge polarizations, excellent reversibility, and ultralong cycling lives (750 and 460 h) than the commercial Pt/C+RuO 2 catalysts, respectively. Notably, Li-O 2 batteries with S-C 2 NA demonstrated an outstanding specific capacity of ∼648.7 mA h g -1 and reversible charge-discharge potentials over 200 cycles, illustrating great potential for commercial next-generation rechargeable power sources of flexible electronics.

Polymer Electrolyte-Based Ambient Temperature Oxygen Microsensors for Environmental Monitoring

Science.gov (United States)

Hunter, Gary W.; Xu, Jennifer C.; Liu, Chung-Chiun

2011-01-01

An ambient temperature oxygen microsensor, based on a Nafion polymer electrolyte, has been developed and was microfabricated using thin-film technologies. A challenge in the operation of Nafion-based sensor systems is that the conductivity of Nafion film depends on the humidity in the film. Nafion film loses conductivity when the moisture content in the film is too low, which can affect sensor operation. The advancement here is the identification of a method to retain the operation of the Nafion films in lower humidity environments. Certain salts can hold water molecules in the Nafion film structure at room temperature. By mixing salts with the Nafion solution, water molecules can be homogeneously distributed in the Nafion film increasing the film s hydration to prevent Nafion film from being dried out in low-humidity environment. The presence of organics provides extra sites in the Nafion film to promote proton (H+) mobility and thus improving Nafion film conductivity and sensor performance. The fabrication of ambient temperature oxygen microsensors includes depositing basic electrodes using noble metals, and metal oxides layer on one of the electrode as a reference electrode. The use of noble metals for electrodes is due to their strong catalytic properties for oxygen reduction. A conducting polymer Nafion, doped with water-retaining components and extra sites facilitating proton movement, was used as the electrolyte material, making the design adequate for low humidity environment applications. The Nafion solution was coated on the electrodes and air-dried. The sensor operates at room temperature in potentiometric mode, which measures voltage differences between working and reference electrodes in different gases. Repeat able responses to 21-percent oxygen in nitrogen were achieved using nitrogen as a baseline gas. Detection of oxygen from 7 to 21 percent has also been demonstrated. The room-temperature oxygen micro sensor developed has extremely low power

Rational Design of a Hierarchical Tin Dendrite Electrode for Efficient Electrochemical Reduction of CO2.

Science.gov (United States)

Won, Da Hye; Choi, Chang Hyuck; Chung, Jaehoon; Chung, Min Wook; Kim, Eun-Hee; Woo, Seong Ihl

2015-09-21

Catalysis is a key technology for the synthesis of renewable fuels through electrochemical reduction of CO2 . However, successful CO2 reduction still suffers from the lack of affordable catalyst design and understanding the factors governing catalysis. Herein, we demonstrate that the CO2 conversion selectivity on Sn (or SnOx /Sn) electrodes is correlated to the native oxygen content at the subsurface. Electrochemical analyses show that the reduced Sn electrode with abundant oxygen species effectively stabilizes a CO2 (.-) intermediate rather than the clean Sn surface, and consequently results in enhanced formate production in the CO2 reduction. Based on this design strategy, a hierarchical Sn dendrite electrode with high oxygen content, consisting of a multi-branched conifer-like structure with an enlarged surface area, was synthesized. The electrode exhibits a superior formate production rate (228.6 μmol h(-1)  cm(-2) ) at -1.36 VRHE without any considerable catalytic degradation over 18 h of operation. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Polarization properties of La0.6Sr0.4Co0.2Fe0.8O3-based double layer-type oxygen electrodes for reversible SOFCs

International Nuclear Information System (INIS)

Tao, Y.; Nishino, H.; Ashidate, S.; Kokubo, H.; Watanabe, M.; Uchida, H.

2009-01-01

We have developed double layer-type (catalyst layer/current collecting layer) oxygen electrodes (DLE) for reversible SOFCs. As the catalyst layer (cathode for SOFC and anode for steam electrolysis) interfaced with a samaria-doped ceria [(CeO 2 ) 0.8 (SmO 1.5 ) 0.2 , SDC] interlayer/YSZ solid electrolyte, mixed conducting La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3 (LSCF) and SDC particles were employed. The current collecting porous LSCF layer was formed on the catalyst layer. By controlling the SDC content, as well as the thickness and porosity of the catalyst layer, the gas diffusion rate and the conduction networks for electrons and oxide ions were optimized, resulting in a marked reduction of the overpotential. The LSCF + SDC/LSCF DLE exhibited higher performance than single-layer electrodes of LSCF + SDC or LSCF; the IR-free anode potential vs. an air reference electrode was 0.12 V (corresponding to an overpotential of 0.08 V) at 0.5 A cm -2 and 900 deg. C under an atmosphere of O 2 (1 atm)

Surface Characterization and Electrocatalytic Properties of the Ti/Ir0.3Ti(0.7-xPbx O2-Coated Electrodes for Oxygen Evolution Reaction in Acidic Media

Directory of Open Access Journals (Sweden)

Oliveira-Sousa Adriana de

2002-01-01

Full Text Available In this work a systematic investigation was carried out of the surface characterization and electrocatalytic activity of Ti/Ir0.3Ti(0.7-xPb x O2-coated electrodes (0 <= x <= 0.7, using the oxygen evolution reaction (OER in 0.5 mol dm-3 H2SO4 as model. The electrodes were prepared by thermal decomposition of IrCl3, TiCl3 and Pb(NO32 at 600 °C for 1 h using Ti as support. X-ray diffraction shows that the layers are crystalline and that the corresponding metal oxides are present. The surface morphology of the samples, before and after use under extensive oxygen evolution (Tafel experiment, was characterized by Scanning Electron Microscopy and the micrograph analyses show that the OER promotes the dissolution of the oxide layer. The redox processes occurring on the surface were characterized by cyclic voltammetry at 20 mV s-1 in 0.5 mol dm-3 aqueous H2SO4, at room temperature, and were controlled by the Ir3+/Ir4+ couple. The measured anodic voltammetric charge is related to the active area of the electrode showing that the replacement of TiO2 by PbO2 increases the surface area with the higher value being at 50 mol% PbO2. After oxygen evolution, the surface area increases slightly. Tafel slopes are independent of Pb content with the values around 60 mV decade-1, which suggest that only Ir sites are active for OER. The values of normalized current (i/q a show some inhibition of the OER as TiO2 is replaced by PbO2 suggesting that PbO2, can be a good choice, with potential to improve the selectivity of the system. The reaction order with respect to H+ ion is zero at constant overpotential and ionic strength. The values of Tafel slope and reaction order indicate that a single reaction mechanism is operating.

Development of high temperature reference electrodes for in-pile application: Part I. Feasibility study of the external pressure balanced Ag/AgCl reference electrode (EPBRE) and the cathodically charged Palladium hydrogen electrode

International Nuclear Information System (INIS)

Bosch, R.W.; Van Nieuwenhove, R.

1998-10-01

The main problems connected with corrosion potential measurements at elevated temperatures and pressures are related to the stability and lifetime of the reference electrode and the correct estimation of the potential related to the Standard Hydrogen Scale (SHE). Under Pressurised Water Reactor (PWR) conditions of 300 degrees Celsius and 150 bar, the choice of materials is also a limiting factor due to the influence of radiation. Investigations on two reference electrodes that can be used under PWR conditions are reported: the cathodically charged palladium hydrogen electrode, and the external pressure balanced silver/silver chloride electrode. Preliminary investigations with the Pd-electrode were focused on the calculation of the required charging time and the influence of dissolved oxygen. High temperature applications are discussed on the basis of results reported in the literature. Investigations with the silver/silver chloride reference electrode mainly dealt with the salt bridge which is necessary to connect the reference electrode with the testing solution. It is shown that the thermal junction potential is independent of the length of the salt bridge. In addition, the high temperature contributes to an increase of the conductivity of the solution, which is beneficial for the salt bridge connection

Investigations of a zirconia solid electrolyte oxygen sensor in liquid lead

Energy Technology Data Exchange (ETDEWEB)

Rivai, Abu Khalid, E-mail: rivai.abukhalid@jaea.go.j [Department of Nuclear Engineering, Graduate School of Science and Engineering, Tokyo Institute of Technology, N1-18, 2-12-1, O-okayama, Meguro-ku, Tokyo 152-8550 (Japan); Takahashi, Minoru, E-mail: mtakahas@nr.titech.ac.j [Research Laboratory for Nuclear Reactors, Tokyo Institute of Technology, N1-18, 2-12-1, O-okayama, Meguro-ku, Tokyo 152-8550 (Japan)

2010-03-15

Investigations of a magnesia-stabilized zirconia solid electrolyte oxygen sensor for oxygen control measurement in liquid lead were carried out. The fluid of Bi/Bi{sub 2}O{sub 3} as a reference electrode and a molybdenum wire as a working electrode to detect the output signal of the sensor were used. The Nernst equation was used to estimate the electromotive force (EMF) values theoretically. The temperatures of liquid lead were 500, 550 and 600 deg. C. The results showed that the injection gas temperatures did not affect the detected EMF, the sensor responded well to quick changes of oxygen activity in liquid lead, and the discrepancy between the measured and theoretical EMF of the oxygen sensor output signal was higher at 500 deg. C than at 550 and 600 deg. C.

21 CFR 868.1200 - Indwelling blood oxygen partial pressure (PO2) analyzer.

Science.gov (United States)

2010-04-01

... 21 Food and Drugs 8 2010-04-01 2010-04-01 false Indwelling blood oxygen partial pressure (PO2... Indwelling blood oxygen partial pressure (PO2) analyzer. (a) Identification. An indwelling blood oxygen... electrode) and that is used to measure, in vivo, the partial pressure of oxygen in blood to aid in...

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).

Enzymatic electrodes nanostructured with functionalized carbon nanotubes for biofuel cell applications

Energy Technology Data Exchange (ETDEWEB)

Nazaruk, E.; Bilewicz, R. [University of Warsaw, Faculty of Chemistry, Warsaw (Poland); Sadowska, K.; Biernat, J.F. [Gdansk University of Technology, Chemical Faculty, Gdansk (Poland); Rogalski, J. [Maria Curie Sklodowska University, Department of Biochemistry, Lublin (Poland); Ginalska, G. [Medical University of Lublin, Department of Biochemistry, Lublin (Poland)

2010-10-15

Nanostructured bioelectrodes were designed and assembled into a biofuel cell with no separating membrane. The glassy carbon electrodes were modified with mediator-functionalized carbon nanotubes. Ferrocene (Fc) and 2,2{sup '}-azino-bis (3-ethylbenzothiazoline-6-sulfonate) diammonium salt (ABTS) bound chemically to the carbon nanotubes were found useful as mediators of the enzyme catalyzed electrode processes. Glucose oxidase from Aspergillus niger AM-11 and laccase from Cerrena unicolor C-139 were incorporated in a liquid-crystalline matrix-monoolein cubic phase. The carbon nanotubes-nanostructured electrode surface was covered with the cubic phase film containing the enzyme and acted as the catalytic surface for the oxidation of glucose and reduction of oxygen. Thanks to the mediating role of derivatized nanotubes the catalysis was almost ten times more efficient than on the GCE electrodes: catalytic current of glucose oxidation was 1 mA cm{sup -2} and oxygen reduction current exceeded 0.6 mA cm{sup -2}. The open circuit voltage of the biofuel cell was 0.43 V. Application of carbon nanotubes increased the maximum power output of the constructed biofuel cell to 100 {mu}W cm{sup -2} without stirring of the solution which was ca. 100 times more efficient than using the same bioelectrodes without nanotubes on the electrode surface. (orig.)

Surface effects of electrode-dependent switching behavior of resistive random-access memory

KAUST Repository

Ke, Jr Jian

2016-09-26

The surface effects of ZnO-based resistive random-access memory (ReRAM) were investigated using various electrodes. Pt electrodes were found to have better performance in terms of the device\\'s switching functionality. A thermodynamic model of the oxygen chemisorption process was proposed to explain this electrode-dependent switching behavior. The temperature-dependent switching voltage demonstrates that the ReRAM devices fabricated with Pt electrodes have a lower activation energy for the chemisorption process, resulting in a better resistive switching performance. These findings provide an in-depth understanding of electrode-dependent switching behaviors and can serve as design guidelines for future ReRAM devices.

Bifunctional electrode performance for zinc-air flow cells with pulse charging

International Nuclear Information System (INIS)

Pichler, Birgit; Weinberger, Stephan; Reščec, Lucas; Grimmer, Ilena; Gebetsroither, Florian; Bitschnau, Brigitte; Hacker, Viktor

2017-01-01

Highlights: •Manufacture of bi-catalyzed bifunctional air electrodes via scalable process. •Direct synthesis of NiCo 2 O 4 on carbon nanofibers or nickel powder support. •450 charge and discharge cycles over 1000 h at 50 mA cm −2 demonstrated. •Pulse charging with 150 mA cm −2 is successfully applied on air electrodes. •Charge and discharge ΔV of <0.8 V at 50 mA cm −2 when supplied with O 2. -- Abstract: Bifunctional air electrodes with tuned composition consisting of two precious metal-free oxide catalysts are manufactured for application in rechargeable zinc-air flow batteries and electrochemically tested via long-term pulse charge and discharge cycling experiments at 50 mA cm −2 (mean). NiCo 2 O 4 spinel, synthesized via direct impregnation on carbon nanofibers or nickel powder and characterized by energy dispersive X-ray spectroscopy and X-ray diffraction experiments, shows high activity toward oxygen evolution reaction with low charge potentials of < 2.0 V vs. Zn/Zn 2+ . La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3 perovskite exhibits bifunctional activity and outperforms the NiCo 2 O 4 spinel in long-term stability tenfold. By combining the catalysts in one bi-catalyzed bifunctional air electrode, stable performances of more than 1000 h and 450 cycles are achieved when supplied with oxygen and over 650 h and 300 cycles when supplied with synthetic air. In addition, the pulse charging method, which is beneficial for compact zinc deposition, is successfully tested on air electrodes during long-term operation. The oxygen evolution potentials during pulse, i.e. at tripled charge current density of 150 mA cm −2 , are only 0.06–0.08 V higher compared to constant charging current densities. Scanning electron microscopy confirms that mechanical degradation caused by bubble formation during oxygen evolution results in slowly decreasing discharge potentials.

A Combined Variable-Temperature Neutron Diffraction and Thermogravimetric Analysis Study on a Promising Oxygen Electrode, SrCo0.9Nb0.1O3-δ, for Reversible Solid Oxide Fuel Cells.

Science.gov (United States)

Yang, Tianrang; Wang, Jie; Chen, Yan; An, Ke; Ma, Dong; Vogt, Thomas; Huang, Kevin

2017-10-11

The present study investigates the temperature-structure-stoichiometry relationship of a promising oxygen electrode SrCo 0.9 Nb 0.1 O 3-δ over a temperature (T) range from room temperature (RT) to 900 °C. The techniques employed are variable-temperature neutron diffraction (VTND) and thermogravimetric analysis (TGA). At T < 75 °C, VTND reveals a tetragonal (P4/mmm) structure with a G-type magnetic ordering. Above 75 °C, the nucleus structure remains the same, while the magnetic ordering disappears. A phase transition from tetragonal (P4/mmm) to cubic (Pm3̅m) is observed at 412 °C, where the two Co sites and three O sites in the P4/mmm phase converge to one equivalent site, respectively. The phase transition temperature coincides with the peak temperature of oxygen uptake obtained by TGA. It is also observed that the Nb dopant has no preferred Co site to occupy. The oxygen vacancies are mostly located at the O3 site surrounding the Co2 site in the P4/mmm structure. The intermediate-spin state of Co 3+ at the Co2 site is responsible for the observed distortions of CoO 6 octahedra, i.e., elongation of Co2O 6 octahedra and shortening of Co1O 6 octahedra along the c-axis, which is a phenomenon known as Jahn-Teller distortion. At high temperatures, large thermal displacement factor for O 2- is observed with high concentration of oxygen vacancies, providing a structural environment favorable to high O 2- conductivity in Nb-doped SrCoO 3 -based oxygen electrode materials.

Light-addressable amperometric electrodes for enzyme sensors based on direct quantum dot-electrode contacts

Science.gov (United States)

Riedel, M.; Göbel, G.; Parak, W. J.; Lisdat, F.

2014-03-01

Quantum dots allow the generation of charge carriers upon illumination. When these particles are attached to an electrode a photocurrent can be generated. This allows their use as a light-switchable layer on the surface. The QDs can not only exchange electronics with the electrode, but can also interact with donor or acceptor compounds in solution providing access to the construction of signal chains starting from an analytic molecule. The magnitude and the direction of the photocurrent depend on several factors such as electrode polarization, solution pH and composition. These defined dependencies have been evaluated with respect to the combination of QD-electrodes with enzyme reactions for sensorial purpose. CdSe/ZnS-QD-modified electrodes can be used to follow enzymatic reactions in solution based on the oxygen sensitivity. In order to develop a photoelectrochemical biosensor, e.g. glucose oxidase is immobilized on the CdSe/ZnS-electrode. One immobilization strategy applies the layer-by-layer-technique of GOD and a polyelectrolyte. Photocurrent measurements of such a sensor show a clear concentration dependent behavior. The principle of combing QD oxidase. The sensitivity of quantum dot electrodes can be influenced by additional nanoparticles, but also by multiple layers of the QDs. In another direction of research it can be influenced by additional nanoparticles, but also by multiple layers of the QDs. In another direction of research it can be demonstrated that direct electron transfer from excited quantum dots can be achieved with the redox protein cytochrome c. This allows the detection of the protein, but also interaction partners such as a enzymes or superoxide.

Internal-reference solid-electrolyte oxygen sensor

International Nuclear Information System (INIS)

Haaland, D.M.

1977-01-01

A new solid-electrolyte oxygen sensor has been developed that eliminates the conventional oxygen reference in previous solid-electrolyte oxygen sensor designs and is, therefore, ideally suited as an insertion device for remote oxygen monitoring applications. It is constructed with two cells of stabilized zirconia sealed into a small unit using a new high-temperature platinum-zirconia seal. One electrochemical cell monitors the ratio of oxygen partial pressures inside and outside the sensor while the other solid-electrolyte cell is used for quantitative electrochemical pumping of oxygen. The internal oxygen reference is generated by initially pumping all oxygen out of the known internal volume of the sensor and then quantitatively pumping oxygen back in until oxygen partial pressures are equal inside and out. This information is used with the ideal gas law to calculate oxygen partial pressures. Tests were conducted from 400 to 1000 0 C in mixtures of oxygen and nitrogen spanning approximately 0.2 to 21 percent oxygen concentration range. Sensors with sputtered platinum and porous platinum paste electrodes were compared

Heme biomolecule as redox mediator and oxygen shuttle for efficient charging of lithium-oxygen batteries

Science.gov (United States)

Ryu, Won-Hee; Gittleson, Forrest S.; Thomsen, Julianne M.; Li, Jinyang; Schwab, Mark J.; Brudvig, Gary W.; Taylor, André D.

2016-01-01

One of the greatest challenges with lithium-oxygen batteries involves identifying catalysts that facilitate the growth and evolution of cathode species on an oxygen electrode. Heterogeneous solid catalysts cannot adequately address the problematic overpotentials when the surfaces become passivated. However, there exists a class of biomolecules which have been designed by nature to guide complex solution-based oxygen chemistries. Here, we show that the heme molecule, a common porphyrin cofactor in blood, can function as a soluble redox catalyst and oxygen shuttle for efficient oxygen evolution in non-aqueous Li-O2 batteries. The heme's oxygen binding capability facilitates battery recharge by accepting and releasing dissociated oxygen species while benefiting charge transfer with the cathode. We reveal the chemical change of heme redox molecules where synergy exists with the electrolyte species. This study brings focus to the rational design of solution-based catalysts and suggests a sustainable cross-link between biomolecules and advanced energy storage. PMID:27759005

Transient photoresponse of nitrogen-doped ultrananocrystalline diamond electrodes in saline solution

Energy Technology Data Exchange (ETDEWEB)

Ahnood, Arman, E-mail: arman.ahnood@unimelb.edu.au; Ganesan, Kumaravelu; Stacey, Alastair; Prawer, Steven [School of Physics, University of Melbourne, Melbourne, Victoria 3010 (Australia); Simonov, Alexandr N.; Spiccia, Leone [School of Chemistry and the ARC Centre of Excellence for Electromaterials Science, Monash University, Melbourne, Victoria 3800 (Australia); Laird, Jamie S. [CSIRO, Minerals Resources Flagship, School of Physics, University of Melbourne, Melbourne, Victoria 3010 (Australia); Maturana, Matias I. [National Vision Research Institute, Australian College of Optometry, Carlton, Victoria 3053 (Australia); NeuroEngineering Laboratory, Department of Electrical and Electronic Engineering, University of Melbourne, Parkville, Victoria 3010 (Australia); Ibbotson, Michael R. [National Vision Research Institute, Australian College of Optometry, Carlton, Victoria 3053 (Australia); ARC Centre of Excellence for Integrative Brain Function, Department of Optometry and Vision Sciences, University of Melbourne, Parkville, Victoria 3010 (Australia)

2016-03-07

Beyond conventional electrically-driven neuronal stimulation methods, there is a growing interest in optically-driven approaches. In recent years, nitrogen-doped ultrananocrystalline diamond (N-UNCD) has emerged as a strong material candidate for use in electrically-driven stimulation electrodes. This work investigates the electrochemical activity of N-UNCD in response to pulsed illumination, to assess its potential for use as an optically-driven stimulation electrode. Whilst N-UNCD in the as-grown state exhibits a weak photoresponse, the oxygen plasma treated film exhibits two orders of magnitude enhancement in its sub-bandgap open circuit photovoltage response. The enhancement is attributed to the formation of a dense network of oxygen-terminated diamond nanocrystals at the N-UNCD surface. Electrically connected to the N-UNCD bulk via sub-surface graphitic grain boundaries, these diamond nanocrystals introduce a semiconducting barrier between the sub-surface graphitic semimetal and the electrolyte solution, leading to a photovoltage under irradiation with wavelengths of λ = 450 nm and shorter. Within the safe optical exposure limit of 2 mW mm{sup −2}, charge injection capacity of 0.01 mC cm{sup −2} is achieved using a 15 × 15 μm electrode, meeting the requirements for extracellular and intercellular stimulation. The nanoscale nature of processes presented here along with the diamond's biocompatibility and biostability open an avenue for the use of oxygen treated N-UNCD as optically driven stimulating electrodes.

Transient photoresponse of nitrogen-doped ultrananocrystalline diamond electrodes in saline solution

International Nuclear Information System (INIS)

Ahnood, Arman; Ganesan, Kumaravelu; Stacey, Alastair; Prawer, Steven; Simonov, Alexandr N.; Spiccia, Leone; Laird, Jamie S.; Maturana, Matias I.; Ibbotson, Michael R.

2016-01-01

Beyond conventional electrically-driven neuronal stimulation methods, there is a growing interest in optically-driven approaches. In recent years, nitrogen-doped ultrananocrystalline diamond (N-UNCD) has emerged as a strong material candidate for use in electrically-driven stimulation electrodes. This work investigates the electrochemical activity of N-UNCD in response to pulsed illumination, to assess its potential for use as an optically-driven stimulation electrode. Whilst N-UNCD in the as-grown state exhibits a weak photoresponse, the oxygen plasma treated film exhibits two orders of magnitude enhancement in its sub-bandgap open circuit photovoltage response. The enhancement is attributed to the formation of a dense network of oxygen-terminated diamond nanocrystals at the N-UNCD surface. Electrically connected to the N-UNCD bulk via sub-surface graphitic grain boundaries, these diamond nanocrystals introduce a semiconducting barrier between the sub-surface graphitic semimetal and the electrolyte solution, leading to a photovoltage under irradiation with wavelengths of λ = 450 nm and shorter. Within the safe optical exposure limit of 2 mW mm"−"2, charge injection capacity of 0.01 mC cm"−"2 is achieved using a 15 × 15 μm electrode, meeting the requirements for extracellular and intercellular stimulation. The nanoscale nature of processes presented here along with the diamond's biocompatibility and biostability open an avenue for the use of oxygen treated N-UNCD as optically driven stimulating electrodes.

Effect of samaria-doped ceria (SDC) interlayer on the performance of La0.6Sr0.4Co0.2Fe0.8O3-δ/SDC composite oxygen electrode for reversible solid oxide fuel cells

International Nuclear Information System (INIS)

Shimura, Kazuki; Nishino, Hanako; Kakinuma, Katsuyoshi; Brito, Manuel E.; Uchida, Hiroyuki

2017-01-01

In order to establish clear criteria for designing highly active and highly durable oxygen electrode for reversible solid oxide fuel cells, we have focused on the effect of samaria-doped ceria (SDC) interlayers prepared on YSZ solid electrolyte surface on the performances of La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ (LSCF)-SDC composite oxygen electrode. Symmetrical cells with the configuration, LSCF-SDC|SDC interlayer|YSZ|SDC interlayer|LSCF-SDC, were constructed. We prepared two kinds of SDC interlayers, one from a mixed solution of cerium 2-ethylhexanoate (denoted as octoate) and samarium octoates (o-interlayer) and another from a mixed solution of cerium and samarium nitrates (n-interlayer). The LSCF-SDC electrodes with o-interlayer and n-interlayer exhibited very similar performances in both the anodic and cathodic reactions at 900 °C. When temperature was decreased to 800 °C, an increase in overpotentials was observed. However, the LSCF-SDC electrode with o-interlayer exhibited superior performance to that with n-interlayer. It was found that the entire surface of the YSZ electrolyte disk was well covered with a dense o-interlayer of uniform thickness. Such an interlayer enables uniform transport of oxide ions to and from the LSCF-SDC electrode, resulting in an enlarged effective reaction zone (ERZ). The I-E performance of the LSCF-SDC|o-interlayer|YSZ cell was found to be comparable to that of the identical electrode prepared on a dense SDC sintered electrolyte disk (as a reference). This observation supports our views regarding the essential role of a dense interlayer with uniform thickness in enhancing the performance of reversible solid oxide cells.

Electrode materials for microbial fuel cells: nanomaterial approach

KAUST Repository

Mustakeem, Mustakeem

2015-11-05

Microbial fuel cell (MFC) technology has the potential to become a major renewable energy resource by degrading organic pollutants in wastewater. The performance of MFC directly depends on the kinetics of the electrode reactions within the fuel cell, with the performance of the electrodes heavily influenced by the materials they are made from. A wide range of materials have been tested to improve the performance of MFCs. In the past decade, carbon-based nanomaterials have emerged as promising materials for both anode and cathode construction. Composite materials have also shown to have the potential to become materials of choice for electrode manufacture. Various transition metal oxides have been investigated as alternatives to conventional expensive metals like platinum for oxygen reduction reaction. In this review, different carbon-based nanomaterials and composite materials are discussed for their potential use as MFC electrodes.

Electrode materials for microbial fuel cells: nanomaterial approach

KAUST Repository

Mustakeem, Mustakeem

2015-01-01

Microbial fuel cell (MFC) technology has the potential to become a major renewable energy resource by degrading organic pollutants in wastewater. The performance of MFC directly depends on the kinetics of the electrode reactions within the fuel cell, with the performance of the electrodes heavily influenced by the materials they are made from. A wide range of materials have been tested to improve the performance of MFCs. In the past decade, carbon-based nanomaterials have emerged as promising materials for both anode and cathode construction. Composite materials have also shown to have the potential to become materials of choice for electrode manufacture. Various transition metal oxides have been investigated as alternatives to conventional expensive metals like platinum for oxygen reduction reaction. In this review, different carbon-based nanomaterials and composite materials are discussed for their potential use as MFC electrodes.

Benzene oxidation at diamond electrodes: comparison of microcrystalline and nanocrystalline diamonds.

Science.gov (United States)

Pleskov, Yu V; Krotova, M D; Elkin, V V; Varnin, V P; Teremetskaya, I G; Saveliev, A V; Ralchenko, V G

2012-08-27

A comparative study of benzene oxidation at boron-doped diamond (BDD) and nitrogenated nanocrystalline diamond (NCD) anodes in 0.5 M K(2)SO(4) aqueous solution is conducted by using cyclic voltammetry and electrochemical impedance spectroscopy. It is shown by measurements of differential capacitance and anodic current that during the benzene oxidation at the BDD electrode, adsorption of a reaction intermediate occurs, which partially blocks the electrode surface and lowers the anodic current. At the NCD electrode, benzene is oxidized concurrently with oxygen evolution, a (quinoid) intermediate being adsorbed at the electrode. The adsorption and the electrode surface blocking are reflected in the impedance-frequency and impedance-potential complex-plane plots. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

ETEM observation of Pt/C electrode catalysts in a moisturized cathode atmosphere

International Nuclear Information System (INIS)

Yoshida, K; Zhang, X; Tanaka, N; Boyes, E D; Gai, P L

2014-01-01

There have been reports of challenges in designing platinum carbon (Pt/C) electrode catalysts for PEMFC. Pt/C electrode catalysts deactivate much faster on the cathode (in moisturized O 2 ) than on the anode (in H 2 ). To understand influences of moisture and oxygen on the deactivation of the Pt/C catalysts in proton-exchange-membrane fuel cells (PEMFCs), spherical-aberration-corrected environmental transmission electron microscopy (AC-ETEM) was applied with a high-speed CCD camera. Structural changes of the Pt/C electrode catalysts were dynamically recorded in moisturized nitrogen, oxygen and hydrogen. The mass spectrometry confirmed the moisture content (between 5 to 30 %) of nitrogen driving gas through a humidifier. Coalescence of platinum nanoparticles (D = 3.24 nm) was carefully evaluated in pure N 2 and moisturized N 2 atmosphere. The Pt/C showed considerable structural weakness in a moisturized N2 atmosphere. Comparable results obtained by AC-ETEM in different gas atmospheres also suggested ways to improve the oxygen reduction reaction (ORR). In this paper, the deactivation process due to moisture (hydroxylation) of carbon supports is discussed using for comparison the movement of platinum nanoparticles measured in moisturized nitrogen and pure nitrogen atmospheres

Electrochemical pretreatment of heavy oil refinery wastewater using a three-dimensional electrode reactor

Energy Technology Data Exchange (ETDEWEB)

Wei Lingyong [State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Beijing 102249 (China); Guo Shaohui, E-mail: cupgsh@163.co [State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Beijing 102249 (China); Yan Guangxu; Chen Chunmao [State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Beijing 102249 (China); Jiang Xiaoyan [Liaohe Petrochemical Branch Company, PetroChina, Panjin 124022 (China)

2010-12-01

The pretreatment of heavy oil refinery wastewater (HORW) was experimentally investigated using a three-dimensional electrode reactor (TDER) with granular activated carbon (GAC) and porous ceramsite particle (PCP) as the combination particle electrode and DSA type anodes as the anode. The results showed that higher chemical oxygen demand (COD) removal was obtained in TDER comparing with the two-dimensional electrode reactor (without particle electrodes packed), and combination particle electrode was favorable to improve the COD removal efficiency and reduce the energy consumption. The treated HORW under the optimal experimental condition (GAC percentage = 75%, current density = 30 mA/cm{sup 2}, pH not adjusted and treatment time = 100 min) presented that the removal efficiencies of COD, total organic carbon and toxicity units were 45.5%, 43.3% and 67.2%, respectively, and the ratio of 5-day biochemical oxygen demand to COD was increased from 0.10 to 0.29, which is beneficial for further biological treatment. Furthermore, the application of electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry to characterize polar compounds in HORW and their oxidation products was well demonstrated to reveal the composition variation.

Electrochemical pretreatment of heavy oil refinery wastewater using a three-dimensional electrode reactor

International Nuclear Information System (INIS)

Wei Lingyong; Guo Shaohui; Yan Guangxu; Chen Chunmao; Jiang Xiaoyan

2010-01-01

The pretreatment of heavy oil refinery wastewater (HORW) was experimentally investigated using a three-dimensional electrode reactor (TDER) with granular activated carbon (GAC) and porous ceramsite particle (PCP) as the combination particle electrode and DSA type anodes as the anode. The results showed that higher chemical oxygen demand (COD) removal was obtained in TDER comparing with the two-dimensional electrode reactor (without particle electrodes packed), and combination particle electrode was favorable to improve the COD removal efficiency and reduce the energy consumption. The treated HORW under the optimal experimental condition (GAC percentage = 75%, current density = 30 mA/cm 2 , pH not adjusted and treatment time = 100 min) presented that the removal efficiencies of COD, total organic carbon and toxicity units were 45.5%, 43.3% and 67.2%, respectively, and the ratio of 5-day biochemical oxygen demand to COD was increased from 0.10 to 0.29, which is beneficial for further biological treatment. Furthermore, the application of electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry to characterize polar compounds in HORW and their oxidation products was well demonstrated to reveal the composition variation.

Accurate Assessment of the Oxygen Reduction Electrocatalytic Activity of Mn/Polypyrrole Nanocomposites Based on Rotating Disk Electrode Measurements, Complemented with Multitechnique Structural Characterizations

Science.gov (United States)

Sánchez, Carolina Ramírez; Taurino, Antonietta; Bozzini, Benedetto

2016-01-01

This paper reports on the quantitative assessment of the oxygen reduction reaction (ORR) electrocatalytic activity of electrodeposited Mn/polypyrrole (PPy) nanocomposites for alkaline aqueous solutions, based on the Rotating Disk Electrode (RDE) method and accompanied by structural characterizations relevant to the establishment of structure-function relationships. The characterization of Mn/PPy films is addressed to the following: (i) morphology, as assessed by Field-Emission Scanning Electron Microscopy (FE-SEM) and Atomic Force Microscope (AFM); (ii) local electrical conductivity, as measured by Scanning Probe Microscopy (SPM); and (iii) molecular structure, accessed by Raman Spectroscopy; these data provide the background against which the electrocatalytic activity can be rationalised. For comparison, the properties of Mn/PPy are gauged against those of graphite, PPy, and polycrystalline-Pt (poly-Pt). Due to the literature lack of accepted protocols for precise catalytic activity measurement at poly-Pt electrode in alkaline solution using the RDE methodology, we have also worked on the obtainment of an intralaboratory benchmark by evidencing some of the time-consuming parameters which drastically affect the reliability and repeatability of the measurement. PMID:28042491

Accurate Assessment of the Oxygen Reduction Electrocatalytic Activity of Mn/Polypyrrole Nanocomposites Based on Rotating Disk Electrode Measurements, Complemented with Multitechnique Structural Characterizations

Directory of Open Access Journals (Sweden)

Patrizia Bocchetta

2016-01-01

Full Text Available This paper reports on the quantitative assessment of the oxygen reduction reaction (ORR electrocatalytic activity of electrodeposited Mn/polypyrrole (PPy nanocomposites for alkaline aqueous solutions, based on the Rotating Disk Electrode (RDE method and accompanied by structural characterizations relevant to the establishment of structure-function relationships. The characterization of Mn/PPy films is addressed to the following: (i morphology, as assessed by Field-Emission Scanning Electron Microscopy (FE-SEM and Atomic Force Microscope (AFM; (ii local electrical conductivity, as measured by Scanning Probe Microscopy (SPM; and (iii molecular structure, accessed by Raman Spectroscopy; these data provide the background against which the electrocatalytic activity can be rationalised. For comparison, the properties of Mn/PPy are gauged against those of graphite, PPy, and polycrystalline-Pt (poly-Pt. Due to the literature lack of accepted protocols for precise catalytic activity measurement at poly-Pt electrode in alkaline solution using the RDE methodology, we have also worked on the obtainment of an intralaboratory benchmark by evidencing some of the time-consuming parameters which drastically affect the reliability and repeatability of the measurement.

Direct reform of graphite oxide electrodes by using ambient plasma for supercapacitor applications

Science.gov (United States)

Kim, Ho Jun; Jeong, Hae Kyung

2017-10-01

Ambient plasma is applied to graphite oxide electrodes directly to improve electrochemical properties for supercapacitor applications. Surface morphology of the electrodes after the plasma treatment changes dramatically and amount of oxygen reduced significantly, demonstrating a reduction effect on the graphite oxide electrode by the ambient plasma. Equivalent series resistance of the electrode also reduced from 108 Ω to 84 Ω after the plasma treatment. Corresponding specific capacitance, therefore, increases from 0.45 F cm-2 to 0.85 F cm-2, proving that the ambient plasma treatment is very efficient, clean, economic, and environment-friendly method to reform the graphite oxide electrodes directly for the supercapacitor applications.

"Imaging" LEIS of micro-patterned solid oxide fuel cell electrodes

Science.gov (United States)

Druce, John; Simrick, Neil; Ishihara, Tatsumi; Kilner, John

2014-08-01

Understanding the kinetics of oxygen exchange between the gas phase and a ceramic electrode is key to optimising the performance of electrochemical energy conversion devices such as Solid Oxide Fuel Cells. Clearly the surface chemistry of these materials is important, and surface sensitive techniques such as Low Energy Ion Scattering (LEIS) can provide important compositional information key to unravelling electrode kinetics. In this work, we use high lateral resolution LEIS to perform local analyses of a micropatterned electrode structure, of the type often used for studies of the geometrical dependences of electrode performance. We find that the results are comparable to those for bulk materials, but detect evidence of cation interdiffusion from the electrode to the electrolyte. Finally, we note that this preliminary study could open the prospect of in situ measurements of cells near operating conditions.

Oxygen bridges between NiO nanosheets and graphene for improvement of lithium storage.

Science.gov (United States)

Zhou, Guangmin; Wang, Da-Wei; Yin, Li-Chang; Li, Na; Li, Feng; Cheng, Hui-Ming

2012-04-24

Graphene has been widely used to dramatically improve the capacity, rate capability, and cycling performance of nearly any electrode material for batteries. However, the binding between graphene and these electrode materials has not been clearly elucidated. Here we report oxygen bridges between graphene with oxygen functional groups and NiO from analysis by X-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy, and Raman spectroscopy and confirm the conformation of oxygen bridges by the first-principles calculations. We found that NiO nanosheets (NiO NSs) are bonded strongly to graphene through oxygen bridges. The oxygen bridges mainly originate from the pinning of hydroxyl/epoxy groups from graphene on the Ni atoms of NiO NSs. The calculated adsorption energies (1.37 and 1.84 eV for graphene with hydroxyl and epoxy) of a Ni adatom on oxygenated graphene by binding with oxygen are comparable with that on graphene (1.26 eV). However, the calculated diffusion barriers of the Ni adatom on the oxygenated graphene surface (2.23 and 1.69 eV for graphene with hydroxyl and epoxy) are much larger than that on the graphene (0.19 eV). Therefore, the NiO NS is anchored strongly on the graphene through a C-O-Ni bridge, which allows a high reversible capacity and excellent rate performance. The easy binding/difficult dissociating characteristic of Ni adatoms on the oxygenated graphene facilitates fast electron hopping from graphene to NiO and thus the reversible lithiation and delithiation of NiO. We believe that the understanding of this oxygen bridge between graphene and NiO will lead to the development of other high-performance electrode materials.

Electrochemical reduction of oxygen on lead-silver alloys in an alkaline medium

International Nuclear Information System (INIS)

Seliverstov, S.D.; Arkhangel'skaya, Z.P.; Lyzlov, N.Y.

1986-01-01

The use of lead-silver alloys as materials for the gas-absorbing electrode in sealed silver-cadmium alkaline storage batteries is desirable primarily from the stanpoint of saving the costly silver. The authors studied reduction of oxygen with the aim of optimizing the composition of the Pb-Ag alloy and of the porous structure of the electrodes. The alloys were made in a muffle furnace in corundum crucibles under a layer of VI-2 flux. Curves are shown which represent the dependence of the ionization current of molecular oxygen on smooth partially immersed electrodes made from alloys differing in composition on the length of the part of the electrode withdrawn from the solution. It is shown that decrease of the corrosion resistance of the alloy in the porous electrode causes partial loss of its mechanical strength. Worsening of the electric contact between the particles of active material is also possible. An alloy of the composition (mass %) 60 Pb-40 Ag is the most suitable from the practical standpoint

Characterization and validation of noninvasive oxygen tension measurements in human glioma xenografts by 19F-MR relaxometry

International Nuclear Information System (INIS)

Sanden, Boudewijn P.J. van der; Heerschap, Arend; Simonetti, Arjan W.; Rijken, Paul F.J.W.; Peters, Hans P.W.; Stbeen, Georg; Kogel, Albert J. van der

1999-01-01

Purpose: The aim of this study was to characterize and to validate noninvasive 19 F-magnetic resonance relaxometry for the measurement of oxygen tensions in human glioma xenografts in nude mice. The following three questions were addressed: 1. When perfluorocarbon compounds (PFCs) are administrated intravenously, which tumor regions are assessed by 19 F-MR relaxometry? 2. Are oxygen tension as detected by 19 F-MR relaxometry (pO 2/relaxo ) comparable to Eppendorf O 2 -electrode measurements (pO 2/electrode )? 3. Can 19 F-MR relaxometry be used to detect oxygen tension changes in tumor tissue during carbogen breathing? Methods and Materials: Slice-selective 19 F-MR relaxometry was carried out with perfluoro-15-crown-5-ether as oxygen sensor. The PFC was injected i.v. 3 days before the 19 F-MR experiments. Two datasets were acquired before and two after the start of carbogen breathing. The distribution of PFCs and necrotic areas were analyzed in 19 F-Spin Echo (SE) density MR images and T 2 -weighted 1 H-SE MR images, respectively. One day after the MR investigations, oxygen tensions were measured by oxygen electrodes in the same slice along two perpendicular tracks. These measurements were followed by (immuno)histochemical analysis of the 2D distribution of perfused microvessels, hypoxic cells, necrotic areas, and macrophages. Results: The PFCs mainly became sequestered in perfused regions at the tumor periphery; thus, 19 F-MR relaxometry probed mean oxygen tensions in these regions throughout the selected MR slice. In perfused regions of the tumor, mean pO 2/relaxo values were comparable to mean pO 2/electrode values, and varied from 0.03 to 9 mmHg. Median pO 2/electrode values of both tracks were lower than mean pO 2/relaxo values, because low pO 2/electrode values that originate from hypoxic and necrotic areas were also included in calculations of median pO 2/electrode values. After 8-min carbogen breathing, the average pO 2/relaxo increase was 3.3 ± 0.8 (SEM

Electrodeposited nanostructured raspberry-like gold-modified electrodes for electrocatalytic applications

Energy Technology Data Exchange (ETDEWEB)

Manivannan, Shanmugam; Ramaraj, Ramasamy, E-mail: ramarajr@yahoo.com [Madurai Kamaraj University, Centre for Photoelectrochemistry, School of Chemistry (India)

2013-10-15

A facile method for fabrication of raspberry-like Au nanostructures (Au NRBs)-modified electrode by electrodeposition and its applications toward the electrocatalytic oxidation of methanol (MOR) in alkaline medium and oxygen reduction reaction (ORR) in both alkaline and acidic media are demonstrated. The Au NRBs are characterized by UV-Vis absorption spectra, SEM, X-ray diffraction, and electrochemical measurements. The growth of Au NRBs was monitored by recording the in-situ absorption spectral changes during electrodeposition using spectroelectrochemical technique. Here we systematically studied the MOR by varying several reaction parameters such as potential scan rate and methanol concentration. The electrocatalytic poisoning effect due to the MOR products are not observed at the Au NRBs-modified electrode. At the alkaline medium the Au NRBs-modified electrode shows the better catalytic activities toward the MOR and ORR when compared to the poly crystalline gold and bare glassy carbon electrodes. The Au NRBs-modified electrode is a promising and inexpensive electrode material for other electrocatalytic applications.Graphical AbstractRaspberry-like Au nanostructures modified electrode is prepared and used for electrocatalytic applications.

Development of oxygen and pH sensors for aqueous systems

International Nuclear Information System (INIS)

Stvartak, C.; Alcock, C.B.; Li, B.; Wang, L.; Fergus, J.W.; Bakshi, N.

1994-04-01

Corrosion science has long recognized that two of the most important parameters in characterizing the corrosivity of an aqueous environment are oxygen chemical potential and pH. These parameters not only determine the thermodynamic driving forces for various corrosion reactions, but also characterize the rates of these reactions and hence the lifetime of a particular component. The primary goal of this project is to develop an electrochemical oxygen and pH sensor for continuous use in the cycle chemistry control of power plants. In the past year, electrochemical sensors with a metal/metal oxide or metal/metal hydride internal reference electrode and a fluoride-based electrolyte tube have been developed and tested in this laboratory. The corrosion tests showed that the LaF 3 -based solid electrolyte was very stable both chemically and physically in water. Furthermore, its electrical conductivity is 4 to 5 orders of magnitude higher than that of stabilized zirconia below 573 K (300 degree C), which is the main advantage of a fluoride-based electrolyte at low temperatures. With this electrolyte and the selected internal oxygen reference electrode (Ag/Ag 2 O), the electrochemical probe demonstrated Nernstian responses to the oxygen chemical potential and pH of the aqueous solution with good reproducibility. A similar cell with Zr/ZrH 1+x as the internal hydrogen reference electrode showed promising pH sensing characteristics. It is proposed that these two cells be combined to form a double-headed electrochemical probe to determine oxygen chemical potential and pH in the solution simultaneously

Development of Novel Electrode Materials for the Electrocatalysis of Oxygen-Transfer and Hydrogen-Transfer Reactions

Energy Technology Data Exchange (ETDEWEB)

Simpson, Brett Kimball [Iowa State Univ., Ames, IA (United States)

2002-01-01

Throughout this thesis, the fundamental aspects involved in the electrocatalysis of anodic O-transfer reactions and cathodic H-transfer reactions have been studied. The investigation into anodic O-transfer reactions at undoped and Fe(III)[doped MnO₂ films] revealed that MnO₂ film electrodes prepared by a cycling voltammetry deposition show improved response for DMSO oxidation at the film electrodes vs. the Au substrate. Doping of the MnO₂ films with Fe(III) further enhanced electrode activity. Reasons for this increase are believed to involve the adsorption of DMSO by the Fe(III) sites. The investigation into anodic O-transfer reactions at undoped and Fe(III)-doped RuO₂ films showed that the Fe(III)-doped RuO₂-film electrodes are applicable for anodic detection of sulfur compounds. The Fe(III) sites in the Fe-RuO₂ films are speculated to act as adsorption sites for the sulfur species while the Ru(IV) sites function for anodic discharge of H₂O to generate the adsorbed OH species. The investigation into cathodic H-transfer reactions, specifically nitrate reduction, at various pure metals and their alloys demonstrated that the incorporation of metals into alloy materials can create a material that exhibits bifunctional properties for the various steps involved in the overall nitrate reduction reaction. The Sb₁₀Sn₂₀Ti₇₀, Cu₆₃Ni₃₇ and Cu₂₅Ni₇₅ alloy electrodes exhibited improved activity for nitrate reduction as compared to their pure component metals. The Cu₆₃Ni₃₇ alloy displayed the highest activity for nitrate reduction. The final investigation was a detailed study of the electrocatalytic activity of cathodic H-transfer reactions (nitrate reduction) at various compositions of Cu-Ni alloy electrodes. Voltammetric response for NO₃^- at the Cu-Ni alloy electrode is superior to

A cold plasma plume with a highly conductive liquid electrode

International Nuclear Information System (INIS)

Chen Guangliang; Chen Wenxing; Chen Shihua; Yang Size

2008-01-01

A cold dielectric barrier discharge (DBD) plasma plume with one highly conductive liquid electrode has been developed to treat thermally sensitive materials, and its preliminary discharging characteristics have been studied. The averaged electron temperature and density is estimated to be 0.6eV and 10 11 /cm 3 , respectively. The length of plasma plume can reach 5 cm with helium gas (He), and the conductivity of the outer electrode affects the plume length obviously. This plasma plume could be touched by bare hand without causing any burning or painful sensation, which may provide potential application for safe aseptic skin care. Moreover, the oxidative particles (e.g., OH, O * , O 3 ) in the downstream oxygen (O2) gas of the plume have been applied to treat the landfill leachate. The results show that the activated O 2 gas can degrade the landfill leachate effectively, and the chemical oxygen demand (COD), conductivity, biochemical oxygen demand (BOD), and suspended solid (SS) can be decreased by 52%, 57%, 76% and 92%, respectively. (fluids, plasmas and electric discharges)

Solid electrolytes in thermodynamic investigations. Investigation of oxygen pressure effect in Ar + O2 type mixtures on cell potentials with CaF2 electrolyte and oxide electrodes

International Nuclear Information System (INIS)

Levitskij, V.A.; Narchuk, N.B.; Kashkarova, S.L.

1982-01-01

An experimental test of the P'sub(Osub(2))=P''sub(Osub(2)) condition (P'sub(Osub(2)) and P''sub(Osub(2)) - oxygen pressure above the first and the second electrodes) necessary for reversible work of the cells is carried out with the (-)O 2 , Pt (CaZrO 3 , 0.18CaOx0.82ZrO 2 )CaF 2 CaF 2 CaHfO 3 , HfO 2 , CaF 2 Pt, O 2 (+) cell as an example. The equilibrium potentials of the given cell are shown to be independent from Psub(Osub(2)) value above both electrodes up to the O 2 pressure equal to approximately 1 Pa at Psub(gen.)=Psub(Osub(2))+Psub(Ar)=10sup(5) Pa. Thermodynamic parameters of the CaO+HfO 2 =CaHfO 3 reaction obtained from the E=f(T) dependence in argon atmosphere under Psub(Osub(2))=1-10sup(2) Pa well agree with analogous values determined for the same cell under Psub(Osub(2)) = 10 5 Pa. Comparison of the results obtained by the e. m. f. method with F - - ion electrolyte both in pure oxygen and in argon atmosphere under low Psub(Osub(2)) with the present literature data testify to perspectives of using the cells of this type under controlled low Psub(Osub(2)) values for thermodynamic investigations

Comparison of electrocatalytic characterization of boron-doped diamond and SnO2 electrodes

International Nuclear Information System (INIS)

Lv, Jiangwei; Feng, Yujie; Liu, Junfeng; Qu, Youpeng; Cui, Fuyi

2013-01-01

Boron-doped diamond (BDD) and SnO 2 electrodes were prepared by direct current plasma chemical vapor deposition (DC-PCVD) and sol–gel method, respectively. Electrochemical characterization of the two electrodes were investigated by phenol electrochemical degradation, accelerated service life test, cyclic voltammetry (CV) in phenol solution, polarization curves in H 2 SO 4 . The surface morphology and crystal structure of two electrodes were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) analysis. The results showed a considerable difference between the two electrodes in their electrocatalytic activity, electrochemical stability and surface properties. Phenol was readily mineralized to CO 2 at BDD electrode, favoring electrochemical combustion, but its degradation was much slower at SnO 2 electrode. The service life of BDD electrode was 10 times longer than that of SnO 2 . Higher electrocatalytic activity and electrochemical stability of BDD electrode arise from its high oxygen evolution potential and the physically absorbed hydroxyl radicals (·OH) on electrode surface.

Comparison between La_0.6Sr_0.4CoO_3-d and LaNi_0.6Co_0.4O_3-d infiltrated oxygen electrodes for long-term durable solid oxide fuel cells

DEFF Research Database (Denmark)

Ovtar, Simona; Hauch, Anne; Veltzé, Sune

2018-01-01

The degradation of infiltrated oxygen electrodes during long-term operation of solid oxide fuel cells (SOFCs) was studied. The infiltrated oxygen electrodes were prepared by infiltration of the electro-catalysts La0.6Sr0.4CoO3-d (LSC) and LaNi0.6Co0.4O3-d (LCN) into a porous yttria stabilized...... conducted and the change of resistance was followed by electrochemical impedance spectroscopy under current load. The cell performance degradation profiles of the LSC and LCN infiltrated cells showed significant differences. The performance of the LSC infiltrated cell stabilized after 700 h of operation...

Organic Photovoltaic Structures as Photo-active Electrodes

International Nuclear Information System (INIS)

Gustafson, Matthew P.; Clark, Noel; Winther-Jensen, Bjorn; MacFarlane, Douglas R.

2014-01-01

This study demonstrated the novel use of a bulk heterojunction (BHJ), as present in modern organic solar cells, as a light-assisted electrocatalyst for water electrolysis reactions. Two separate organic photo-voltaic electrode structures were designed for targeting both the reduction, (ITO-PET/PEDOT:PSS/P3HT:PCBM)* and oxidation, (ITO-PET/ZnO/P3HT:PCBM)* reactions of water, denoted as OPE-R and OPE-O respectively. The OPE-R electrode supported both the proton reduction reaction (PRR) and oxygen reduction reaction (ORR) achieving photocurrents of -0.04 mAcm −2 (ORR) and -0.03 mAcm −2 (PRR) and a photovoltage of 0.50 V (ORR) and onset photovoltage at -0.59 V (PRR). By comparison, the OPE-O electrode achieved photocurrents of 0.15 mAcm −2 and photovoltages of 0.35 V for the water oxidation reaction (WOR). Both BHJ designs confirmed evidence of photo-enhanced Bulk Heterojunction Electrode (BHE) activity. The stability and sources of electrode degradation were also studied, with the OPE-O electrode proving to be more stable than the OPE-R electrode, most likely due to the PEDOT:PSS layer and PSS migration in the presence of water. *Indium Tin Oxide (ITO), Polyethylene Terephthalate (PET), Poly(3,4-ethylenedioxythiophene) (PEDOT), Polystyrenesulfonate acid (PSS), Poly(3-hexylthiophene) (P3HT), Phenyl-C 61 -Butyric acid Methyl ester (PCBM), Zinc Oxide (ZnO)

Electrochemical synthesis of hydrogen peroxide: Rotating disk electrode and fuel cell studies

International Nuclear Information System (INIS)

Lobyntseva, Elena; Kallio, Tanja; Alexeyeva, Nadezda; Tammeveski, Kaido; Kontturi, Kyoesti

2007-01-01

The electrochemical reduction of oxygen on various catalysts was studied using the thin-layer rotating disk electrode (RDE) method. High-surface-area carbon was modified with an anthraquinone derivative and gold nanoparticles. Polytetrafluoroethylene (PTFE) and cationic polyelectrolyte (FAA) were used as binders in the preparation of thin-film electrodes. Our primary goal was to find a good electrocatalyst for the two-electron reduction of oxygen to hydrogen peroxide. All electrochemical measurements were carried out in 0.1 M KOH. Cyclic voltammetry was used in order to characterise the surface processes of the modified electrodes in O 2 -free electrolyte. The RDE results revealed that the carbon-supported gold nanoparticles are active catalysts for the four-electron reduction of oxygen in alkaline solution. Anthraquinone-modified high-area carbon catalyses the two-electron reduction at low overpotentials, which is advantageous for hydrogen peroxide production. In addition, the polymer electrolyte fuel cell technology was used for the generation of hydrogen peroxide. The cell was equipped with a bipolar membrane which consisted of commercial Nafion 117 as a cation-exchange layer and FT-FAA as an anion-exchange layer. The bipolar membranes were prepared by a hot pressing method. Use of the FAA ionomer as a binder for the anthraquinone-modified carbon catalyst resulted in production of hydrogen peroxide

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.

“Imaging” LEIS of micro-patterned solid oxide fuel cell electrodes

Energy Technology Data Exchange (ETDEWEB)

Druce, John, E-mail: john.druce@i2cner.kyushu-u.ac.jp [International Institute for Carbon Neutral Energy Research (wpi-I2CNER), Kyushu University, Fukuoka 819-0395 (Japan); Simrick, Neil [Department of Materials, Imperial College London, London SW7 2BP (United Kingdom); Ishihara, Tatsumi [International Institute for Carbon Neutral Energy Research (wpi-I2CNER), Kyushu University, Fukuoka 819-0395 (Japan); Kilner, John [International Institute for Carbon Neutral Energy Research (wpi-I2CNER), Kyushu University, Fukuoka 819-0395 (Japan); Department of Materials, Imperial College London, London SW7 2BP (United Kingdom)

2014-08-01

Understanding the kinetics of oxygen exchange between the gas phase and a ceramic electrode is key to optimising the performance of electrochemical energy conversion devices such as Solid Oxide Fuel Cells. Clearly the surface chemistry of these materials is important, and surface sensitive techniques such as Low Energy Ion Scattering (LEIS) can provide important compositional information key to unravelling electrode kinetics. In this work, we use high lateral resolution LEIS to perform local analyses of a micropatterned electrode structure, of the type often used for studies of the geometrical dependences of electrode performance. We find that the results are comparable to those for bulk materials, but detect evidence of cation interdiffusion from the electrode to the electrolyte. Finally, we note that this preliminary study could open the prospect of in situ measurements of cells near operating conditions.

A highly sensitive amperometric sensor for oxygen based on iron(II) tetrasulfonated phthalocyanine and iron(III) tetra-(N-methyl-pyridyl)-porphyrin multilayers

International Nuclear Information System (INIS)

Duarte, Juliana C.; Luz, Rita C.S.; Damos, Flavio S.; Tanaka, Auro A.; Kubota, Lauro T.

2008-01-01

The development of a highly sensitive sensor for oxygen is proposed using a glassy carbon (GC) electrode modified with alternated layers of iron(II) tetrasulfonated phthalocyanine (FeTsPc) and iron(III) tetra-(N-methyl-pyridyl)-porphyrin (FeT4MPyP). The modified electrode showed excellent catalytic activity for the oxygen reduction. The reduction potential of the oxygen was shifted about 330 mV toward less negative values with this modified electrode, presenting a peak current much higher than those observed on a bare GC electrode. Cyclic voltammetry and rotating disk electrode (RDE) experiments indicated that the oxygen reduction reaction involves 4 electrons with a heterogenous rate constant (k obs ) of 3 x 10 5 mol -1 L s -1 . A linear response range from 0.2 up to 6.4 mg L -1 , with a sensitivity of 4.12 μA L mg -1 (or 20.65 μA cm -2 L mg -1 ) and a detection limit of 0.06 mg L -1 were obtained with this sensor. The repeatability of the proposed sensor, evaluated in terms of relative standard deviation (R.S.D.) was 2.0% for 10 measurements of a solution of 6.4 mg L -1 oxygen. The sensor was applied to determine oxygen in pond and tap water samples showing to be a promising tool for this purpose

Modified cermet fuel electrodes for solid oxide electrochemical cells

Science.gov (United States)

Ruka, Roswell J.; Spengler, Charles J.

1991-01-01

An exterior porous electrode (10), bonded to a solid oxygen ion conducting electrolyte (13) which is in contact with an interior electrode (14), contains coarse metal particles (12) of nickel and/or cobalt, having diameters from 3 micrometers to 35 micrometers, where the coarse particles are coated with a separate, porous, multiphase layer (17) containing fine metal particles of nickel and/or cobalt (18), having diameters from 0.05 micrometers to 1.75 micrometers and conductive oxide (19) selected from cerium oxide, doped cerium oxide, strontium titanate, doped strontium titanate and mixtures thereof.

Computer assisted optimization of sensitivity of the catalytic polarography wave of uranly/nitrate system

International Nuclear Information System (INIS)

Betteridge, D.; Wade, A.P.; Neves, E.A.; Gutz, I.

1982-01-01

The utilization of 'Simplex' optimization program, writes in Basic language, used to the study of catalytic polarographic wave procedure the reaction of uranium (III) with nitrate in acidic medium at the mercury electrode/solution interface is described. This 'Simplex' optimization requires a much smaller number of experiments to reach an improved condition without increase of the number of trial and error experiments. (C.G.C.) [pt

Characterisation of the oxygen fluxes in the division, elongation and mature zones of Vitis roots: influence of oxygen availability.

Science.gov (United States)

Mancuso, Stefano; Boselli, Maurizio

2002-03-01

Oxygen fluxes into and from root cells of Vitis rupestris (flooding sensitive), V. riparia (flooding tolerant) and V. vinifera (medium tolerance to flooding) were measured under different levels of O2 availability using a recently developed polarographic O2-selective, vibrating-microelectrode system. The system enables fluxes to be measured with a spatial resolution of 2-3 microm and a temporal resolution of 10 s. No difference in root porosity was found among the genotypes when grown for 30 days in an aerated solution. Under normoxic conditions, O2 influx was characterised by two distinct peaks, one in the division zone and the other in the elongation zone of the roots. This pattern was found in all three species studied, although the fluxes showed a different magnitude. The peak in the elongation zone coincided with maximum relative elemental growth rates. When the energetics of the cell was disturbed by cyanide, both growth and oxygen O2 influxes ceased at the same time. Under hypoxic conditions, V. riparia plants showed a precise strategy directed toward the maintenance of enough O2 for the respiratory needs of mitosis in the apical meristem of the roots. Thus, whereas in the division zone of V. rupestris and V. vinifera, at bulk O2 concentrations of 0.094 mol x m(-3), the O2 influx was reduced by 70.5 and 38.5%, respectively, for V. riparia no variation in the O2 influx was detected down to bulk O2 concentrations of 0.078 mol x m(-3). Moreover, in accordance with the different tolerances of the plants, the Vitis genotypes were found to differ in their radial O2 loss from the adventitious roots when in an O2-free environment. The results are discussed in terms of possible mechanisms of response to anoxia in Vitis species with different tolerances to flooding.

Persistent increase in oxygen consumption and impaired neurovascular coupling after spreading depression in rat neocortex.

Science.gov (United States)

Piilgaard, Henning; Lauritzen, Martin

2009-09-01

Cortical spreading depression (CSD) is associated with a dramatic failure of brain ion homeostasis and increased energy metabolism. There is strong clinical and experimental evidence to suggest that CSD is the mechanism of migraine, and involved in progressive neuronal injury in stroke and head trauma. Here we tested the hypothesis that single episodes of CSD induced acute hypoxia, and prolonged impairment of neurovascular and neurometabolic coupling. Cortical spreading depression was induced in rat frontal cortex, whereas cortical electrical activity and local field potentials (LFPs) were recorded by glass microelectrodes, cerebral blood flow (CBF) by laser-Doppler flowmetry, and tissue oxygen tension (tpO(2)) with polarographic microelectrodes. Cortical spreading depression increased cerebral metabolic rate of oxygen (CMRO(2)) by 71%+/-6.7% and CBF by 238%+/-48.1% for 1 to 2 mins. For the following 2 h, basal tpO(2) and CBF were reduced whereas basal CMRO(2) was persistently elevated by 8.1%+/-2.9%. In addition, within first hour after CSD we found impaired neurovascular coupling (LFP versus CBF), whereas neurometabolic coupling (LFP versus CMRO(2)) remained unaffected. Impaired neurovascular coupling was explained by both reduced vascular reactivity and suppressed function of cortical inhibitory interneurons. The protracted effects of CSD on basal CMRO(2) and neurovascular coupling may contribute to cellular dysfunction in patients with migraine and acutely injured cerebral cortex.

Amperometric detection and electrochemical oxidation of aliphatic amines and ammonia on silver-lead oxide thin-film electrodes

Energy Technology Data Exchange (ETDEWEB)

Ge, Jisheng [Iowa State Univ., Ames, IA (United States)

1996-01-08

This thesis comprises three parts: Electrocatalysis of anodic oxygen-transfer reactions: aliphatic amines at mixed Ag-Pb oxide thin-film electrodes; oxidation of ammonia at anodized Ag-Pb eutectic alloy electrodes; and temperature effects on oxidation of ethylamine, alanine, and aquated ammonia.

A novel ethanol/oxygen microfluidic fuel cell with enzymes immobilized onto cantilevered porous electrodes

Science.gov (United States)

Desmaële, D.; Nguyen-Boisse, T. T.; Renaud, L.; Tingry, S.

2016-11-01

This paper introduces a novel design of membraneless microfluidic biofuel cell that incorporates three-dimensional porous electrodes containing immobilized enzymes to catalyze redox reactions occurring in the presence of ethanol/O2 co-laminar flows. In order to maximize the penetration depth of the reactants inside the porous medium, we report on the preliminary evaluation of cantilevered bioelectrodes, namely the fibrous electrodes protrude along the internal walls of the miniature electrochemical chamber. As a first proof-of-concept, we demonstrate the integration of a bioanode and a biocathode into a lamination-based microfluidic cell fabricated via rapid prototyping. With enzymes deposited into the fibrous structure of 25 mm long, 1 mm wide and 0.11 mm thick carbon paper electrodes, the volumetric power density reached 1.25 mW cm-3 at 0.43 V under a flow rate of 50 μL min-1. An advantage of the presented microfluidic biofuel cell is that it can be adapted to include a larger active electrode volume via the vertical stacking of multiple thin bioelectrodes. We therefore envision that our design would be amenable to reach the level of net power required to supply energy to a plurality of low-consumption electronic devices.

Influence of BaO in perovskite electrodes for the electrochemical reduction of NOx

DEFF Research Database (Denmark)

Simonsen, Vibe Louise Ernlund; Johnsen, M.M.; Kammer Hansen, Kent

2007-01-01

Using the point electrode method, the effect of BaO on electrochemical reduction of NO (x) was investigated using the perovskites La0.85Sr0.15MnO3 (LSM15) and La0.85Sr0.15CoO3 (LSCo15) as electrode materials. The experiments were carried out in the temperature range 400-600 degrees C in 1% NO and...... favored oxygen reduction compared to reduction of nitric oxide. The LSCO15 electrode containing BaO reacted to form a K2NiF4-structure and was not tested further....

Three-dimensional B,N-doped Graphene Foam as a Metal-free Catalyst for Oxygen Reduction Reaction

Science.gov (United States)

2013-01-01

evaluated by the cyclic voltammetry and linear sweep voltammetry techniques on rotating disk electrodes ( RDE ). Durability testing of the BN-GF...conditions. Fig. 8 (a) RDE voltammograms of the undoped GF/GC electrode, the B-GF/GC electrode, the N-GF/GC electrode, the BN-GF/GC electrode, and the...Pt–C/GC electrode in an oxygen saturated 0.1 M KOH solution at a rotation rate of 1600 rpm. Scan rate: 10 mV s1. (b) RDE voltammograms of the BN-GF

Rotating disk electrode system for elevated pressures and temperatures.

Science.gov (United States)

Fleige, M J; Wiberg, G K H; Arenz, M

2015-06-01

We describe the development and test of an elevated pressure and temperature rotating disk electrode (RDE) system that allows measurements under well-defined mass transport conditions. As demonstrated for the oxygen reduction reaction on polycrystalline platinum (Pt) in 0.5M H2SO4, the setup can easily be operated in a pressure range of 1-101 bar oxygen, and temperature of 140 °C. Under such conditions, diffusion limited current densities increase by almost two orders of magnitude as compared to conventional RDE setups allowing, for example, fuel cell catalyst studies under more realistic conditions. Levich plots demonstrate that the mass transport is indeed well-defined, i.e., at low electrode potentials, the measured current densities are fully diffusion controlled, while at higher potentials, a mixed kinetic-diffusion controlled regime is observed. Therefore, the setup opens up a new field for RDE investigations under temperature and current density conditions relevant for low and high temperature proton exchange membrane fuel cells.

Rotating disk electrode system for elevated pressures and temperatures

International Nuclear Information System (INIS)

Fleige, M. J.; Wiberg, G. K. H.; Arenz, M.

2015-01-01

We describe the development and test of an elevated pressure and temperature rotating disk electrode (RDE) system that allows measurements under well-defined mass transport conditions. As demonstrated for the oxygen reduction reaction on polycrystalline platinum (Pt) in 0.5M H 2 SO 4 , the setup can easily be operated in a pressure range of 1–101 bar oxygen, and temperature of 140 °C. Under such conditions, diffusion limited current densities increase by almost two orders of magnitude as compared to conventional RDE setups allowing, for example, fuel cell catalyst studies under more realistic conditions. Levich plots demonstrate that the mass transport is indeed well-defined, i.e., at low electrode potentials, the measured current densities are fully diffusion controlled, while at higher potentials, a mixed kinetic-diffusion controlled regime is observed. Therefore, the setup opens up a new field for RDE investigations under temperature and current density conditions relevant for low and high temperature proton exchange membrane fuel cells

Rotating disk electrode system for elevated pressures and temperatures

Energy Technology Data Exchange (ETDEWEB)

Fleige, M. J.; Wiberg, G. K. H.; Arenz, M. [Department of Chemistry and Nano-Science Center, University of Copenhagen, Universitetsparken 5, 2100 Ø Copenhagen (Denmark)

2015-06-15

We describe the development and test of an elevated pressure and temperature rotating disk electrode (RDE) system that allows measurements under well-defined mass transport conditions. As demonstrated for the oxygen reduction reaction on polycrystalline platinum (Pt) in 0.5M H{sub 2}SO{sub 4}, the setup can easily be operated in a pressure range of 1–101 bar oxygen, and temperature of 140 °C. Under such conditions, diffusion limited current densities increase by almost two orders of magnitude as compared to conventional RDE setups allowing, for example, fuel cell catalyst studies under more realistic conditions. Levich plots demonstrate that the mass transport is indeed well-defined, i.e., at low electrode potentials, the measured current densities are fully diffusion controlled, while at higher potentials, a mixed kinetic-diffusion controlled regime is observed. Therefore, the setup opens up a new field for RDE investigations under temperature and current density conditions relevant for low and high temperature proton exchange membrane fuel cells.

Rotating disk electrode system for elevated pressures and temperatures

Science.gov (United States)

Fleige, M. J.; Wiberg, G. K. H.; Arenz, M.

2015-06-01

We describe the development and test of an elevated pressure and temperature rotating disk electrode (RDE) system that allows measurements under well-defined mass transport conditions. As demonstrated for the oxygen reduction reaction on polycrystalline platinum (Pt) in 0.5M H2SO4, the setup can easily be operated in a pressure range of 1-101 bar oxygen, and temperature of 140 °C. Under such conditions, diffusion limited current densities increase by almost two orders of magnitude as compared to conventional RDE setups allowing, for example, fuel cell catalyst studies under more realistic conditions. Levich plots demonstrate that the mass transport is indeed well-defined, i.e., at low electrode potentials, the measured current densities are fully diffusion controlled, while at higher potentials, a mixed kinetic-diffusion controlled regime is observed. Therefore, the setup opens up a new field for RDE investigations under temperature and current density conditions relevant for low and high temperature proton exchange membrane fuel cells.

Testing and performance of electrolytic oxygen meters for use in liquid sodium

International Nuclear Information System (INIS)

Taylor, R.G.; Thompson, R.

1983-01-01

The performance of yttria-doped thoria ceramic electrochemical oxygen meters in liquid sodium is described. Tests were carried out using laboratory loops. Temperature coefficients of the oxygen meters have been measured between 380 0 C and 480 0 C, and the response to changes in oxygen level using cold-trap temperatures from 125 0 C to 250 0 C was determined. The ceramic has been shown to give good performance over lifetimes exceeding 400 days in some cases. The temperature coefficients and response to oxygen level changes are in good agreement with thermodynamic predictions. The effect of running the meters in high-oxygen sodium has been studied and a general mode of failure has been shown to be grain-boundary attack by oxygen/sodium solutions. The effect of #betta#-radiation on the meters has been studied. The meters with a metal/metal oxide reference electrode were unaffected by dose rates up to 52860 mGy h - 1 . Meters with an air reference electrode do show an effect as a voltage reduction at levels down to 2420 mGy h - 1 . This effect was temperature-dependent and was insignificant at 500 0 C. (orig.)

Electrochemical capacity fading of polyaniline electrode in supercapacitor: An XPS analysis

Directory of Open Access Journals (Sweden)

Jinxing Deng

2017-04-01

Full Text Available To understand the electrochemical capacity fading of the polyaniline (PANI electrodes in supercapacitors, for the first time, their chemical structure change during electrochemical cycles was traced with XPS analysis after the HCl doped PANI electrodes were subjected to the cyclic voltammetry test in 1.0 M H2SO4 electrolyte for different cycle numbers. The results showed that the chlorine disappeared in the electrode surface, while the surface element contents of sulfur and oxygen increased with the electrochemical cycles increased. It demonstrated that the hydrolytic degradation of the PANI chains and exchange of dopant occurred during the electrochemical cycling, causing the fading in the mechanical and electrochemical performance of the PANI electrodes. This understanding should lead to better design of the conductive polymer-based energy storage devices.

Electrochemical investigations of activation and degradation of hydrogen storage alloy electrodes in sealed Ni/MH battery

Energy Technology Data Exchange (ETDEWEB)

Chen, W.X.; Xu, Z.D. [Zhejiang University, Hangzhou (China). Dept. of Chemistry; Tu, J.P. [Zhejiang University, Hangzhou (China). Dept. of Materials Science and Engineering

2002-04-01

The M1Ni{sub 0.4}Co{sub 0.6}Al{sub 0.4} alloy was treated with hot alkaline solution containing a small amount of KBH{sub 4} and its effect on the activation and degradation behaviors of the hydrogen storage alloy electrodes in sealed Ni/MH batteries was investigated. It was found that the treated alloy electrode exhibited a better activation property than the untreated one in the sealed battery as well as in open cell. For the treated alloy electrode activating, the polarization resistance in the sealed battery was almost equal to that in the open cell. But in the case of the untreated alloy electrode activating, the polarization resistance in the sealed battery was larger than that in the open cell. The reason is that the oxide film on the untreated alloy surface suppressed the combination of the oxygen evolved on the positive electrode with hydrogen on the negative alloy surface. In addition, the decaying of capacity of the untreated alloy electrode was much faster than that of the treated one. The reasons were, that after surface treatment, the Ni-rich and Al-poor layer on the alloy surface not only had a high electrocatalytic activity for hydrogen electrode reaction, but also facilitated the combination of the oxygen with hydrogen and hydrogen adsorption on the alloy surface. (author)

Polarization characteristics of composite electrodes in electrochemical cells with solid electrolytes based on CeO2 and LaGaO3

International Nuclear Information System (INIS)

Yaroslavtsev, I. Yu.; Kuzin, B. L.; Bronin, D. I.; Bogdanovich, N. M.

2005-01-01

For two types of electrochemical cells with oxygen-conducting solid electrolytes based on lanthanum gallate (LSGM) and cerium oxide (SDC) studied are the temperature dependences of the polarization conductivity of air electrodes prepared from lanthanum strontium manganite (LSM) and composites LSM-LSGM, LSM-SDC, and LSM-SSZ (SSZ is zirconium dioxide-based electrolyte). Effect of praseodymium oxide, added into these electrodes as a modifier, on their electrochemical properties is examined. Electrochemical systems with an LSM/LSGM interface exhibit low electrochemical activity toward the oxygen reaction, because during the formation of electrodes, LSM interacts with LSGM to form a poorly conducting product [ru

Binary cobalt ferrite nanomesh arrays as the advanced binder-free electrode for applications in oxygen evolution reaction and supercapacitors

Science.gov (United States)

Liu, Li; Zhang, Huijuan; Mu, Yanping; Bai, Yuanjuan; Wang, Yu

2016-09-01

The porous CoFe2O4nanomesh arrays are successfully synthesized on nickel foam substrate through a high temperature and pressure hydrothermal method, following by the thermal post-treatment in air. The CoFe2O4 nanomesh arrays own numerous pores and large specific surface area, which is in favor of exposing more active sites. In consideration of the structural preponderances and versatility of the materials, the CoFe2O4 nanomesh arrays have been researched as the binder-free electrode materials for electrocatalysis and supercapacitors. When the CoFe2O4nanomesh arrays on nickel foam (CoFe2O4 NM-As/Ni) directly act as the free-binder catalyst toward catalyzing the oxygen evolution reaction (OER) of electrochemical water splitting, CoFe2O4 NM-As/Ni exhibits an admirable OER property with a low onset potential of 1.47 V(corresponding to the onset overpotential of 240 mV), a minimal overpotential (η10 = 253 mV), a small Tafel slope (44 mV dec-1), large anodic currents and long-term durability for 35 h in alkaline media. In addition, as an electrode of supercapacitors, CoFe2O4 NM-As/Ni obtains a desired specific capacitance (1426 F/g at the current density of 1 A/g), remarkable rate capability (1024 F/g at the current density of 20 A/g) and eminent capacitance retention (92.6% after 3000 cycles). The above results demonstrate the CoFe2O4 NM-As/Ni possesses great potential application in electrocatalysis and supercapacitors.

Mechanisms of Furfural Reduction on Metal Electrodes: Distinguishing Pathways for Selective Hydrogenation of Bioderived Oxygenates

International Nuclear Information System (INIS)

Chadderdon, Xiaotong H.; Chadderdon, David J.; Matthiesen, John E.

2017-01-01

Electrochemical reduction of biomass-derived platform molecules is an emerging route for the sustainable production of fuels and chemicals. Understanding gaps between reaction conditions, underlying mechanisms, and product selectivity have limited the rational design of active, stable, and selective catalyst systems. Here, the mechanisms of electrochemical reduction of furfural, an important biobased platform molecule and model for aldehyde reduction, are explored through a combination of voltammetry, preparative electrolysis, thiol-electrode modifications, and kinetic isotope studies. It is demonstrated that two distinct mechanisms are operable on metallic Cu electrodes in acidic electrolytes: (i) electrocatalytic hydrogenation (ECH) and (ii) direct electroreduction. The contributions of each mechanism to the observed product distribution are clarified by evaluating the requirement for direct chemical interactions with the electrode surface and the role of adsorbed hydrogen. Further analysis reveals that hydrogenation and hydrogenolysis products are generated by parallel ECH pathways. By understanding the underlying mechanisms it enables the manipulation of furfural reduction by rationally tuning the electrode potential, electrolyte pH, and furfural concentration to promote selective formation of important biobased polymer precursors and fuels.

Mechanisms of Furfural Reduction on Metal Electrodes: Distinguishing Pathways for Selective Hydrogenation of Bioderived Oxygenates.

Science.gov (United States)

Chadderdon, Xiaotong H; Chadderdon, David J; Matthiesen, John E; Qiu, Yang; Carraher, Jack M; Tessonnier, Jean-Philippe; Li, Wenzhen

2017-10-11

Electrochemical reduction of biomass-derived platform molecules is an emerging route for the sustainable production of fuels and chemicals. However, understanding gaps between reaction conditions, underlying mechanisms, and product selectivity have limited the rational design of active, stable, and selective catalyst systems. In this work, the mechanisms of electrochemical reduction of furfural, an important biobased platform molecule and model for aldehyde reduction, are explored through a combination of voltammetry, preparative electrolysis, thiol-electrode modifications, and kinetic isotope studies. It is demonstrated that two distinct mechanisms are operable on metallic Cu electrodes in acidic electrolytes: (i) electrocatalytic hydrogenation (ECH) and (ii) direct electroreduction. The contributions of each mechanism to the observed product distribution are clarified by evaluating the requirement for direct chemical interactions with the electrode surface and the role of adsorbed hydrogen. Further analysis reveals that hydrogenation and hydrogenolysis products are generated by parallel ECH pathways. Understanding the underlying mechanisms enables the manipulation of furfural reduction by rationally tuning the electrode potential, electrolyte pH, and furfural concentration to promote selective formation of important biobased polymer precursors and fuels.

Investigations on the kinetics of the oxygen reduction in high temperature fuel cells

International Nuclear Information System (INIS)

Erning, J.W.

1998-07-01

Lanthan-Strontium-Manganite perowskites are the most widespread materials in use for solid oxide fuel cell cathodes. The electrode reaction taking place, i.e. the reduction of oxygen supplied by air, was investigated by electrochemical means to obtain further knowledge about the electrode processes. The high activation energy of this reaction (200 kJ/mol), preventing lower operation temperatures of the SOFC, was the starting point for the investigation. Quasi steady state current voltage measurements and impedance spectroscopy were performed in a three electrode configuration. The electrodes were of circular shape with a diameter of 10 mm. The preparation was made by screen printing as well as wet powder spraying onto plates made of Yttria-stabilized zirconia. Perowskite powders of varying chemical and stoichiometric composition were used. To obtain higher power densities and, more important, lower apparent activation energies, catalytic layers were added at the interface electrode/electrolyte. Additionally, a less complex system, a model electrode/electrolyte setup made from single-crystal YSZ as electrolyte and gold in liquid and solid state as electrode was developed to create a better defined system. This setup was used to investigate the behaviour of the electrode/electrolyte interface. Reliable, reproducible results could be obtained using either setup. The experimental conditions i.e. oxygen partial pressure, temperature and overpotential were varied in order to determine the kinetic properties of the electrodes. Apparent activation energies, pre-exponential factors, apparent charge-transfer coefficients and electrochemical orders of reaction were calculated from the current-voltage data in order to propose possible reaction steps. (orig.)

Study of the electrooxidation of ethanol on hydrophobic electrodes by DEMS and HPLC

International Nuclear Information System (INIS)

Gonzalez Pereira, M.; Davila Jimenez, M.; Elizalde, M.P.; Manzo-Robledo, A.; Alonso-Vante, N.

2004-01-01

The electrochemical oxidation of ethanol in alkaline solution has been studied on Cu-PVC electrode and Ni/Cu-PVC composite electrodes modified by ruthenium nanoparticles. The techniques used were cyclic voltammetry (CV), steady-state potentiostatic method, on line differential electrochemical mass spectrometry (DEMS), and high-performance liquid chromatography (HPLC). The chemical products: acetaldehyde and acetic acid were detected measuring the proper mass charge (m/z) ratios. These products were also confirmed by HPLC. The surface modification of composite electrodes by ruthenium nanoparticles promotes the formation of acetaldehyde. As shown by DEMS, the surface modification shifts the onset potential for oxygen evolution reaction on the Cu-PVC composite electrode towards more anodic values

Study of the electrooxidation of ethanol on hydrophobic electrodes by DEMS and HPLC

Energy Technology Data Exchange (ETDEWEB)

Gonzalez Pereira, M.; Davila Jimenez, M.; Elizalde, M.P.; Manzo-Robledo, A.; Alonso-Vante, N

2004-09-15

The electrochemical oxidation of ethanol in alkaline solution has been studied on Cu-PVC electrode and Ni/Cu-PVC composite electrodes modified by ruthenium nanoparticles. The techniques used were cyclic voltammetry (CV), steady-state potentiostatic method, on line differential electrochemical mass spectrometry (DEMS), and high-performance liquid chromatography (HPLC). The chemical products: acetaldehyde and acetic acid were detected measuring the proper mass charge (m/z) ratios. These products were also confirmed by HPLC. The surface modification of composite electrodes by ruthenium nanoparticles promotes the formation of acetaldehyde. As shown by DEMS, the surface modification shifts the onset potential for oxygen evolution reaction on the Cu-PVC composite electrode towards more anodic values.

Variations in tumour oxygen tension (pO2) during accelerated radiotherapy of head and neck carcinoma

International Nuclear Information System (INIS)

Guichard, M.; Eschwege, F.; Luboinski, B.; Wibault, P.; Weeger, P.; Lusinchi, A.; Lartigau, E.

1998-01-01

The study was performed to assess the effect of accelerated radiotherapy on oxygenation of primary tumours and metastatic nodes in patients with advanced head and neck tumours. In 14 patients with head and neck tumour, oxygen tension (pO 2 ) was evaluated in normal tissues and tumours (primary tumour or metastatic neck node) before (0 Gy) and after 2 weeks (32 Gy) of accelerated radiotherapy (70 Gy in 3.5 weeks, with three daily fractions). Radiotherapy was combined with carbogen breathing in 5 patients. pO 2 was measured using a polarographic technique. For pooled normal tissues, median pO 2 was 38 mmHg before treatment and 46 mmHg after 2 weeks. For tumours, very low values ( 2 12 mmHg before treatment versus 26 mmHg after 2 weeks, P 2 was 44 mmHg at 2 weeks, compared with 13.5 mmHg before treatment (P=0.05). Very low pO 2 values, corresponding to tumour hypoxia, were found in the tumours (primary and metastatic neck nodes) prior to accelerated treatment. During the first 2 weeks of accelerated treatment, an increase in median pO 2 was found in nine of the 14 tumours, together with a decrease in the frequency of very low values. (Copyright (c) 1998 Elsevier Science B.V., Amsterdam. All rights reserved.)

Oxygen, hydrogen, ethylene and CO 2 development in lithium-ion batteries

Science.gov (United States)

Holzapfel, M.; Würsig, A.; Scheifele, W.; Vetter, J.; Novák, P.

Gas evolution has been examined for different types of battery-related electrode materials via in situ differential electrochemical mass spectrometry (DEMS). Besides standard graphite also a novel silicon-based negative electrode was examined and it was shown that the evolution of hydrogen and ethylene is considerably reduced on this material compared to graphite. Oxygen evolution was proven to happen on the oxidative reaction of a Li 2O 2 electrode, besides a certain oxidation of the electrolyte. The 4.5 V plateau upon the oxidation of Li[Ni 0.2Li 0.2Mn 0.6]O 2 was likewise proven to be linked to oxygen evolution. Also in this case electrolyte oxidation was shown to be a side reaction. Layered positive electrode materials Li(Ni,Co,Al)O 2 and Li(Ni,Mn,Co)O 2 were also examined. The influence of different parameters on the CO 2 evolution in lithium-ion batteries was shown up. The amount of CO 2 formation is increased by high temperatures and cell voltages, while the addition of vinylene carbonate (VC) decreases it. Li(Ni,Mn,Co)O 2 shows much less CO 2 evolution than Li(Ni,Co,Al)O 2.

Diffusion-controlled oxygen reduction on multi-copper oxidase-adsorbed carbon aerogel electrodes without mediator

Energy Technology Data Exchange (ETDEWEB)

Tsujimura, S.; Kamitaka, Y.; Kano, K. [Division of Applied Life Sciences, Graduate School of Agriculture, Kyoto University, Sakyo-ku, Kyoto (Japan)

2007-12-15

Bioelectrocatalytic reduction of O{sub 2} into water was archived at diffusion-controlled rate by using enzymes (laccase from Trametes sp. and bilirubin oxidase from Myrothecium verrucaria, which belong to the family of multi-copper oxidase) adsorbed on mesoporous carbon aerogel particle without a mediator. The current density was predominantly controlled by the diffusion of dissolved O{sub 2} in rotating-disk electrode experiments, and reached a value as large as 10 mA cm{sup -2} at 1 atm O{sub 2}, 25 C, and 8,000 rpm on the laccase-adsorbed electrode. The overpotential of the bioelectrocatalytic reduction of O{sub 2} was 0.4-0.55 V smaller than that observed on a Pt disk electrode. Without any optimization, the laccase-adsorbed biocathode showed stable current intensity of the O{sub 2} reduction in an air-saturated buffer at least for 10 days under continuous flow system. (Abstract Copyright [2007], Wiley Periodicals, Inc.)

Optimisation of oxygen ion transport in materials for ceramic membrane devices.

Science.gov (United States)

Kilner, J A

2007-01-01

Oxygen transport in ceramic oxide materials has received much attention over the past few decades. Much of this interest has stemmed from the desire to construct high temperature electrochemical devices for energy conversion, an example being the solid oxide fuel cell. In order to achieve high performance for these devices, insights are needed in how to achieve optimum performance from the functional components such as the electrolytes and electrodes. This includes the optimisation of oxygen transport through the crystal lattice of electrode and electrolyte materials and across the homogeneous (grain boundary) and heterogeneous interfaces that exist in real devices. Strategies are discussed for the optimisation of these quantities and current problems in the characterisation of interfacial transport are explored.

Spillover Phenomena and Its Striking Impacts in Electrocatalysis for Hydrogen and Oxygen Electrode Reactions

Directory of Open Access Journals (Sweden)

Georgios D. Papakonstantinou

2011-01-01

striking target issue of the present paper, has been shown to be the superior for substantiation of the revertible cell assembly for spontaneous reversible alterpolar interchanges between PEMFC and WE. The main target of the present thorough review study has been to throw some specific insight light on the overall spillover phenomena and their effects in electrocatalysis of oxygen and hydrogen electrode reactions from diverse angles of view and broad contemporary experimental methods and approaches (XPS, FTIR, DRIFT, XRD, potentiodynamic spectra, UHRTEM.

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

5V-class bulk-type all-solid-state rechargeable lithium batteries with electrode-solid electrolyte composite electrodes prepared by aerosol deposition

Science.gov (United States)

Iriyama, Yasutoshi; Wadaguchi, Masaki; Yoshida, Koki; Yamamoto, Yuta; Motoyama, Munekazu; Yamamoto, Takayuki

2018-05-01

Composite electrodes (∼9 μm in thickness) composed of 5V-class electrode of LiNi0.5Mn1.5O4 (LNM) and high Li+ conductive crystalline-glass solid electrolyte (LATP, Ohara Inc.) were prepared at room temperature by aerosol deposition (AD) on platinum sheets. The resultant LNM-LATP composite electrodes were combined with LiPON and Li, and 5V-class bulk-type all-solid-state rechargeable lithium batteries (SSBs) were prepared. The crystallnity of the LNM in the LNM-LATP composite electrode was improved by annealing. Both thermogravimetry-mass spectroscopy analysis and XRD analysis clarified that the side reactions between the LNM and the LATP occurred over 500 °C with oxygen release. From these results, annealing temperature of the LNM-LATP composite electrode system was optimized at 500 °C due to the improved crystallinity of the LNM with avoiding the side-reactions. The SSBs with the composite electrodes (9 μm in thickness, 40 vol% of the LNM) annealed at 500 °C delivered 100 mAh g-1 at 10 μA cm-2 at 100 °C. Degradation of the discharge capacity with the repetition of the charge-discharge reactions was observed, which will originate from large volume change of the LNM (∼6.5%) during the reactions.

Dosing of traces of oxygenated water by polarography; Dosage de traces d'eau oxygenee par polarographie

Energy Technology Data Exchange (ETDEWEB)

Faure, A. M.; Malterre, J.

1960-07-01

As dosing oxygenated water by using polarography has been envisaged within the framework of water purity controls for the Melusine pile, the objective of the authors is here to see whether the polarographic method could be satisfying for routine analyses, and would result in a higher dosing sensitivity. They describe the polarography principle, indicate devices which are used, specify and comment conditions under which polarography is performed [French] Le dosage de l'eau oxygenee par polarographie a ete envisage dans le cadre des controles de purete de l'eau de la pile Melusine. La methode calorimetrique dans les conditions de fonctionnement de Melusine a puissance maxima, avait mis en evidence des teneurs en H{sub 2}O{sub 2} produites par radiolyse de l'eau, inferieures a 20 ppm. Le but de cette etude, a ete de voir si la methode polarographique pouvait donner satisfaction en analyse de routine a ces teneurs la et permettre une plus grande sensibilite de dosage, la colorimetrie se limitant pratiquement a 1 ppm avec une precision de 20 pour cent environ. (auteurs)

Experience at J.E.N. with electrochemical cells for measurement of oxygen activity

International Nuclear Information System (INIS)

La Torre, M.de; Lapena, J.; Couchoud, M.

1981-01-01

The experience gained at the J.E.N. with oxygen meters since 1974 till 1980 is presented. Thirteen oxygen meters were tested. Eight with Cu/Cu/ 2 O reference electrode and the rest with Sn/SnO 2 , and two types of electrolyte tube produced by zircoa under specifications development by UNC and HEDL. The cells equiped with Cu/Cu 2 O showed an anomalous performance giving an e.m.f. higher than the theoretical value, and one of them was in close agreement to cells using air as reference electrode. An explanation is given. The performance of the cells with Sn/SnO 2 is in good agreement with those obtained in others laboratories. To calculate the theoretical value, it has derived a correlation colubility for oxygen with 262 data obtained by the vacuum distillation method. Various recommendations are pointed out on the future development of the oxygen meters to improve its performance. (author)

Effects of motexafin gadolinium on tumor oxygenation and cellular oxygen consumption

International Nuclear Information System (INIS)

Donnelly, E.T.; Liu, Y.; Rockwell, S.; Magda, D.

2003-01-01

Full text: Recent work in our laboratory showed that motexafin gadolinium (MGd, Xcytrin), a drug currently in Phase III clinical trials as an adjuvant to radiation therapy, modulates the oxygen tensions in EMT6 tumors. The median pO 2 increased from the control value of 1.5±0.4 mmHg to 7.4 ± 3.8 mmHg six hours after treatment with 40 μmol/kg MGd and the percentage of severely hypoxic readings in the tumors ( 7 plateau phase EMT6 cells in 3 mL Dulbecco's Modified Eagle's Medium supplemented with 10% dialyzed fetal bovine serum, which contains no ascorbic acid. In the absence of ascorbic acid, 100 μM MGd did not alter the cellular oxygen consumption rate for EMT6 cells significantly. Marked inhibition of cellular oxygen consumption was observed when cells were incubated with 100 μM MGd in medium supplemented with equimolar ascorbic acid (a 31.5% decrease in consumption was observed after 6 hours of treatment). The 5% mannitol vehicle solution with equimolar ascorbic acid had no discernible effect on cellular oxygen consumption. Ascorbic acid may facilitate cellular uptake of MGd via the intermediate formation of a MGd-oxalate complex. These studies suggest that changes in cellular oxygen consumption could contribute to the changes in tumor oxygenation seen after administration of MGd. These experiments were supported by Pharmacyclics and training grant T32CA09085 from the NIH (E.T.D.). We thank Dr. Raymond Russell for allowing us to use his oxygen electrode apparatus

Fabrication and electrochemical characterization of multi-walled carbon nanotube electrodes for applications to nano-electrochemical sensing

International Nuclear Information System (INIS)

Hwang, Sookhyun; Choi, Hyonkwang; Jeon, Minhyon; Vedala, Harindra; Kim, Taehyung; Choi, Wonbong

2010-01-01

In this study, we fabricated and electrochemically characterized two types of individual carbon nanotube electrodes: an as-produced multi-walled carbon nanotube (MWNT) electrode and a modified MWNT electrode. As-produced MWNTs were electrically contacted with Au/Ti layers by using nanolithography and RF magnetron sputtering. Open-ended modified MWNT electrodes were fabricated by using a reactive ion etching treatment under an oxygen atmosphere. We also performed cyclic voltammetry measurements to detect aqueous dopamine solutions with different concentrations. We found that an individual MWNT electrode, which had a small effective area, showed good electrochemical performance. The electrocatalytic behavior of the modified electrode, which had 'broken' open ends were better than that of the as-produced electrode with respect to sensitivity. The modified electrode was capable of detecting dopamine at the picomolar level. Therefore, an individual modified MWNT electrode has potential for applications to active components in nanobiosensors.

Integrating a redox-coupled dye-sensitized photoelectrode into a lithium-oxygen battery for photoassisted charging.

Science.gov (United States)

Yu, Mingzhe; Ren, Xiaodi; Ma, Lu; Wu, Yiying

2014-10-03

With a high theoretical specific energy, the non-aqueous rechargeable lithium-oxygen battery is a promising next-generation energy storage technique. However, the large charging overpotential remains a challenge due to the difficulty in electrochemically oxidizing the insulating lithium peroxide. Recently, a redox shuttle has been introduced into the electrolyte to chemically oxidize lithium peroxide. Here, we report the use of a triiodide/iodide redox shuttle to couple a built-in dye-sensitized titanium dioxide photoelectrode with the oxygen electrode for the photoassisted charging of a lithium-oxygen battery. On charging under illumination, triiodide ions are generated on the photoelectrode, and subsequently oxidize lithium peroxide. Due to the contribution of the photovoltage, the charging overpotential is greatly reduced. The use of a redox shuttle to couple a photoelectrode and an oxygen electrode offers a unique strategy to address the overpotential issue of non-aqueous lithium-oxygen batteries and also a distinct approach for integrating solar cells and batteries.

Microscopic origin of the 1.3 G0 conductance observed in oxygen-doped silver quantum point contacts

KAUST Repository

Tu, Xingchen

2014-11-21

© 2014 AIP Publishing LLC. Besides the peak at one conductance quantum, G0, two additional features at ∼0.4 G0 and ∼1.3 G0 have been observed in the conductance histograms of silver quantum point contacts at room temperature in ambient conditions. In order to understand such feature, here we investigate the electronic transport and mechanical properties of clean and oxygen-doped silver atomic contacts by employing the non-equilibrium Green\\'s function formalism combined with density functional theory. Our calculations show that, unlike clean Ag single-atom contacts showing a conductance of 1 G0, the low-bias conductance of oxygen-doped Ag atomic contacts depends on the number of oxygen impurities and their binding configuration. When one oxygen atom binds to an Ag monatomic chain sandwiched between two Ag electrodes, the low-bias conductance of the junction always decreases. In contrast, when the number of oxygen impurities is two and the O-O axis is perpendicular to the Ag-Ag axis, the transmission coefficients at the Fermi level are, respectively, calculated to be 1.44 for the junction with Ag(111) electrodes and 1.24 for that with Ag(100) electrodes, both in good agreement with the measured value of ∼1.3 G0. The calculated rupture force (1.60 nN for the junction with Ag(111) electrodes) is also consistent with the experimental value (1.66 ± 0.09 nN), confirming that the measured ∼1.3 G0 conductance should originate from Ag single-atom contacts doped with two oxygen atoms in a perpendicular configuration.

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

Carbon materials modified by plasma treatment as electrodes for supercapacitors

Energy Technology Data Exchange (ETDEWEB)

Lota, Grzegorz; Frackowiak, Elzbieta [Institute of Chemistry and Technical Electrochemistry, Poznan University of Technology, Piotrowo 3, 60-965 Poznan (Poland); Tyczkowski, Jacek; Kapica, Ryszard [Technical University of Lodz, Faculty of Process and Environmental Engineering, Division of Molecular Engineering, Wolczanska 213, 90-924 Lodz (Poland); Lota, Katarzyna [Institute of Non-Ferrous Metals Branch in Poznan, Central Laboratory of Batteries and Cells, Forteczna 12, 61-362 Poznan (Poland)

2010-11-15

The carbon material was modified by RF plasma with various reactive gases: O{sub 2}, Ar and CO{sub 2}. Physicochemical properties of the final carbon products were characterized using different techniques such as gas adsorption method and XPS. Plasma modified materials enriched in oxygen functionalities were investigated as electrodes for supercapacitors in acidic medium. The electrochemical measurements have been carried out using cyclic voltammetry, galvanostatic charge/discharge and impedance spectroscopy. The electrochemical measurements have confirmed that capacity characteristics are closely connected with a type of plasma exposition. Modification processes have an influence on the kind and amount of surface functional groups in the carbon matrix. The moderate increase of capacity of carbon materials modified by plasma has been observed using symmetric two-electrode systems. Whereas investigations made in three-electrode system proved that the suitable selection of plasma modification parameters allows to obtain promising negative and positive electrode materials for supercapacitor application. (author)

Investigation of the oxygen exchange mechanism on Pt|yttria stabilized zirconia at intermediate temperatures: Surface path versus bulk path

International Nuclear Information System (INIS)

Opitz, Alexander K.; Lutz, Alexander; Kubicek, Markus; Kubel, Frank; Hutter, Herbert; Fleig, Juergen

2011-01-01

Highlights: → Oxygen exchange kinetics of Pt on YSZ investigated by means of Pt model electrodes. → Two different geometry dependencies of the polarization resistance identified. → At higher temperatures the oxygen exchange reaction proceeds via a Pt surface path. → At lower temperatures a bulk path through the Pt thin film electrode is discussed. - Abstract: The oxygen exchange kinetics of platinum on yttria-stabilized zirconia (YSZ) was investigated by means of geometrically well-defined Pt microelectrodes. By variation of electrode size and temperature it was possible to separate two temperature regimes with different geometry dependencies of the polarization resistance. At higher temperatures (550-700 deg. C) an elementary step located close to the three phase boundary (TPB) with an activation energy of ∼1.6 eV was identified as rate limiting. At lower temperatures (300-400 deg. C) the rate limiting elementary step is related to the electrode area and exhibited a very low activation energy in the order of 0.2 eV. From these observations two parallel pathways for electrochemical oxygen exchange are concluded. The nature of these two elementary steps is discussed in terms of equivalent circuits. Two combinations of parallel rate limiting reaction steps are found to explain the observed geometry dependencies: (i) Diffusion through an impurity phase at the TPB in parallel to diffusion of oxygen through platinum - most likely along Pt grain boundaries - as area-related process. (ii) Co-limitation of oxygen diffusion along the Pt|YSZ interface and charge transfer at the interface with a short decay length of the corresponding transmission line (as TPB-related process) in parallel to oxygen diffusion through platinum.

Anodic oxidation with doped diamond electrodes: a new advanced oxidation process

International Nuclear Information System (INIS)

Kraft, Alexander; Stadelmann, Manuela; Blaschke, Manfred

2003-01-01

Boron-doped diamond anodes allow to directly produce OH· radicals from water electrolysis with very high current efficiencies. This has been explained by the very high overvoltage for oxygen production and many other anodic electrode processes on diamond anodes. Additionally, the boron-doped diamond electrodes exhibit a high mechanical and chemical stability. Anodic oxidation with diamond anodes is a new advanced oxidation process (AOP) with many advantages compared to other known chemical and photochemical AOPs. The present work reports on the use of diamond anodes for the chemical oxygen demand (COD) removal from several industrial wastewaters and from two synthetic wastewaters with malic acid and ethylenediaminetetraacetic (EDTA) acid. Current efficiencies for the COD removal between 85 and 100% have been found. The formation and subsequent removal of by-products of the COD oxidation has been investigated for the first time. Economical considerations of this new AOP are included

Understanding anodic wear at boron doped diamond film electrodes

International Nuclear Information System (INIS)

Chaplin, Brian P.; Hubler, David K.; Farrell, James

2013-01-01

This research investigated the mechanisms associated with anodic wear of boron-doped diamond (BDD) film electrodes. Cyclic voltammetry (CV), x-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and electrochemical impedance spectroscopy (EIS) were used to measure changes in electrode response and surface chemistry as a function of the charge passed and applied current density. Density functional theory (DFT) modeling was used to evaluate possible reaction mechanisms. The initial hydrogen-terminated surface was electrochemically oxidized at lower potentials than water oxidation (≤ 1.83 V/SHE), and was not catalyzed by the hydrogen-terminated surface. In the region where water oxidation produces hydroxyl radicals (OH·), the hydrogen-terminated surface may also be oxidized by chemical reaction with OH·. Oxygen atoms became incorporated into the surface via reaction of carbon atoms with OH·, forming both C = O and C-OH functional groups, that were also detected by XPS measurements. Experimental and DFT modeling results indicate that the oxygenated diamond surface lowers the potential for activationless water oxidation from 2.74 V/SHE for the hydrogen terminated surface to 2.29 V/SHE for the oxygenated surface. Electrode wear was accelerated at high current densities (i.e., 500 mA cm −2 ), where SEM results indicated oxidation of the BDD film resulted in significant surface roughening. These results are supported by EIS measurements that document an increase in the double-layer capacitance as a function of the charge passed. DFT simulations provide a possible mechanism that explains the observed diamond oxidation. DFT simulation results indicate that BDD edge sites (=CH 2 ) can be converted to COOH functional groups, which are further oxidized via reactions with OH· to form H 2 CO 3(aq.) with an activation energy of 58.9 kJ mol −1

Application of wire beam electrode technique to investigate initiation and propagation of rebar corrosion

International Nuclear Information System (INIS)

Shi, Wei; Dong, Ze Hua; Kong, De Jie; Guo, Xing Peng

2013-01-01

Multi-electrode technique named as wire beam electrode (WBE) was used to study pitting corrosion of rebar under concrete cover. When WBE embedded mortar sample was immersed in NaCl solution, uneven distributions of galvanic current and open circuit potential (OCP) on the WBE were observed due to the initiation of pitting corrosion. The following oxygen depletion in mortar facilitated the negative shift of the OCP and the smoothing of the current and potential distributions. Wetting–drying cycle experiments showed that corrosion products instead of oxygen in wet mortar specimen sustained the propagation of pitting corrosion due to Fe (III) taking part in cathodic depolarization during oxygen-deficient wet period, which was confirmed by micro-Raman spectroscopy. In addition, new pitting corrosion occurred mainly near the corrosion products, leading to preferentially horizontal propagation of rust layer on the WBE. A localized corrosion factor was further presented to quantify the localised corrosion based on galvanic current maps

Application of wire beam electrode technique to investigate initiation and propagation of rebar corrosion

Energy Technology Data Exchange (ETDEWEB)

Shi, Wei; Dong, Ze Hua, E-mail: zehua.dong@gmail.com; Kong, De Jie; Guo, Xing Peng

2013-06-15

Multi-electrode technique named as wire beam electrode (WBE) was used to study pitting corrosion of rebar under concrete cover. When WBE embedded mortar sample was immersed in NaCl solution, uneven distributions of galvanic current and open circuit potential (OCP) on the WBE were observed due to the initiation of pitting corrosion. The following oxygen depletion in mortar facilitated the negative shift of the OCP and the smoothing of the current and potential distributions. Wetting–drying cycle experiments showed that corrosion products instead of oxygen in wet mortar specimen sustained the propagation of pitting corrosion due to Fe (III) taking part in cathodic depolarization during oxygen-deficient wet period, which was confirmed by micro-Raman spectroscopy. In addition, new pitting corrosion occurred mainly near the corrosion products, leading to preferentially horizontal propagation of rust layer on the WBE. A localized corrosion factor was further presented to quantify the localised corrosion based on galvanic current maps.

Electrode-electrolyte interface model of tripolar concentric ring electrode and electrode paste.

Science.gov (United States)

Nasrollaholhosseini, Seyed Hadi; Steele, Preston; Besio, Walter G

2016-08-01

Electrodes are used to transform ionic currents to electrical currents in biological systems. Modeling the electrode-electrolyte interface could help to optimize the performance of the electrode interface to achieve higher signal to noise ratios. There are previous reports of accurate models for single-element biomedical electrodes. In this paper we develop a model for the electrode-electrolyte interface for tripolar concentric ring electrodes (TCRE) that are used to record brain signals.

Construction and direct electrochemistry of orientation controlled laccase electrode.

Science.gov (United States)

Li, Ying; Zhang, Jiwei; Huang, Xirong; Wang, Tianhong

2014-03-28

A laccase has multiple redox centres. Chemisorption of laccases on a gold electrode through a polypeptide tag introduced at the protein surface provides an isotropic orientation of laccases on the Au surface, which allows the orientation dependent study of the direct electrochemistry of laccase. In this paper, using genetic engineering technology, two forms of recombinant laccase which has Cys-6×His tag at the N or C terminus were generated. Via the Au-S linkage, the recombinant laccase was assembled orientationally on gold electrode. A direct electron transfer and a bioelectrocatalytic activity toward oxygen reduction were observed on the two orientation controlled laccase electrodes, but their electrochemical behaviors were found to be quite different. The orientation of laccase on the gold electrode affects both the electron transfer pathway and the electron transfer efficiency of O2 reduction. The present study is helpful not only to the in-depth understanding of the direct electrochemistry of laccase, but also to the development of laccase-based biofuel cells. Copyright © 2014 Elsevier Inc. All rights reserved.

Anodic oxidation of anthraquinone dye Alizarin Red S at Ti/BDD electrodes

Energy Technology Data Exchange (ETDEWEB)

Sun Jianrui; Lu Haiyan [College of Chemistry, Jilin University, Changchun 130012 (China); Du Lili [State Key Laboratory of Superhard Materials, Jilin University, Changchun 130012 (China); Lin Haibo, E-mail: lhb910@jlu.edu.cn [College of Chemistry, Jilin University, Changchun 130012 (China); State Key Laboratory of Theoretical and Computational Chemistry, Jilin University, Changchun 130012 (China); Li Hongdong, E-mail: hdli@jlu.edu.cn [State Key Laboratory of Superhard Materials, Jilin University, Changchun 130012 (China)

2011-05-15

The boron-doped diamond (BDD) thin-film electrode with high quality using industrially titanium plate (Ti/BDD) as substrate has been prepared and firstly used in the oxidation of anthraquinone dye Alizarin Red S (ARS) in wastewaters. The Ti/BDD electrodes are shown to have high concentration of sp{sup 3}-bonded carbon and wide electrochemical window. The results of the cyclic voltammetries show that BDD has unique properties such as high anodic stability and the production of active intermediates at the high potential. The oxidation regions of ARS and water are significantly separated at the Ti/BDD electrode, and the peak current increases linearly with increasing ARS concentration. The bulk electrolysis shows that removal of chemical oxygen demand (COD) and color can be completely reached and the electrooxidation of ARS behaves as a mass-transfer-controlled process at the Ti/BDD electrode. It is demonstrated that the performances of the Ti/BDD electrode for anodic oxidation ARS have been significantly improved with respect to the traditional electrodes.

Layered Cu-based electrode for high-dielectric constant oxide thin film-based devices

International Nuclear Information System (INIS)

Fan, W.; Saha, S.; Carlisle, J.A.; Auciello, O.; Chang, R.P.H.; Ramesh, R.

2003-01-01

Ti-Al/Cu/Ta multilayered electrodes were fabricated on SiO 2 /Si substrates by ion beam sputtering deposition, to overcome the problems of Cu diffusion and oxidation encountered during the high dielectric constant (κ) materials integration. The Cu and Ta layers remained intact through the annealing in oxygen environment up to 600 deg. C. The thin oxide layer, formed on the Ti-Al surface, effectively prevented the oxygen penetration toward underneath layers. Complex oxide (Ba x Sr 1-x )TiO 3 (BST) thin films were grown on the layered Ti-Al/Cu/Ta electrodes using rf magnetron sputtering. The deposited BST films exhibited relatively high permittivity (150), low dielectric loss (0.007) at zero bias, and low leakage current -8 A/cm 2 at 100 kV/cm

Preparation and Performance of Sb-SnO2 / Ti Electrode Modified with Carbon Nanotubes

Directory of Open Access Journals (Sweden)

WEI Jin-zhi

2017-06-01

Full Text Available In order to improve the electro-catalytic oxidation activity and stability of Sb-SnO2 /Ti electrode，the CNTs-Sb-SnO2 /Ti electrode was prepared by sol-gel-thermal decomposition method. The microstructure and electrochemical properties of the modified electrode was characterized via SEM electrochemical impedance spectroscope ( EIS ，polarization curve and congo red degradation experiments. Furthermore，its the stability was investigated by accelerated life test. The results indicate that when the optimal doping amount of CNTs is 2. 0 g /L the congo red removal rate increases by 14. 7% using the CNTs-Sb-SnO2 /Ti electrode compared with the Sb-SnO2 /Ti electrode. Meanwhile pore structure appears and roughness increases on the surface of modified electrodes leading to larger specific surface area of electrode. Then the modified electrodes exhibit higher oxygen evolution potential and lower charge transfer resistance. Additionally，accelerated life tests reveal that the modified electrode has better electro-catalytic stability while the service life increases by

Dissolved hydrogen and oxygen sensors using semiconductor devices

International Nuclear Information System (INIS)

Hara, Nobuyoshi; Sugimoto, Katsuhisa

1995-01-01

The concentrations of DH and DO in aqueous solution are the factors that determine the equilibrium potential of hydrogen and oxygen electrode reactions, respectively, and are the quantities which directly related to the rates of hydrogen generation type and oxygen consumption type corrosion reactions, therefore, they have the important meaning in the electrochemistry of corrosion. In the hydrogen injection into BWR cooling water, the concentration of hydrogen must be controlled strictly, accordingly DH and DO sensors and electrochemical potential sensors are required. For the chemical sensors used in reactor cooling water, the perfectly solid state sensors made of high corrosion resistance materials, which are small size and withstand high temperature and high pressure, must be developed. The structure and the characteristics of the semiconductor devices used as gas sensors, and the principles of DH and DO sensors are described. If the idea of porous or discontinuous membrane gate is developed, the ion sensor of solid structure with one-body reference electrode may be made. (K.I.)

[The oxygen consumption of ostrich embryos during incubation].

Science.gov (United States)

Reiner, G; Dzapo, V

1995-02-01

This work deals with the oxygen consumption of ostrich chicks during incubation. Brood eggs were incubated in a hermetic isolated acrylic-glass cylinder. Reduction of oxygen content in the air surrounding the egg was measured using an oxygen-sensitive electrode. A sigmoid curve could be drawn during incubation, with the steepest phase being around day 26. Maximum oxygen consumption was reached on day 36. It was slightly decreased until day 39, when the embryo switches to lung circulation, followed again by an increase until hatching. Average oxygen consumptions for the whole brood interval were calculated to 63.6 liters. Oxygen volumes consumed on day 36 result in a demand about to 240 liters of fresh air per egg and day. Oxygen consumption of the embryos on day 36 was significantly positive correlated with their vitality. Numb or less vital embryos could be clearly differentiated from others. The higher a chick's oxygen consumption, the earlier and shorter its hatching. Possible applications of the method in regard to the evaluation of incubation parameters or chicken constitution are discussed.

Polarographic study of the Cu(II)/Cu(I) system in the presence of 1-ascorbic acid and 0,1 M ClK; Estudio polarografico del sistema Cu(II)/Cu(I) en presencia del acido 1-ascorbico y en ClK 0,1 M

Energy Technology Data Exchange (ETDEWEB)

Alonso Lopez, J

1969-07-01

While studying the catalytic effect of Cu{sup {down_arrow}}2 ions on the oxidation process of 1-ascorbic acid, it has been observed that, in a 0,1 M solution of K1 at a pH 6 to 7, the above acid gives rise in the presence of Cu{sup {down_arrow}}2 ions to a polarographic wave of half-wave potential of -0,41 V (vs. S.C.E.). (Author) 14 refs.

Amperometric bienzyme glucose biosensor based on carbon nanotube modified electrode with electropolymerized poly(toluidine blue O) film

International Nuclear Information System (INIS)

Wang Wenju; Wang Fang; Yao Yanli; Hu Shengshui; Shiu, Kwok-Keung

2010-01-01

The amperometric bienzyme glucose biosensor utilizing horseradish peroxidase (HRP) and glucose oxidase (GOx) immobilized in poly(toluidine blue O) (PTBO) film was constructed on multi-walled carbon nanotube (MWNT) modified glassy carbon electrode. The HRP layer could be used to analyze hydrogen peroxide with toluidine blue O (TBO) mediators, while the bienzyme system (HRP + GOx) could be utilized for glucose determination. Glucose underwent biocatalytic oxidation by GOx in the presence of oxygen to yield H 2 O 2 which was further reduced by HRP at the MWNT-modified electrode with TBO mediators. In the absence of oxygen, glucose oxidation proceeded with electron transfer between GOx and the electrode mediated by TBO moieties without H 2 O 2 production. The bienzyme electrode offered high sensitivity for amperometric determination of glucose at low potential, displaying Michaelis-Menten kinetics. The bienzyme glucose biosensor displayed linear response from 0.1 to 1.2 mM with a sensitivity of 113 mA M -1 cm -2 at an applied potential of -0.10 V in air-saturated electrolytes.

A glassy carbon electrode modified with an iron N4-macrocycle and reduced graphene oxide for voltammetric sensing of dissolved oxygen

International Nuclear Information System (INIS)

Silva, Saimon M.; Aguiar, Lucas F.; Carvalho, Rita M. S.; Tanaka, Auro A.; Damos, Flavio S.; Luz, Rita C. S.

2016-01-01

The authors describe a platform for the electrochemical reduction of oxygen. It is based on the use of a glassy carbon electrode (GCE) that was modified in a single-step microwave assisted reaction with a N4-macrocycle containing iron(III) (FeN4) and with reduced graphene oxide. The FeN4/rGO composite was characterized by cyclic voltammetry, differential pulse voltammetry, and scanning electrochemical microscopy (SECM). Cyclic voltammetry showed the composite to enable efficient reduction of O_2 at a very low overpotential (−0.05 V vs. Ag/AgCl). SECM measurements were carried out to map (in the redox competition mode) the activity of a GCE microelectrode modified with FeN4/rGO. Under optimized conditions, the response to dissolved O_2 ranges from 0.8 up to 25 mg⋅L"-"1, and the limit of detection is 0.2 mg⋅L"-"1. (author)

Performance evaluation of thermally treated graphite felt electrodes for vanadium redox flow battery and their four-point single cell characterization

Science.gov (United States)

Mazúr, P.; Mrlík, J.; Beneš, J.; Pocedič, J.; Vrána, J.; Dundálek, J.; Kosek, J.

2018-03-01

In our contribution we study the electrocatalytic effect of oxygen functionalization of thermally treated graphite felt on kinetics of electrode reactions of vanadium redox flow battery. Chemical and morphological changes of the felts are analysed by standard physico-chemical characterization techniques. A complex method four-point method is developed and employed for characterization of the felts in a laboratory single-cell. The method is based on electrochemical impedance spectroscopy and load curves measurements of positive and negative half-cells using platinum wire pseudo-reference electrodes. The distribution of ohmic and faradaic losses within a single-cell is evaluated for both symmetric and asymmetric electrode set-up with respect to the treatment conditions. Positive effect of oxygen functionalization is observed only for negative electrode, whereas kinetics of positive electrode reaction is almost unaffected by the treatment. This is in a contradiction to the results of typically employed cyclovoltammetric characterization which indicate that both electrodes are enhanced by the treatment to a similar extent. The developed four-point characterization method can be further used e.g., for the component screening and in-situ durability studies on single-cell scale redox flow batteries of various chemistries.

Towards Synergistic Electrode-Electrolyte Design Principles for Nonaqueous Li-O[Formula: see text] batteries.

Science.gov (United States)

Khetan, Abhishek; Krishnamurthy, Dilip; Viswanathan, Venkatasubramanian

2018-03-20

One route toward sustainable land and aerial transportation is based on electrified vehicles. To enable electrification in transportation, there is a need for high-energy-density batteries, and this has led to an enormous interest in lithium-oxygen batteries. Several critical challenges remain with respect to realizing a practical lithium-oxygen battery. In this article, we present a detailed overview of theoretical efforts to formulate design principles for identifying stable electrolytes and electrodes with the desired functionality and stability. We discuss design principles relating to electrolytes and the additional stability challenges that arise at the cathode-electrolyte interface. Based on a thermodynamic analysis, we discuss two important requirements for the cathode: the ability to nucleate the desired discharge product, Li[Formula: see text]O[Formula: see text], and the ability to selectively activate only this discharge product while suppressing lithium oxide, the undesired secondary discharge product. We propose preliminary guidelines for determining the chemical stability of the electrode and illustrate the challenge associated with electrode selection using the examples of carbon cathodes and transition metals. We believe that a synergistic design framework for identifying electrolyte-electrode formulations is needed to realize a practical Li-O[Formula: see text] battery.

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.

Oxygen reduction and evolution at single-metal active sites

DEFF Research Database (Denmark)

Calle-Vallejo, F.; Martínez, J.I.; García Lastra, Juan Maria

2013-01-01

A worldwide spread of clean technologies such as low-temperature fuel cells and electrolyzers depends strictly on their technical reliability and economic affordability. Currently, both conditions are hardly fulfilled mainly due to the same reason: the oxygen electrode, which has large overpotent...

Activated carbon electrodes: electrochemical oxidation coupled with desalination for wastewater treatment.

Science.gov (United States)

Duan, Feng; Li, Yuping; Cao, Hongbin; Wang, Yi; Crittenden, John C; Zhang, Yi

2015-04-01

The wastewater usually contains low-concentration organic pollutants and some inorganic salts after biological treatment. In the present work, the possibility of simultaneous removal of them by combining electrochemical oxidation and electrosorption was investigated. Phenol and sodium chloride were chosen as representative of organic pollutants and inorganic salts and a pair of activated carbon plate electrodes were used as anode and cathode. Some important working conditions such as oxygen concentration, applied potential and temperature were evaluated to reach both efficient phenol removal and desalination. Under optimized 2.0 V of applied potential, 38°C of temperature, and 500 mL min(-1) of oxygen flow, over 90% of phenol, 60% of TOC and 20% of salinity were removed during 300 min of electrolysis time. Phenol was removed by both adsorption and electrochemical oxidation, which may proceed directly or indirectly by chlorine and hypochlorite oxidation. Chlorophenols were detected as degradation intermediates, but they were finally transformed to carboxylic acids. Desalination was possibly attributed to electrosorption of ions in the pores of activated carbon electrodes. The charging/regeneration cycling experiment showed good stability of the electrodes. This provides a new strategy for wastewater treatment and recycling. Copyright © 2014 Elsevier Ltd. All rights reserved.

Electrocatalytic properties of Ti/Pt–IrO2 anode for oxygen evolution in PEM water electrolysis

DEFF Research Database (Denmark)

Ye, Feng; Li, Jianling; Wang, Xindong

2010-01-01

A novel Pt–IrO2 electrocatalyst was prepared using the dip-coating/calcinations method on titanium substrates. Titanium electrodes coated with oxides were investigated for oxygen evolution. Experimental results showed that Ti/Pt–IrO2 electrode containing 30mol% Pt in the coating exhibited signifi...

Scanning electrochemical microscopy. 47. Imaging electrocatalytic activity for oxygen reduction in an acidic medium by the tip generation-substrate collection mode.

Science.gov (United States)

Fernández, José L; Bard, Allen J

2003-07-01

The oxygen reduction reaction (ORR) in acidic medium was studied on different electrode materials by scanning electrochemical microscopy (SECM) operating in a new variation of the tip generation-substrate collection mode. An ultramicroelectrode tip placed close to the substrate electrode oxidizes water to oxygen at a constant current. The substrate is held at a potential where the tip-generated oxygen is reduced and the resulting substrate current is measured. By changing the substrate potential, it is possible to obtain a polarization (current-potential) curve, which depends on the electrocatalytic activity of the substrate material. The main difference between this mode and the classical feedback SECM mode of operation is that the feedback diffusion process is not required for the measurement, allowing its application for studying the ORR in acidic solutions. Activity-sensitive images of heterogeneous surfaces, e.g., with Pt and Au electrodes, were obtained from the substrate current when the x-y plane was scanned with the tip. The usefulness of this technique for imaging electrocatalytic activity of smooth metallic electrodes and of highly dispersed fuel cell-type electrocatalysts was demonstrated. The application of this method to the combinatorial chemical analysis of electrode materials and electrocatalysts is discussed.

A survey of reference electrodes for high temperature waters

International Nuclear Information System (INIS)

Molander, A.; Eriksson, Sture; Pein, K.

2000-11-01

In nuclear power plants, corrosion potential measurements are used to follow the conditions for different corrosion types in reactor systems, particularly IGSCC in BWRs. The goal of this work has been to give a survey of reference electrodes for high temperature water, both those that are used for nuclear environments and those that are judged to possible future development. The reference electrodes that are used today in nuclear power plants for corrosion potential measurements are of three types. Silver chloride electrodes, membrane electrodes and platinum electrodes (hydrogen electrodes). The principals for their function is described as well as the conversion of measured potentials to the SHE scale (Standard Hydrogen Electrode). Silver chloride electrodes consist of an inner reference system of silver chloride in equilibrium with a chloride solution. The silver chloride electrode is the most common reference electrode and can be used in several different systems. Platinum electrodes are usually more robust and are particularly suitable to use in BWR environment to follow the hydrogen dosage, but have limitations at low and no hydrogen dosage. Ceramic membrane electrodes can be with different types of internal reference system. They were originally developed for pH measurements in high temperature water. If pH is constant, the membrane electrode can be used as reference electrode. A survey of ceramic reference electrodes for high temperature water is given. A ceramic membrane of the type used works as an oxygen conductor, so the potential and pH in surrounding medium is in equilibrium with the internal reference system. A survey of the lately development of electrodes is presented in order to explain why the different types of electrodes are developed as well as to give a background to the possibilities and limitations with the different electrodes. Possibilities of future development of electrodes are also given. For measurements at low or no hydrogen dosage

Ag nanoparticle-modified MnO2 nanorods catalyst for use as an air electrode in zinc–air battery

International Nuclear Information System (INIS)

Goh, F.W. Thomas; Liu, Zhaolin; Ge, Xiaoming; Zong, Yun; Du, Guojun; Hor, T.S. Andy

2013-01-01

In this paper, we report the synthesis, characterization and application of an inexpensive yet efficient bifunctional catalyst composed of Ag nanocrystals (∼11 nm) anchored on α-MnO 2 nanorods. The nanostructured Ag–MnO 2 catalysts exhibit improved oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) performance in aqueous alkaline media, in terms of onset potential, generated current density and Tafel slopes. Rotating disk electrode results show that near-four electrons per oxygen molecule were transferred during ORR of Ag–MnO 2 . A zinc–air battery prototype employing Ag–MnO 2 in the air electrode was successfully operated for 270 cycles under light discharge–charge condition. Ag–MnO 2 is an efficient bifunctional catalyst for electrochemical devices such as metal–air batteries and alkaline fuel cells

Design of a neutral three-dimensional electro-Fenton system with foam nickel as particle electrodes for wastewater treatment

International Nuclear Information System (INIS)

Liu, Wei; Ai, Zhihui; Zhang, Lizhi

2012-01-01

Highlights: ► Remove RhB by a novel 3D-E-Fenton system using foam nickel as particle electrodes. ► The 3D-E-Fenton system exhibit much higher RhB removal efficiency than the counterpart 3D-E and E-Fenton system. ► Foam nickel as a particle electrode displays good oxygen reduction activity. ► The performance of RhB removal was optimized by some operating parameters and the optimization pH was the neutral. - Abstract: In this work, we demonstrate a novel three-dimensional electro-Fenton system (3D-E-Fenton) for wastewater treatment with foam nickel, activated carbon fiber and Ti/RuO 2 –IrO 2 as the particle electrodes, the cathode, and the anode respectively. This 3D-E-Fenton system could exhibit much higher rhodamine B removal efficiency (99%) than the counterpart three-dimensional electrochemical system (33%) and E-Fenton system (19%) at neutral pH in 30 min. The degradation efficiency enhancement was attributed to much more hydroxyl radicals generated in the 3D-E-Fenton system because foam nickel particle electrodes could activate molecular oxygen to produce ·O 2 − via a single-electron transfer pathway to subsequently generate more H 2 O 2 and hydroxyl radicals. This is the first observation of molecular oxygen activation over the particle electrodes in the three-dimensional electrochemical system. These interesting findings could provide some new insight on the development of high efficient E-Fenton system for wastewater treatment at neutral pH.

Oxygen ion transference number of doped lanthanum gallate

Science.gov (United States)

Wang, Shizhong; Wu, Lingli; Gao, Jie; He, Qiong; Liu, Meilin

The transference numbers for oxygen ion (t O) in several LaGaO 3-based materials are determined from oxygen concentration cells using the materials as the electrolyte, including La 0.8Sr 0.2Ga 0.8Mg 0.2O 3- δ (LSGM8282), La 0.8Sr 0.2Ga 0.8Mg 0.15Co 0.05O 3- δ (LSGMC5) and La 0.8Sr 0.2Ga 0.8Mg 0.115Co 0.085O 3- δ (LSGMC8.5). Analysis indicates that the accuracy in determination of oxygen ion transference number depends on the electrode polarization resistances of the concentration cell as well as the transport properties of the materials studied. For example, the ratio of open cell voltage to Nernst potential is a good approximation to the ionic transference number for LSGM8282. However, this approximation is no longer adequate for LSGMC5 and LSGMC8.5; the effect of electrode polarization resistances must be taken into consideration in estimation of the ionic transference numbers. In particular, the ionic transference number for LSGMC5 is as high as 0.99, suggesting that it is a promising electrolyte material for low-temperature solid-state electrochemical applications.

Data on treatment of sewage wastewater by electrocoagulation using punched aluminum electrode and characterization of generated sludge

Directory of Open Access Journals (Sweden)

Vinita Khandegar

2018-06-01

Full Text Available The electrocoagulation setup must be optimized in order to design an economically feasible process. Therefore, in this work, the effect of the punched aluminum electrode on the performance of the electrocoagulation (EC has been investigated. A series of experiments were performed for treatment of sewage wastewater using plane electrode and compare with punched electrodes. Effect of contact time, voltage, electrode spacing and stirring speed has been optimized for removal of Biochemical oxygen demand (BOD and Total dissolved solids (TDS. It was observed that the performance of electrocoagulation process increased using punched electrode. Also, the less operating cost noticed in punched electrode as compared to a plane electrode for (70–80% removal of BOD and TDS. These data would be useful in designing of an EC reactor to obtain high removal efficiency at low energy consumption. Keywords: Electrocoagulation, Sewage wastewater, Aluminum, Plane, Punched electrode

Theoretical Verification of Photoelectrochemical Water Oxidation Using Nanocrystalline TiO2 Electrodes

Directory of Open Access Journals (Sweden)

Shozo Yanagida

2015-05-01

Full Text Available Mesoscopic anatase nanocrystalline TiO2 (nc-TiO2 electrodes play effective and efficient catalytic roles in photoelectrochemical (PEC H2O oxidation under short circuit energy gap excitation conditions. Interfacial molecular orbital structures of (H2O3 &OH(TiO29H as a stationary model under neutral conditions and the radical-cation model of [(H2O3&OH(TiO29H]+ as a working nc-TiO2 model are simulated employing a cluster model OH(TiO29H (Yamashita/Jono’s model and a H2O cluster model of (H2O3 to examine excellent H2O oxidation on nc-TiO2 electrodes in PEC cells. The stationary model, (H2O3&OH(TiO29H reveals that the model surface provides catalytic H2O binding sites through hydrogen bonding, van der Waals and Coulombic interactions. The working model, [(H2O3&OH(TiO29H]+ discloses to have a very narrow energy gap (0.3 eV between HOMO and LUMO potentials, proving that PEC nc-TiO2 electrodes become conductive at photo-irradiated working conditions. DFT-simulation of stepwise oxidation of a hydroxide ion cluster model of OH−(H2O3, proves that successive two-electron oxidation leads to hydroxyl radical clusters, which should give hydrogen peroxide as a precursor of oxygen molecules. Under working bias conditions of PEC cells, nc-TiO2 electrodes are now verified to become conductive by energy gap photo-excitation and the electrode surface provides powerful oxidizing sites for successive H2O oxidation to oxygen via hydrogen peroxide.

Virtual electrodes for high-density electrode arrays

Science.gov (United States)

Cela, Carlos J.; Lazzi, Gianluca

2015-10-13

The present embodiments are directed to implantable electrode arrays having virtual electrodes. The virtual electrodes may improve the resolution of the implantable electrode array without the burden of corresponding complexity of electronic circuitry and wiring. In a particular embodiment, a virtual electrode may include one or more passive elements to help steer current to a specific location between the active electrodes. For example, a passive element may be a metalized layer on a substrate that is adjacent to, but not directly connected to an active electrode. In certain embodiments, an active electrode may be directly coupled to a power source via a conductive connection. Beneficially, the passive elements may help to increase the overall resolution of the implantable array by providing additional stimulation points without requiring additional wiring or driver circuitry for the passive elements.

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...

Improving startup performance with carbon mesh anodes in separator electrode assembly microbial fuel cells

KAUST Repository

Zhang, Fang; Xia, Xue; Luo, Yong; Sun, Dan; Call, Douglas F.; Logan, Bruce E.

2013-01-01

In a separator electrode assembly microbial fuel cell, oxygen crossover from the cathode inhibits current generation by exoelectrogenic bacteria, resulting in poor reactor startup and performance. To determine the best approach for improving startup

Monitoring and measurement of oxygen concentrations in liquid sodium

International Nuclear Information System (INIS)

Smith, D.L.

1976-01-01

The measurement of oxygen concentrations in sodium at levels of interest for LMFBR applications is reviewed. Additional data are presented to support the validity of the vanadium-equilibration method as a reference for determination of oxygen concentrations in sodium at levels equal to or less than 15 ppM. Operating experience with electrochemical oxygen meters that have a thoria-yttria electrolyte and a Na--Na 2 O reference electrode is described. Meter lifetimes in excess of one year have generally been achieved for operating temperatures of 352 and 402 0 C, and fairly stable emfs have been observed for periods of several months. 7 fig, 21 references

Dependence of Initial Oxygen Concentration on Ozone Yield Using Inductive Energy Storage System Pulsed Power Generator

Science.gov (United States)

Go, Tomio; Tanaka, Yasushi; Yamazaki, Nobuyuki; Mukaigawa, Seiji; Takaki, Koichi; Fujiwara, Tamiya

Dependence of initial oxygen concentration on ozone yield using streamer discharge reactor driven by an inductive energy storage system pulsed power generator is described in this paper. Fast recovery type diodes were employed as semiconductor opening switch to interrupt a circuit current within 100 ns. This rapid current change produced high-voltage short pulse between a secondary energy storage inductor. The repetitive high-voltage short pulse was applied to a 1 mm diameter center wire electrode placed in a cylindrical pulse corona reactor. The streamer discharge successfully occurred between the center wire electrode and an outer cylinder ground electrode of 2 cm inner diameter. The ozone was produced with the streamer discharge and increased with increasing pulse repetition rate. The ozone yield changed in proportion to initial oxygen concentration contained in the injected gas mixture at 800 ns forward pumping time of the current. However, the decrease of the ozone yield by decreasing oxygen concentration in the gas mixture at 180 ns forward pumping time of the current was lower than the decrease at 800 ns forward pumping time of the current. This dependence of the initial oxygen concentration on ozone yield at 180 ns forward pumping time is similar to that of dielectric barrier discharge reactor.

The Development of Nano-Composite Electrodes for Solid Oxide Electrolyzers

Energy Technology Data Exchange (ETDEWEB)

Gorte, Raymond J.; Vohs, John M.

2014-03-26

Solid oxide fuel cells (SOFC) and electrolyzers (SOE) offer an attractive means for converting between electrical and chemical energy. Because they operate at high temperatures and are usually based on electrolytes that are oxygen-ion conducting ceramics, such as yttria-stabilized zirconia (YSZ), they are equally capable of converting between CO and CO2 as between H2 and H2O. When operated in the SOFC mode, they are able to operate on hydrocarbon fuels so long as there are no materials within the anode that can catalyze carbon formation. Compared to other types of electrolyzers, SOE can exhibit the highest efficiencies because the theoretical Nernst potential is lower at high temperatures and because the electrode overpotentials in SOE tend to be much lower. Finally, pure H2 can be produced without an external electrical source by electrolysis of steam at one electrode and oxidation of any fuel at the other electrode through a process known as Natural-Gas Assisted Steam Electrolysis. This final report describes results from studies of novel electrodes for SOE and SOFC prepared by infiltration methods.

ELECTROCATALYTIC ACTIVITY FOR O2 REDUCTION OF UNSUBSTITUTED AND PERCHLORINATED IRON PHTHALOCYANINES ADSORBED ON AMINO-TERMINATED MULTIWALLED CARBON NANOTUBES DEPOSITED ON GLASSY CARBON ELECTRODES

OpenAIRE

CAÑETE, PAULINA; SILVA, J. FRANCISCO; ZAGAL, JOSÉ H

2014-01-01

Amino-functionalized multiwalled carbon nanotubes (MWCNT-NH2) were modified with Fe phthalocyanine (FePc) and perchlorinated Fe phthalocyanine (16(Cl)FePc) and deposited on glassy carbon electrodes (GCE). The electrocatalytic activity of these hybrid electrodes was examined for the reduction of molecular oxygen in alkaline media (0.2 M NaOH) using stationary and rotating disk electrodes. Electrodes containing 16(Cl)FePc are more active than those containing FePc. Electrodes containing CNTs ar...

Room-temperature spin-polarized organic light-emitting diodes with a single ferromagnetic electrode

Energy Technology Data Exchange (ETDEWEB)

Ding, Baofu, E-mail: b.ding@ecu.edu.au; Alameh, Kamal, E-mail: k.alameh@ecu.edu.au [Electron Science Research Institute, Edith Cowan University, 270 Joondalup Drive, Joondalup WA 6027 Australia (Australia); Song, Qunliang [Institute for Clean Energy and Advanced Materials, Southwest University, Chongqing 400715 (China)

2014-05-19

In this paper, we demonstrate the concept of a room-temperature spin-polarized organic light-emitting diode (Spin-OLED) structure based on (i) the deposition of an ultra-thin p-type organic buffer layer on the surface of the ferromagnetic electrode of the Spin-OLED and (ii) the use of oxygen plasma treatment to modify the surface of that electrode. Experimental results demonstrate that the brightness of the developed Spin-OLED can be increased by 110% and that a magneto-electroluminescence of 12% can be attained for a 150 mT in-plane magnetic field, at room temperature. This is attributed to enhanced hole and room-temperature spin-polarized injection from the ferromagnetic electrode, respectively.

All conducting polymer electrodes for asymmetric solid-state supercapacitors

KAUST Repository

Kurra, Narendra

2015-02-16

In this study, we report the fabrication of solid-state asymmetric supercapacitors (ASCs) based on conducting polymer electrodes on a plastic substrate. Nanostructured conducting polymers of poly(3,4-ethylenedioxythiophene), PEDOT, and polyaniline (PANI) are deposited electrochemically over Au-coated polyethylene naphthalate (PEN) plastic substrates. Due to the electron donating nature of the oxygen groups in the PEDOT, reduction potentials are higher, allowing it to be used as a negative electrode material. In addition, the high stability of PEDOT in its oxidised state makes it capable to exhibit electrochemical activity in a wide potential window. This can qualify PEDOT to be used as a negative electrode in fabricating asymmetric solid state supercapacitors with PANI as a positive electrode while employing polyvinyl alcohol (PVA)/H2SO4 gel electrolyte. The ASCs exhibit a maximum power density of 2.8 W cm−3 at an energy density of 9 mW h cm−3, which is superior to the carbonaceous and metal oxide based ASC solid state devices. Furthermore, the tandem configuration of asymmetric supercapacitors is shown to be capable of powering a red light emitting diode for about 1 minute after charging for 10 seconds.

Oxygen vacancy as fatigue evidence of La0.5Sr0.5CoO3/PbZr0.4Ti0.6O3/La0.5Sr0.5CoO3 capacitors

Science.gov (United States)

Liu, B. T.; Chen, J. E.; Sun, J.; Wei, D. Y.; Chen, J. H.; Li, X. H.; Bian, F.; Zhou, Y.; Guo, J. X.; Zhao, Q. X.; Guan, L.; Wang, Y. L.; Guo, Q. L.; Ma, L. X.

2010-09-01

La0.5Sr0.5CoO3 (LSCO) films grown on SrTiO3 substrates, cooled at reduced oxygen pressures, ranging from 8×104 to 1×10-4 Pa, from the depostion temperature, are used as the bottom electrodes of PbZr0.4Ti0.6O3 (PZT) capacitors to study the impact of oxygen stoichiometry of the LSCO bottom electrodes on the structural and physical properties of LSCO/PZT/LSCO capacitors. It is found that the tetragonality, polarization and fatigue-resistance of PZT films decrease with the decrease of the cooling oxygen pressure. Almost 60% polarization degradation occurs for the PZT capacitor with the LSCO bottom electrode cooled in 1×10-4 Pa oxygen up to 1010 switching cycles, indicating that the oxygen vacancy of the bottom electrode can result in fatigue of the LSCO/PZT/LSCO capacitor.

CAD/CAM–designed 3D-printed electroanalytical cell for the evaluation of nanostructured gas-diffusion electrodes

International Nuclear Information System (INIS)

Chervin, Christopher N; Parker, Joseph F; Nelson, Eric S; Rolison, Debra R; Long, Jeffrey W

2016-01-01

The ability to effectively screen and validate gas-diffusion electrodes is critical to the development of next-generation metal–air batteries and regenerative fuel cells. The limiting electrode in a classic two-terminal device such as a battery or fuel cell is difficult to discern without an internal reference electrode, but the flooded electrolyte characteristic of three-electrode electroanalytical cells negates the prime function of an air electrode—a void volume freely accessible to gases. The nanostructured catalysts that drive the energy-conversion reactions (e.g., oxygen reduction and evolution in the air electrode of metal–air batteries) are best evaluated in the electrode structure as-used in the practical device. We have designed, 3D-printed, and characterized an air-breathing, thermodynamically referenced electroanalytical cell that allows us to mimic the Janus arrangement of the gas-diffusion electrode in a metal–air cell: one face freely exposed to gases, the other wetted by electrolyte. (paper)

CAD/CAM-designed 3D-printed electroanalytical cell for the evaluation of nanostructured gas-diffusion electrodes

Science.gov (United States)

Chervin, Christopher N.; Parker, Joseph F.; Nelson, Eric S.; Rolison, Debra R.; Long, Jeffrey W.

2016-04-01

The ability to effectively screen and validate gas-diffusion electrodes is critical to the development of next-generation metal-air batteries and regenerative fuel cells. The limiting electrode in a classic two-terminal device such as a battery or fuel cell is difficult to discern without an internal reference electrode, but the flooded electrolyte characteristic of three-electrode electroanalytical cells negates the prime function of an air electrode—a void volume freely accessible to gases. The nanostructured catalysts that drive the energy-conversion reactions (e.g., oxygen reduction and evolution in the air electrode of metal-air batteries) are best evaluated in the electrode structure as-used in the practical device. We have designed, 3D-printed, and characterized an air-breathing, thermodynamically referenced electroanalytical cell that allows us to mimic the Janus arrangement of the gas-diffusion electrode in a metal-air cell: one face freely exposed to gases, the other wetted by electrolyte.

Preparation and characterization of PbO2–ZrO2 nanocomposite electrodes

International Nuclear Information System (INIS)

Yao Yingwu; Zhao Chunmei; Zhu Jin

2012-01-01

PbO 2 –ZrO 2 nanocomposite electrodes were prepared by the anodic codeposition in the lead nitrate plating bath containing ZrO 2 nanoparticles. The influences of the ZrO 2 nanoparticles concentration, current density, temperature and stirring rate of the plating bath on the composition of the nanocomposite electrodes were investigated. The surface morphology and the structure of the nanocomposite electrodes were characterized by scanning electronic microscopy (SEM) and X-ray diffraction (XRD), respectively. The experimental results show that the addition of ZrO 2 nanoparticles in the electrodeposition process of lead dioxide significantly increases the lifetime of nanocomposite electrodes. The PbO 2 –ZrO 2 nanocomposite electrodes have a service life of 141 h which is almost four times longer than that of the pure PbO 2 electrodes. The morphology of PbO 2 –ZrO 2 nanocomposite electrodes is more compact and finer than that of PbO 2 electrodes. The relative surface area of the composite electrodes is approximately 2 times that of the pure PbO 2 electrodes. The structure test shows that the addition of ZrO 2 nanoparticles into the plating bath decreases the grain size of the PbO 2 –ZrO 2 nanocomposite electrodes. The anodic polarization curves show that the oxygen evolution overpotential of PbO 2 –ZrO 2 nanocomposite electrodes is higher than PbO 2 electrodes. The pollutant anodic oxidation experiment show that the PbO 2 –ZrO 2 nanocomposite electrode exhibited the better performance for the degradation of 4-chlorophenol than PbO 2 electrode, the removal ratio of COD reached 96.2%.

Method of making sulfur tolerant composite cermet electrodes for solid oxide electrochemical cells

Science.gov (United States)

Isenberg, Arnold O.

1989-01-01

An electrochemical apparatus is made containing an exterior electorde bonded to the exterior of a tubular, solid, oxygen ion conducting electrolyte where the electrolyte is also in contact with an interior electrode, said exterior electrode comprising particles of an electronic conductor contacting the electrolyte, where a ceramic metal oxide coating partially surrounds the particles and is bonded to the electrolyte, and where a coating of an ionic-electronic conductive material is attached to the ceramic metal oxide coating and to the exposed portions of the particles.

3D PIC-MCC simulations of discharge inception around a sharp anode in nitrogen/oxygen mixtures

Science.gov (United States)

Teunissen, Jannis; Ebert, Ute

2016-08-01

We investigate how photoionization, electron avalanches and space charge affect the inception of nanosecond pulsed discharges. Simulations are performed with a 3D PIC-MCC (particle-in-cell, Monte Carlo collision) model with adaptive mesh refinement for the field solver. This model, whose source code is available online, is described in the first part of the paper. Then we present simulation results in a needle-to-plane geometry, using different nitrogen/oxygen mixtures at atmospheric pressure. In these mixtures non-local photoionization is important for the discharge growth. The typical length scale for this process depends on the oxygen concentration. With 0.2% oxygen the discharges grow quite irregularly, due to the limited supply of free electrons around them. With 2% or more oxygen the development is much smoother. An almost spherical ionized region can form around the electrode tip, which increases in size with the electrode voltage. Eventually this inception cloud destabilizes into streamer channels. In our simulations, discharge velocities are almost independent of the oxygen concentration. We discuss the physical mechanisms behind these phenomena and compare our simulations with experimental observations.

Superoxide Stabilization and a Universal KO2 Growth Mechanism in Potassium-Oxygen Batteries.

Science.gov (United States)

Wang, Wanwan; Lai, Nien-Chu; Liang, Zhuojian; Wang, Yu; Lu, Yi-Chun

2018-04-23

Rechargeable potassium-oxygen (K-O 2 ) batteries promise to provide higher round-trip efficiency and cycle life than other alkali-oxygen batteries with satisfactory gravimetric energy density (935 Wh kg -1 ). Exploiting a strong electron-donating solvent, for example, dimethyl sulfoxide (DMSO) strongly stabilizes the discharge product (KO 2 ), resulting in significant improvement in electrode kinetics and chemical/electrochemical reversibility. The first DMSO-based K-O 2 battery demonstrates a much higher energy efficiency and stability than the glyme-based electrolyte. A universal KO 2 growth model is developed and it is demonstrated that the ideal solvent for K-O 2 batteries should strongly stabilize superoxide (strong donor ability) to obtain high electrode kinetics and reversibility while providing fast oxygen diffusion to achieve high discharge capacity. This work elucidates key electrolyte properties that control the efficiency and reversibility of K-O 2 batteries. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

ZnS nanoparticles electrodeposited onto ITO electrode as a platform for fabrication of enzyme-based biosensors of glucose

International Nuclear Information System (INIS)

Du, Jian; Yu, Xiuping; Wu, Ying; Di, Junwei

2013-01-01

The electrochemical and photoelectrochemical biosensors based on glucose oxidase (GOD) and ZnS nanoparticles modified indium tin oxide (ITO) electrode were investigated. The ZnS nanoparticles were electrodeposited directly on the surface of ITO electrode. The enzyme was immobilized on ZnS/ITO electrode surface by sol–gel method to fabricate glucose biosensor. GOD could electrocatalyze the reduction of dissolved oxygen, which resulted in a great increase of the reduction peak current. The reduction peak current decreased linearly with the addition of glucose, which could be used for glucose detection. Moreover, ZnS nanoparticles deposited on ITO electrode surface showed good photocurrent response under illumination. A photoelectrochemical biosensor for the detection of glucose was also developed by monitoring the decreases in the cathodic peak photocurrent. The results indicated that ZnS nanoparticles deposited on ITO substrate were a good candidate material for the immobilization of enzyme in glucose biosensor construction. - Highlights: ► ZnS nanoparticles were electrodeposited directly on ITO surface. ► The direct electron transfer of GOD immobilized on ZnS surface was obtained. ► The enzyme electrode was used to the determination of glucose in the presence of oxygen. ► The response of photoelectrochemical biosensor towards glucose was more sensitive

ZnS nanoparticles electrodeposited onto ITO electrode as a platform for fabrication of enzyme-based biosensors of glucose

Energy Technology Data Exchange (ETDEWEB)

Du, Jian; Yu, Xiuping; Wu, Ying; Di, Junwei, E-mail: djw@suda.edu.cn

2013-05-01

The electrochemical and photoelectrochemical biosensors based on glucose oxidase (GOD) and ZnS nanoparticles modified indium tin oxide (ITO) electrode were investigated. The ZnS nanoparticles were electrodeposited directly on the surface of ITO electrode. The enzyme was immobilized on ZnS/ITO electrode surface by sol–gel method to fabricate glucose biosensor. GOD could electrocatalyze the reduction of dissolved oxygen, which resulted in a great increase of the reduction peak current. The reduction peak current decreased linearly with the addition of glucose, which could be used for glucose detection. Moreover, ZnS nanoparticles deposited on ITO electrode surface showed good photocurrent response under illumination. A photoelectrochemical biosensor for the detection of glucose was also developed by monitoring the decreases in the cathodic peak photocurrent. The results indicated that ZnS nanoparticles deposited on ITO substrate were a good candidate material for the immobilization of enzyme in glucose biosensor construction. - Highlights: ► ZnS nanoparticles were electrodeposited directly on ITO surface. ► The direct electron transfer of GOD immobilized on ZnS surface was obtained. ► The enzyme electrode was used to the determination of glucose in the presence of oxygen. ► The response of photoelectrochemical biosensor towards glucose was more sensitive.

Electrokinetic and impedimetric dynamics of FeCo-nanoparticles on glassy carbon electrode

CSIR Research Space (South Africa)

Ikpo, CO

2013-01-01

Full Text Available voltammetric experiments revealed a diffusion-controlled electron transfer process on the GCE/FeCo electrode surface. Further interrogation on the electrochemical properties of the FeCo nanoelectrode in an oxygen saturated 1 M LiClO4 containing 1:1 v/v ethylene...

Long-term performance of Aanderaa optodes and sea-bird SBE-43 dissolved-oxygen sensors bottom mounted at 32 m in Massachusetts Bay

Science.gov (United States)

Martini, Marinna A.; Butman, Bradford; Mickelson, Michael J.

2007-01-01

A field evaluation of two new dissolved-oxygen sensing technologies, the Aanderaa Instruments AS optode model 3830 and the Sea-Bird Electronics, Inc., model SBE43, was carried out at about 32-m water depth in western Massachusetts Bay. The optode is an optical sensor that measures fluorescence quenching by oxygen molecules, while the SBE43 is a Clark polarographic membrane sensor. Optodes were continuously deployed on bottom tripod frames by exchanging sensors every 4 months over a 19-month period. A Sea-Bird SBE43 was added during one 4-month deployment. These moored observations compared well with oxygen measurements from profiles collected during monthly shipboard surveys conducted by the Massachusetts Water Resources Authority. The mean correlation coefficient between the moored measurements and shipboard survey data was >0.9, the mean difference was 0.06 mL L−1, and the standard deviation of the difference was 0.15 mL L−1. The correlation coefficient between the optode and the SBE43 was >0.9 and the mean difference was 0.07 mL L−1. Optode measurements degraded when fouling was severe enough to block oxygen molecules from entering the sensing foil over a significant portion of the sensing window. Drift observed in two optodes beginning at about 225 and 390 days of deployment is attributed to degradation of the sensing foil. Flushing is necessary to equilibrate the Sea-Bird sensor. Power consumption by the SBE43 and required pump was 19.2 mWh per sample, and the optode consumed 0.9 mWh per sample, both within expected values based on manufacturers’ specifications.

Label-free electrochemical detection of singlet oxygen protein damage

Czech Academy of Sciences Publication Activity Database

Vargová, Veronika; Gimenez, R.E.; Černocká, Hana; Trujillo, D.C.; Tulli, F.; Zanini, V.I.P.; Paleček, Emil; Borsarelli, C.D.; Ostatná, Veronika

2016-01-01

Roč. 187, JAN 2016 (2016), s. 662-669 ISSN 0013-4686 R&D Projects: GA ČR GA13-00956S Institutional support: RVO:68081707 Keywords : singlet oxygen protein damage * surface-attached protein stability * mercury and carbon electrodes Subject RIV: BO - Biophysics Impact factor: 4.798, year: 2016

Oxygen permeability of the pigmented material used in cosmetic daily disposable contact lenses

Directory of Open Access Journals (Sweden)

Galas S

2016-12-01

Full Text Available Stephen Galas, Lenora L Copper Johnson & Johnson Vision Care Inc., Jacksonville, FL, USA Purpose: To evaluate the individual contributions of pigment colorant and packing solution containing polyvinyl pyrrolidone (PVP on the oxygen permeability (Dk of a cosmetic printed etafilcon A daily disposable contact lens packaged with PVP. Method: The oxygen transport of a contact lens is evaluated through the central optical zone of the lens. Cosmetic printed contact lenses contain pigment colorant in the periphery or mid-periphery of the lens. Therefore, to assess the impact of cosmetic print on oxygen permeability, special lenses need to be produced that contain the colorant within the central optical zone. This technique was used to obtain multiple measurements of nonedge-corrected Dk/t of both the center pigmented lens and its nonpigmented equivalent, using a polarographic measurement described in International Organization for Standardization (ISO 18369-4:2006(E, and the Dk derived for each measurement is corrected for edge effect. In addition, the edge-corrected Dk values of lenses made from the same monomer batch were measured. The lenses were packaged and autoclaved with and without proprietary technology which embeds PVP in the contact lens during autoclaving. The resulting Dk value of the printed lens material was then used with thickness data to generate true Dk/t profiles for a given lens power. Results: The edge-corrected Dk of the printed etafilcon A lens with offset pigment colorant was measured to be 19.7×10-11 (cm2/s (mL O2/mL·mmHg at 35°C. This was within ±20% tolerance range as specified in ISO 18369-2:2012(E for the edge-corrected Dk of the nonpigmented etafilcon A control lens evaluated during the same session, 19.5×10-11 (cm2/s (mL O2/mL·mmHg. The edge-corrected Dk values of the lenses packaged with PVP (mean 20.1, standard deviation [SD] 0.3 were also within the ±20% tolerance range compared to those packaged without PVP

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

Reductive cleavage of chlorine from 6-chloronicotinic acid on mercury electrodes

International Nuclear Information System (INIS)

Ruiz Montoya, M.; Pintado, S.; Rodriguez Mellado, J.M.

2011-01-01

Highlights: → Dissociation constants (as pK) of 6 chloronicotinic acid (6CNA) obtained by UV-vis spectroscopy: -0.80 ± 0.05 (-COOH group) and 3.2 ± 0.1 (pyridinic nitrogen). → Electrolysis of 6CNA evidenced the reductive cleavage of chlorine from the molecule. → Kinetic parameters (Tafel slopes and reaction orders) determined at the foot of the waves. → Reduction pathways have been proposed. - Abstract: This paper presents polarographic (direct current, dc, and differential pulse, DP) and voltammetric (linear-sweep cyclic voltammetry) studies on the electroreduction of 6-chloronicotinic acid (6CNA) on mercury electrodes. In order to obtain the dissociation constants of 6CNA, UV-vis spectra were recorded as a function of pH. pK values of -0.80 ± 0.05 (-COOH group) and 3.2 ± 0.1 (pyridinic nitrogen) were obtained. The electrochemical studies were performed in the acidity range 6 M H 2 SO 4 to pH 8. Above the last pH value no signals were obtained. Electrolysis made at potentials corresponding to the limiting current of the first wave indicates that there is a reductive cleavage of chlorine from the molecule. This was confirmed by dc and DP polarografic results and also by voltammetric results. Kinetic parameters such as Tafel slopes and electrochemical reaction orders have been determined at potentials corresponding to the foot of the waves. From these results, together with those obtained by cyclic voltammetry, a reaction pathway is proposed, in which the rate-determining step of the process is the release of a chloride ion from the radical formed after the uptake of a H + ion and an electron.

Reductive cleavage of chlorine from 6-chloronicotinic acid on mercury electrodes

Energy Technology Data Exchange (ETDEWEB)

Ruiz Montoya, M., E-mail: mmontoya@uhu.e [Departamento de Ingenieria Quimica, Quimica Fisica y Quimica Organica, Universidad de Huelva, Campus El Carmen, Facultad de Ciencias Experimentales, E-21071 Huelva (Spain); Pintado, S., E-mail: q02pibes@uco.e [Departamento de Quimica Fisica y Termodinamica Aplicada, Universidad de Cordoba, Campus Universitario de Rabanales, edificio ' Marie Curie' ., E-14014 Cordoba (Spain); Rodriguez Mellado, J.M., E-mail: jmrodriguez@uco.e [Departamento de Quimica Fisica y Termodinamica Aplicada, Universidad de Cordoba, Campus Universitario de Rabanales, edificio ' Marie Curie' ., E-14014 Cordoba (Spain)

2011-04-30

Highlights: Dissociation constants (as pK) of 6 chloronicotinic acid (6CNA) obtained by UV-vis spectroscopy: -0.80 {+-} 0.05 (-COOH group) and 3.2 {+-} 0.1 (pyridinic nitrogen). Electrolysis of 6CNA evidenced the reductive cleavage of chlorine from the molecule. Kinetic parameters (Tafel slopes and reaction orders) determined at the foot of the waves. Reduction pathways have been proposed. - Abstract: This paper presents polarographic (direct current, dc, and differential pulse, DP) and voltammetric (linear-sweep cyclic voltammetry) studies on the electroreduction of 6-chloronicotinic acid (6CNA) on mercury electrodes. In order to obtain the dissociation constants of 6CNA, UV-vis spectra were recorded as a function of pH. pK values of -0.80 {+-} 0.05 (-COOH group) and 3.2 {+-} 0.1 (pyridinic nitrogen) were obtained. The electrochemical studies were performed in the acidity range 6 M H{sub 2}SO{sub 4} to pH 8. Above the last pH value no signals were obtained. Electrolysis made at potentials corresponding to the limiting current of the first wave indicates that there is a reductive cleavage of chlorine from the molecule. This was confirmed by dc and DP polarografic results and also by voltammetric results. Kinetic parameters such as Tafel slopes and electrochemical reaction orders have been determined at potentials corresponding to the foot of the waves. From these results, together with those obtained by cyclic voltammetry, a reaction pathway is proposed, in which the rate-determining step of the process is the release of a chloride ion from the radical formed after the uptake of a H{sup +} ion and an electron.

Oxygen ion transference number of doped lanthanum gallate

Energy Technology Data Exchange (ETDEWEB)

Wang, Shizhong; Wu, Lingli; Gao, Jie; He, Qiong [Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian 361005 (China); Liu, Meilin [School of Materials Science and Engineering, Georgia Institute of Technology, Atlanta, GA 30332-0245 (United States)

2008-12-01

The transference numbers for oxygen ion (t{sub O}) in several LaGaO{sub 3}-based materials are determined from oxygen concentration cells using the materials as the electrolyte, including La{sub 0.8}Sr{sub 0.2}Ga{sub 0.8}Mg{sub 0.2}O{sub 3-{delta}} (LSGM8282), La{sub 0.8}Sr{sub 0.2}Ga{sub 0.8}Mg{sub 0.15}Co{sub 0.05}O{sub 3-{delta}} (LSGMC5) and La{sub 0.8}Sr{sub 0.2}Ga{sub 0.8}Mg{sub 0.115}Co{sub 0.085}O{sub 3-{delta}} (LSGMC8.5). Analysis indicates that the accuracy in determination of oxygen ion transference number depends on the electrode polarization resistances of the concentration cell as well as the transport properties of the materials studied. For example, the ratio of open cell voltage to Nernst potential is a good approximation to the ionic transference number for LSGM8282. However, this approximation is no longer adequate for LSGMC5 and LSGMC8.5; the effect of electrode polarization resistances must be taken into consideration in estimation of the ionic transference numbers. In particular, the ionic transference number for LSGMC5 is as high as 0.99, suggesting that it is a promising electrolyte material for low-temperature solid-state electrochemical applications. (author)

Characterization of porous texture of cermet electrode for steam electrolysis at intermediate temperature

International Nuclear Information System (INIS)

Deslouis, C.; Keddam, M.; Rahmouni, K.; Takenouti, H.; Grasset, F.; Lacroix, O.; Sala, B.

2011-01-01

Electrodes designed for PCEC (Proton Conducting Electrolyzing Cell) should ensure both electron and proton conductions and also allowed the supply or the draining of gaseous phase such as steam, hydrogen and oxygen. Porous cermet electrodes fulfil these requirements: percolated metallic phase for electron conduction, ceramic for proton conduction, and pores for transport of reactant and products in gas phase. The electrochemical reactions will take place at boundaries of these three phases, commonly named triple points. Therefore, the cermet electrode has to possess a sufficient open porosity and the expanded metallic surface area exposed to pores as large as possible. In this work, the pore texture of cermet electrodes was characterized by means of Electrochemical Impedance Spectroscopy in aprotic liquid medium. The parameter regression calculation based on de Levie's transmission-line model allowed us to determine the pore texture characterized by expanded surface area, number, mean radius of pores, and open porosity.

Generation of Transparent Oxygen Evolution Electrode Consisting of Regularly Ordered Nanoparticles from Self-Assembly Cobalt Phthalocyanine as a Template

KAUST Repository

Ziani, Ahmed

2016-11-04

The decoration of (photo)electrodes for efficient photoresponse requires the use of electrocatalysts with good dispersion and high transparency for efficient light absorption by the photoelectrode. As a result of the ease of thermal evaporation and particulate self-assembly growth, the phthalocyanine molecular species can be uniformly deposited layer-by-layer on the surface of substrates. This structure can be used as a template to achieve a tunable amount of catalysts, high dispersion of the nanoparticles, and transparency of the catalysts. In this study, we present a systematic study of the structural and optical properties, surface morphologies, and electrochemical oxygen evolution reaction (OER) performance of cobalt oxide prepared from a phthalocyanine metal precursor. Cobalt phthalocyanine (CoPc) films with different thicknesses were deposited by thermal evaporation on different substrates. The films were annealed at 400 °C in air to form a material with the cobalt oxide phase. The final Co oxide catalysts exhibit high transparency after thermal treatment. Their OER measurements demonstrate well expected mass activity for OER. Thermally evaporated and treated transition metal oxide nanoparticles are attractive for the functionalization of (photo)anodes for water oxidation.

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.

Electrode kinetics of ytterbium (III) in acrylate and crotonate media

Energy Technology Data Exchange (ETDEWEB)

Rao, A L.J.; Singh, M

1982-07-01

The polarographic reduction of Yb(III) in acrylate and crotonate media gives well-defined, diffusion-controlled irreversible waves. The forward rate constant (sub(f,h)Ksup(0)) and transfer coefficient (..cap alpha..) have been calculated by Koutecky's theoretical treatment as extended by Meites and Israel. This has also been made the basis of a method for the determination of Yb(III) in the presence of diverse ions and rare earth ions. Under optimum conditions. Yb(III) in the range 4 x 10/sup -4/ M to 1.6 x 10/sup -3/ M could be successfully determined in various mixtures, using any of the two acids.

Amperometric micro pH measurements in oxygenated saliva.

Science.gov (United States)

Chaisiwamongkhol, Korbua; Batchelor-McAuley, Christopher; Compton, Richard G

2017-07-24

An amperometric micro pH sensor has been developed based on the chemical oxidation of carbon fibre surfaces (diameter of 9 μm and length of ca. 1 mm) to enhance the population of surface quinone groups for the measurement of salivary pH. The pH analysis utilises the electrochemically reversible two-electron, two-proton behaviour of surface quinone groups on the micro-wire electrodes. A Nernstian response is observed across the pH range 2-8 which is the pH range of many biological fluids. We highlight the measurement of pH in small volumes of biological fluids without the need for oxygen removal and specifically the micro pH electrode is examined by measuring the pH of commercial synthetic saliva and authentic human saliva samples. The results correspond well with those obtained by using commercial glass pH electrodes on large volume samples.

Electrochemiluminescence of fluorescein in alkaline solution at a polycrystalline gold electrode

International Nuclear Information System (INIS)

Shi Mingjuan; Cui Hua

2007-01-01

The electrochemiluminescence (ECL) behavior of fluorescein at a polycrystalline gold electrode was studied under conventional cyclic voltammetric conditions. Five ECL peaks were observed at 0.94 (ECL-1), 1.51 (ECL-2), 1.34 (ECL-3), -0.06 (ECL-4), -0.73 to -1.11 V (ECL-5, a broad weak wave) (vs. SCE), respectively, on the curve of ECL intensity versus potential. These ECL peaks were found to depend on the pH of the solution, supporting electrolyte, potential scan ranges and directions. The emitter of ECL peaks was identified as fluorescein or eosin Y produced on the electrode by analyzing the ECL spectra and fluorescence spectra. The mechanisms for ECL peaks have been proposed due to the reactions of fluorescein and the electro-oxidation product of fluorescein with various oxygen-containing species in the solution or electrogenerated at different applied potentials such as O 2 , O 2 .- , HO 2 - , and BrO - . Singlet molecular oxygen was generated during the reactions and transferred its energy to the ECL emitter such as fluorescein or eosin Y, emitting light

Influence of Electric Fields on Biofouling of Carbonaceous Electrodes.

Science.gov (United States)

Pandit, Soumya; Shanbhag, Sneha; Mauter, Meagan; Oren, Yoram; Herzberg, Moshe

2017-09-05

Biofouling commonly occurs on carbonaceous capacitive deionization electrodes in the process of treating natural waters. Although previous work reported the effect of electric fields on bacterial mortality for a variety of medical and engineered applications, the effect of electrode surface properties and the magnitude and polarity of applied electric fields on biofilm development has not been comprehensively investigated. This paper studies the formation of a Pseudomonas aeruginosa biofilm on a Papyex graphite (PA) and a carbon aerogel (CA) in the presence and the absence of an electric field. The experiments were conducted using a two-electrode flow cell with a voltage window of ±0.9 V. The CA was less susceptible to biofilm formation compared to the PA due to its lower surface roughness, lower hydrophobicity, and significant antimicrobial properties. For both positive and negative applied potentials, we observed an inverse relationship between biofilm formation and the magnitude of the applied potential. The effect is particularly strong for the CA electrodes and may be a result of cumulative effects between material toxicity and the stress experienced by cells at high applied potentials. Under the applied potentials for both electrodes, high production of endogenous reactive oxygen species (ROS) was indicative of bacterial stress. For both electrodes, the elevated specific ROS activity was lowest for the open circuit potential condition, elevated when cathodically and anodically polarized, and highest for the ±0.9 V cases. These high applied potentials are believed to affect the redox potential across the cell membrane and disrupt redox homeostasis, thereby inhibiting bacterial growth.

Multilayered architecture of graphene nanosheets and MnO2 nanowires as an electrode material for high-performance supercapacitors

International Nuclear Information System (INIS)

Wu, Mao-Sung; Lin, Chih-Jui; Ho, Chia-Ling

2012-01-01

Highlights: ► Multilayered architecture of the graphene/MnO 2 electrode is fabricated. ► The composite provides horizontal and vertical channels for electrolyte access. ► Graphene (GN) layer provides fast electron conduction in the composite. ► MnO 2 nanowire layer on the GN layer suppresses the oxygen evolution reaction. ► Capacitance behavior is enhanced by the multilayered architecture of GN/MnO 2 . - Abstract: Multilayered graphene/MnO 2 nanocomposite electrode prepared by anodic electrodeposition and electrophoresis exhibited superior capacitive behavior compared to the bare MnO 2 and graphene electrodes. The multilayered architecture provided both the horizontal and vertical channels for electrolyte access during fast charging and discharging. The graphene layer turned out to play an important role in enhancing the electron conduction in the multilayered architecture. Therefore, the improved electrochemical behavior might result from the significantly improved ion transport and electron conduction in the multilayered architecture of the graphene/MnO 2 composite electrode. Furthermore, the MnO 2 nanowire layer coated on the graphene layer could significantly suppress the oxygen evolution reaction, broadening the potential window of water stability.

Boron-doped diamond electrode: synthesis, characterization, functionalization and analytical applications.

Science.gov (United States)

Luong, John H T; Male, Keith B; Glennon, Jeremy D

2009-10-01

In recent years, conductive diamond electrodes for electrochemical applications have been a major focus of research and development. The impetus behind such endeavors could be attributed to their wide potential window, low background current, chemical inertness, and mechanical durability. Several analytes can be oxidized by conducting diamond compared to other carbon-based materials before the breakdown of water in aqueous electrolytes. This is important for detecting and/or identifying species in solution since oxygen and hydrogen evolution do not interfere with the analysis. Thus, conductive diamond electrodes take electrochemical detection into new areas and extend their usefulness to analytes which are not feasible with conventional electrode materials. Different types of diamond electrodes, polycrystalline, microcrystalline, nanocrystalline and ultrananocrystalline, have been synthesized and characterized. Of particular interest is the synthesis of boron-doped diamond (BDD) films by chemical vapor deposition on various substrates. In the tetrahedral diamond lattice, each carbon atom is covalently bonded to its neighbors forming an extremely robust crystalline structure. Some carbon atoms in the lattice are substituted with boron to provide electrical conductivity. Modification strategies of doped diamond electrodes with metallic nanoparticles and/or electropolymerized films are of importance to impart novel characteristics or to improve the performance of diamond electrodes. Biofunctionalization of diamond films is also feasible to foster several useful bioanalytical applications. A plethora of opportunities for nanoscale analytical devices based on conducting diamond is anticipated in the very near future.

Correspondence between Experiment and Theory of Bulk Electrocrystallisation at Solid Electrodes in Aqueous Electrolyte

DEFF Research Database (Denmark)

Andersen, Jens Enevold Thaulov

2009-01-01

A model of electrodeposition and electrodissolution at electrode surfaces in aqueous solution is presented. The description is based on the assumption that redox reaction of water is the more important process controlling the electrode kinetics. Chronoamperometric measurements and experiments...... of cyclic voltammetry indicate that the current fundamentally is proportional to inverse time. It was proposed that redox-active species different from water never touch the surface but they predominantly interact with surface-active hydrogen or oxygen formed at the surface by redox processes of water...

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...

Analytical chemistry

International Nuclear Information System (INIS)

Choi, Jae Seong

1993-02-01

This book is comprised of nineteen chapters, which describes introduction of analytical chemistry, experimental error and statistics, chemistry equilibrium and solubility, gravimetric analysis with mechanism of precipitation, range and calculation of the result, volume analysis on general principle, sedimentation method on types and titration curve, acid base balance, acid base titration curve, complex and firing reaction, introduction of chemical electro analysis, acid-base titration curve, electrode and potentiometry, electrolysis and conductometry, voltammetry and polarographic spectrophotometry, atomic spectrometry, solvent extraction, chromatograph and experiments.

Analytical chemistry

Energy Technology Data Exchange (ETDEWEB)

Choi, Jae Seong

1993-02-15

This book is comprised of nineteen chapters, which describes introduction of analytical chemistry, experimental error and statistics, chemistry equilibrium and solubility, gravimetric analysis with mechanism of precipitation, range and calculation of the result, volume analysis on general principle, sedimentation method on types and titration curve, acid base balance, acid base titration curve, complex and firing reaction, introduction of chemical electro analysis, acid-base titration curve, electrode and potentiometry, electrolysis and conductometry, voltammetry and polarographic spectrophotometry, atomic spectrometry, solvent extraction, chromatograph and experiments.

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,

Development of oxygen sensors using zirconia solid electrolyte for fuel rods

International Nuclear Information System (INIS)

Hiura, Nobuo; Endou, Yasuichi; Yamaura, Takayuki; Matui, Yoshinori; Niimi, Motoji; Hoshiya, Taiji; Kobiyama, Mamoru; Motohashi, Yoshinobu

1999-01-01

The oxygen potential in oxide fuel pellet is an important parameter to understand behavior of high burn up fuel and its integrity. Zirconia solid electrolyte which is durable under irradiation and high temperature is considered as candidate material for the oxygen potential. Combined use of solid electrolyte and Ni/NiO as a solid standard electrode will realize small size oxygen sensor which can be easily loaded in the fuel rod. Prototypes of the oxygen sensor made of these materials were irradiated with neutrons the Japan Materials Testing Reactor (JMTR), and characteristics of electromotive force (EMF) by sensors were examined under irradiation. For a prototype using zirconia solid electrolyte stabilized by Y 2 O 3 (YSZ), measured EMF under irradiation was nearly equivalent to the value under unirradiated condition, and very stable within a range of neutron fluence (E>1 MeV) up to 1.52 x 10 23 m -2 and for the time of 600 h. However, the measured EMFs were slightly smaller than the theoretical values. The reason for this decrease of the EMF was thought as due to insufficient adhesion forces between solid electrolyte and standard electrode. After modification of the sensor to increase adhesion force, EMF was measured again under irradiation. The results showed improvement of the characteristics of the sensor in which measured EMFs were almost equivalent to the theoretical values. (author)

Differential pulse polarographic determination of trace antimony in standard biological samples after preconcentration using 2-nitroso-1-naphthol-4-sulfonic acid

International Nuclear Information System (INIS)

Taher, M. A.

2003-01-01

A highly selective, rapid and economical differential polarographic method has been developed for the determination of trace amounts of antimony in various standard alloys and biological samples after of its 2-naphthol-4 sulfonic acid tetradecyl dimethylbenzylammonium chloride on microcrystalline naphthalene in the ph range of 7.5-11.0. After filtration, the solid mass is shaken with 8-10 ml of 1 M hydrochloric acid (with preconcentration factor of 10) and antimony is determined by differential pulse polarography. Antimony can alternatively be quantitatively absorbed on 2-nitroso-1-naphthol-4-sulfonic acid tetradecyl dimethylbenzylammonium-naphthalene absorbed packed in a column (with preconcentration factor of 30) and determined similarly. In this case, 1.5 μg of antimony can be concentrated in a column from 300 ml of aqueous sample, where its concentration is as low as 5 ng/ml. Characterization of the electro active process included an examination of the degree of reversibility. The results show that the irreversibility of antimony. Various parameters such as the effect of ph, volume of aqueous phase, HCl concentration, reagent concentration, naphthalene concentration, shaking time and interference of a number of metal ions on the determination of antimony have been studied in detail to optimize the conditions for determination in standard alloys and standard biological samples

Oxygen delivery to the fish eye: root effect as crucial factor for elevated retinal PO2.

Science.gov (United States)

Waser, W; Heisler, N

2005-11-01

Although the retina has one of the highest metabolic rates among tissues, certain teleost fishes lack any vascular supply to this organ which, in combination with the overall thickness of the organ, results in extremely long diffusion distances. As the only way to compensate for these obstacles, oxygen partial pressure (PO2) in the eyes of such fish is elevated far above atmospheric values. Although not supported by any direct evidence, the enhancement of PO2 is considered to be related to the Root effect, the release upon acidification of Hb-bound O2 into physical dissolution, possibly supported by counter-current multiplication similar to the loop of Henle. The present study evaluates the magnitude of intraocular PO2 enhancement under tightly controlled physiological conditions, to directly confirm the involvement of the Root effect on intraocular PO2 in the retina of rainbow trout Oncorhynchus mykiss. Intraocular PO2 was determined with special polarographic microelectrodes inserted into the eye. PO2 profiles established in vivo by driving electrodes through the entire retina yielded average PO2 values between 10 mmHg (1.3 kPa) at the inner retinal surface and 382 mmHg (50.9 kPa) close to the outer retinal limit (Bruch's membrane). According to estimates on the basis of the diffusion distances determined from sections of the retina (approximately 436 microm at the site of PO2 measurement) and literature data on specific oxygen consumption, the in vivo determined values would be sufficient to cover the oxygen demand of the retina with some safety margin. For a clear and direct in-tissue-test as to the involvement of the Root effect, an isolated in vitro eye preparation was established in order to avoid the problem of indirect blood supply to the eye from the dorsal aorta only via the pseudobranch, a hemibranch thought to modulate blood composition before entry of the eye. Any humoral effects (e.g. catecholamines) were eliminated by perfusing isolated eyes

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.

Polarographic validation of chemical speciation models

International Nuclear Information System (INIS)

Duffield, J.R.; Jarratt, J.A.

2001-01-01

It is well established that the chemical speciation of an element in a given matrix, or system of matrices, is of fundamental importance in controlling the transport behaviour of the element. Therefore, to accurately understand and predict the transport of elements and compounds in the environment it is a requirement that both the identities and concentrations of trace element physico-chemical forms can be ascertained. These twin requirements present the analytical scientist with considerable challenges given the labile equilibria, the range of time scales (from nanoseconds to years) and the range of concentrations (ultra-trace to macro) that may be involved. As a result of this analytical variability, chemical equilibrium modelling has become recognised as an important predictive tool in chemical speciation analysis. However, this technique requires firm underpinning by the use of complementary experimental techniques for the validation of the predictions made. The work reported here has been undertaken with the primary aim of investigating possible methodologies that can be used for the validation of chemical speciation models. However, in approaching this aim, direct chemical speciation analyses have been made in their own right. Results will be reported and analysed for the iron(II)/iron(III)-citrate proton system (pH 2 to 10; total [Fe] = 3 mmol dm -3 ; total [citrate 3- ] 10 mmol dm -3 ) in which equilibrium constants have been determined using glass electrode potentiometry, speciation is predicted using the PHREEQE computer code, and validation of predictions is achieved by determination of iron complexation and redox state with associated concentrations. (authors)

Visible light induced photoelectrochemical biosensing based on oxygen-sensitive quantum dots

Energy Technology Data Exchange (ETDEWEB)

Wang Wenjing; Bao Lei [State Key Laboratory of Analytical Chemistry for Life Science, Department of Chemistry, Nanjing University, Nanjing 210093 (China); Lei Jianping, E-mail: jpl@nju.edu.cn [State Key Laboratory of Analytical Chemistry for Life Science, Department of Chemistry, Nanjing University, Nanjing 210093 (China); Tu Wenwen [State Key Laboratory of Analytical Chemistry for Life Science, Department of Chemistry, Nanjing University, Nanjing 210093 (China); Ju Huangxian, E-mail: hxju@nju.edu.cn [State Key Laboratory of Analytical Chemistry for Life Science, Department of Chemistry, Nanjing University, Nanjing 210093 (China)

2012-09-26

Highlights: Black-Right-Pointing-Pointer The near-infrared QDs are synthesized in an aqueous solution. Black-Right-Pointing-Pointer QDs-based biosensor exhibits visible-light induced cathodic photocurrent. Black-Right-Pointing-Pointer The oxygen dependency of the photocurrent is verified. Black-Right-Pointing-Pointer A photoelectrochemical strategy is established by coupling with enzymatic reaction. Black-Right-Pointing-Pointer Photoelectrochemical sensor shows high upper detection limit, acceptable stability and accuracy. - Abstract: A visible light induced photoelectrochemical biosensing platform based on oxygen-sensitive near-infrared quantum dots (NIR QDs) was developed for detection of glucose. The NIR QDs were synthesized in an aqueous solution, and characterized with scanning electron microscopy and X-ray photoelectron spectroscopy. The as-prepared NIR QDs were employed to construct oxygen-sensitive photoelectrochemical biosensor on a fluorine-doped tin oxide (FTO) electrode. The oxygen dependency of the photocurrent was investigated at as-prepared electrode, which demonstrated the signal of photocurrent is suppressed with the decreasing of oxygen. Coupling with the consumption of oxygen during enzymatic reaction, a photoelectrochemical strategy was proposed for the detection of substrate. Using glucose oxidase (GOx) as a model enzyme, that is, GOx was covalently attached to the surface of CdTe QDs, the resulting biosensor showed the sensitive response to glucose. Under the irradiation of visible light of a wavelength at 505 nm, the proposed photoelectrochemical method could detect glucose ranging from 0.1 mM to 11 mM with a detection limit of 0.04 mM. The photoelectrochemical biosensor showed a good performance with high upper detection limit, acceptable stability and accuracy, providing an alternative method for monitoring biomolecules and extending the application of near-infrared QDs.

Oxygen permeability of the pigmented material used in cosmetic daily disposable contact lenses.

Science.gov (United States)

Galas, Stephen; Copper, Lenora L

2016-01-01

To evaluate the individual contributions of pigment colorant and packing solution containing polyvinyl pyrrolidone (PVP) on the oxygen permeability (Dk) of a cosmetic printed etafilcon A daily disposable contact lens packaged with PVP. The oxygen transport of a contact lens is evaluated through the central optical zone of the lens. Cosmetic printed contact lenses contain pigment colorant in the periphery or mid-periphery of the lens. Therefore, to assess the impact of cosmetic print on oxygen permeability, special lenses need to be produced that contain the colorant within the central optical zone. This technique was used to obtain multiple measurements of nonedge-corrected Dk/t of both the center pigmented lens and its nonpigmented equivalent, using a polarographic measurement described in International Organization for Standardization (ISO) 18369-4:2006(E), and the Dk derived for each measurement is corrected for edge effect. In addition, the edge-corrected Dk values of lenses made from the same monomer batch were measured. The lenses were packaged and autoclaved with and without proprietary technology which embeds PVP in the contact lens during autoclaving. The resulting Dk value of the printed lens material was then used with thickness data to generate true Dk/t profiles for a given lens power. The edge-corrected Dk of the printed etafilcon A lens with offset pigment colorant was measured to be 19.7×10 -11 (cm 2 /s) (mL O 2 /mL·mmHg) at 35°C. This was within ±20% tolerance range as specified in ISO 18369-2:2012(E) for the edge-corrected Dk of the nonpigmented etafilcon A control lens evaluated during the same session, 19.5×10 -11 (cm 2 /s) (mL O 2 /mL·mmHg). The edge-corrected Dk values of the lenses packaged with PVP (mean 20.1, standard deviation [SD] 0.3) were also within the ±20% tolerance range compared to those packaged without PVP (mean 20.0, SD 0.3). The pigment colorant and PVP embedded in the contact lens during autoclaving were not found to

Electrochemical Detectors in HPLC and Ion Chromatography.

Science.gov (United States)

Horvai, George; Pungor, ErnÕ

1989-01-01

Back in 1952, the renowned Polish electrochemist Wiktor Kemula introduced chromato-polarography, 1 i.e., polaro-graphic detection for liquid chromatography. This technique continued to develop slowly until the early 1970s (for a review see Reference 2) when modem high-performance liquid chromatography (HPLC) emerged. This new, highly efficient chromatographc method could only be. used with detectors ensuring low dispersion. It was not easy to modify the dropping mercury electrode cells to satisfy this requirement. However, at the same time, electroanalytical chemists, who already had much experience in using carbon-based electrodes for oxidative detection in flow analysis, put forward the idea of oxidative amperometric detection in liquid chromatography. 3,4 In this technique, solid or quasi-solid (paste) electrodes were used and this made possible the construction of miniaturized cells with just a few microliter volume.

Carbon Deposition during CO2 Electrolysis in Ni-Based Solid-Oxide-Cell Electrodes

DEFF Research Database (Denmark)

Skafte, Theis Løye; Graves, Christopher R.; Blennow, P.

2015-01-01

. Electrochemical impedance spectroscopy in both H2/H2O and CO/CO2 revealed an increase in resistance of the fuel electrode after each CO2 electrolysis current-voltage curve, indicating possible carbon deposition. The difference in partial oxygen pressure between inlet and outlet was analyzed to verify carbon...... in detail. In an attempt to mitigate the degradation due to carbon deposition, the Ni-YSZ electrode was infiltrated with a gadolinium doped ceria (CGO) solution. Initial results indicate that the coking tolerance was not enhanced, but it is still unclear whether infiltrated cells degrade less. However......, infiltrated cells display a significant performance enhancement before coking, especially under electrolysis current. The investigation thus indicated carbon formation in the Ni containing fuel electrode before the thermodynamically calculated threshold for average measurements of the cell was reached...

Work function of oxygen exposed lead and lead/indium alloy films

International Nuclear Information System (INIS)

Gundlach, K.H.; Hellemann, H.P.; Hoelzl, J.

1982-01-01

The effect of indium in superconducting tunnel junctions with lead/indium alloy base electrodes is investigated by measuring the vacuum work function of lead, indium, and lead/indium alloy films. It is found that the anomalous decrease of the work function of lead upon exposure to oxygen, explained by the penetration of oxygen into the inner surface of the lead film, is reversed into a slight increase in work function when some indium is added to the lead. This result indicates that the addition of indium provides a protection by suppressing the penetration of oxygen (and probably other gases) into the interior of the thin film

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.

Progress report on the analytical determination of Ag2+

International Nuclear Information System (INIS)

Van Alsenoy, V.

1997-01-01

The strong oxidising properties of Ag 2+ have been used in the chemical and nuclear industry to destroy organic waste. We aim to apply the process on radioactive graphite, organic resins and effluents. The reaction mechanisms have been studied, taking into account the thermodynamic and kinetic properties of the different reactions involved. For the experimental analysis of these reactions, the accurate analytical determination of all species involved, including Ag 2+ , is needed. The results of a systematic study of the volumetric quantification of Ag 2+ using Tl + and BrO 3 - , and of the spectrophotometric and polarographic quantification of Ag + and Ag 2+ are described. The influence of the nitric acid during the quantification of Tl + by titration with KBrO 3 is investigated and the optimal analytical conditions for our purposes were determined. The best analytical results were obtained when the titration was carried out with maximum 3 M HNO 3 and 0.5 M NaCl. When those conditions are used, the determination is accurate and reproducible. The prepared Ag 2+ solutions were analysed for Ag + using polarography with a platinum electrode. The benefits and the limitation of the polarographic measurement of Ag + using a platinum electrode are described. An indirect measurement was performed by the determination of Ce 4+ after reaction with Ce 3+ . The produced Ce 4+ was measured by direct spectrophotometry. In the future, the quantification of Ag 2+ by measuring the Ce 4+ concentration produced by the reaction with Ce 3+ , will also be verified using potentiometric titration with Fe 2+ . Ag 2+ can also be determined by the direct spectrophotometry. There is a region in which the absorbance of Ag 2+ changes linearly with the concentration. Further evaluation of the titrimetric, spectrophotometric and polarographic methods will continue, until two methods give comparable Ag 2+ concentrations, beginning with the potentiometric titration of Ce 4+ with Fe 2+

The limitations of tissue-oxygen measurement and positron emission tomography as additional methods for postoperative breast reconstruction free-flap monitoring.

Science.gov (United States)

Schrey, Aleksi; Niemi, Tarja; Kinnunen, Ilpo; Minn, Heikki; Vahlberg, Tero; Kalliokoski, Kari; Suominen, Erkki; Grénman, Reidar; Aitasalo, Kalle

2010-02-01

Twelve patients who underwent breast reconstruction with a microvascular flap were monitored postoperatively with continuous partial tissue oxygenation (p(ti)O(2)) measurement. The regional blood flow (BF) of the entire flap was evaluated with positron emission tomography (PET) using oxygen-15-labelled water on the first postoperative (POP) morning to achieve data of the perfusion of the entire flap. A re-exploration was carried out if the p(ti)O(2) value remained lower than 15 mmHg for over 30 min. The mean p(ti)O(2) value of the flaps was 52.9+/-5.5 mmHg, whereas the mean BF values were 3.3+/-1.0 ml per 100 g min(-1). One false-positive result was detected by p(ti)O(2) measurement, resulting in an unnecessary re-exploration. Another re-operation suggested by the low p(ti)O(2) results was avoided due to the normal BF results assessed with PET. Totally, three flaps were re-explored. This prospective study suggests that continuous tissue-oxygen measurement with a polarographic needle probe is reliable for monitoring free breast flaps from one part of the flap, but assessing perfusion of the entire flap requires more complex monitoring methods, for example, PET. Clinical examination by experienced personnel remains important in free-breast-flap monitoring. PET could be useful in assessing free-flap perfusion in selected high-risk patients as an alternative to a re-operation when clinical examination and evaluation by other means are unreliable or present controversial results. 2008 British Association of Plastic, Reconstructive and Aesthetic Surgeons. Published by Elsevier Ltd. All rights reserved.

Production and characterization of TI/PbO2 electrodes by a thermal-electrochemical method

Directory of Open Access Journals (Sweden)

Laurindo Edison A.

2000-01-01

Full Text Available Looking for electrodes with a high overpotential for the oxygen evolution reaction (OER, useful for the oxidation of organic pollutants, Ti/PbO2 electrodes were prepared by a thermal-electrochemical method and their performance was compared with that of electrodeposited electrodes. The open-circuit potential for these electrodes in 0.5 mol L-1 H2SO4 presented quite stable similar values. X-ray diffraction analyses showed the thermal-electrochemical oxide to be a mixture of ort-PbO, tetr-PbO and ort-PbO2. On the other hand, the electrodes obtained by electrodeposition were in the tetr-PbO2 form. Analyses by scanning electron microscopy showed that the basic morphology of the thermal-electrochemical PbO2 is determined in the thermal step, being quite distinct from that of the electrodeposited electrodes. Polarization curves in 0.5 mol L-1 H2SO4 showed that in the case of the thermal-electrochemical PbO2 electrodes the OER was shifted to more positive potentials. However, the values of the Tafel slopes, quite high, indicate that passivating films were possibly formed on the Ti substrates, which could eventually explain the somewhat low current values for OER.

Controlled atmosphere for fabrication of cermet electrodes

Science.gov (United States)

Ray, Siba P.; Woods, Robert W.

1998-01-01

A process for making an inert electrode composite wherein a metal oxide and a metal are reacted in a gaseous atmosphere at an elevated temperature of at least about 750.degree. C. The metal oxide is at least one of the nickel, iron, tin, zinc and zirconium oxides and the metal is copper, silver, a mixture of copper and silver or a copper-silver alloy. The gaseous atmosphere has an oxygen content that is controlled at about 5-3000 ppm in order to obtain a desired composition in the resulting composite.

Modelling porous active layer electrodes of proton exchange membrane fuel cells; Modelisation des couches actives d'electrodes volumiques de piles a combustible a membrane echangeuse de protons

Energy Technology Data Exchange (ETDEWEB)

Bultel, Yann

1997-07-01

This work focusses on the modeling of mass, charge and heat transfer in the active layers of the volume electrodes of proton exchange membrane fuel cells (PEMFC). A first part describes the structure of fuel cells and the physico-chemical processes taking place at the electrodes. An analysis of the classical models encountered in the literature shows that they all assume that the electro-catalysts is uniformly distributed in a plane or in volume. In a second part, the modeling of mass and charge transport phenomena has been carried out with a numerical calculation software which uses the finite-elements method and which allows to take into consideration the discrete distribution of the catalyst in nano-particulates. The simulations show the limitations of the catalyst use because of the diffusion and ionic ohmic drop both at the electrolyte and particulates scale. In order to improve the modeling of PEMFC fuel cells, the classical models have been modified to consider these local contributions. They require only simple numerical methods, like the finite-differences one. When applied to the oxygen reduction at the cathode or to the hydrogen oxidation at the anode, these models allow to determine the kinetics parameters (exchange current densities and slopes of the Tafel lines) after correction of the active layer diffusion. A modeling of the heat transfers at the active layers scale is proposed. The model takes into account the convective heat transfers between the solid phases and the gas, the electro-osmosis water transfer, and the generation of heat by joule effect and by the electrochemical reactions. Finally, the last chapter presents a study of the reaction mechanisms in the case of porous electrodes using the impedances method. Numerical and analytical models have been developed to calculate the electrode impedances and are applied to the study of oxygen reduction and hydrogen oxidation. (J.S.)

Atomic oxygen dynamics in an air dielectric barrier discharge: a combined diagnostic and modeling approach

Science.gov (United States)

Baldus, Sabrina; Schröder, Daniel; Bibinov, Nikita; Schulz-von der Gathen, Volker; Awakowicz, Peter

2015-06-01

Cold atmospheric pressure plasmas are a promising alternative therapy for treatment of chronic wounds, as they have already shown in clinical trials. In this study an air dielectric barrier discharge (DBD) developed for therapeutic use in dermatology is characterized with respect to the plasma produced reactive oxygen species, namely atomic oxygen and ozone, which are known to be of great importance to wound healing. To understand the plasma chemistry of the applied DBD, xenon-calibrated two-photon laser-induced fluorescence spectroscopy and optical absorption spectroscopy are applied. The measured spatial distributions are shown and compared to each other. A model of the afterglow chemistry based on optical emission spectroscopy is developed to cross-check the measurement results and obtain insight into the dynamics of the considered reactive oxygen species. The atomic oxygen density is found to be located mostly between the electrodes with a maximum density of {{n}\\text{O}}=6× {{10}16} cm-3 . Time resolved measurements reveal a constant atomic oxygen density between two high voltage pulses. The ozone is measured up to 3 mm outside the active plasma volume, reaching a maximum value of {{n}{{\\text{O}3}}}=3× {{10}16} cm-3 between the electrodes.

Development of high temperature reference electrodes for potentiometric analyses in supercritical water environments

International Nuclear Information System (INIS)

Tung Yuming; Yeh Tsungkuang; Wang Meiya

2014-01-01

A specifically designed reference electrode was developed for analyzing the electrochemical behaviors of alloy materials in supercritical water (SCW) environments and identifying the associated electrochemical parameters. In this study, Ag/AgCl reference electrodes and Zr/ZrO 2 reference electrodes suitable for high-temperature applications were manufactured and adopted to measure the electrochemical corrosion potentials (ECPs) of 304L stainless steel (SS) and nickel-based alloy 625 in SCW environments with various amounts of dissolved oxygen (DO). The Ag/AgCl reference electrode made in this laboratory was used as a calibration base for the laboratory-made Zr/ZrO 2 reference electrode at high temperatures up to 400degC. The two reference electrodes were then used for ECP measurements of 304L SS and alloy 625 specimens in 400degC SCW with various DO levels of 300 ppb, 1 ppm, 8.3 ppm, and 32 ppm and under deaerated conditions. The outcome indicated that concentration increases in DO in the designated SCW environment would yield increases in ECP of the two alloys and they exhibited different ECP responses to DO levels. In addition, the laboratory-made Zr/ZrO 2 reference electrode was able to continuously operate for several months and delivered consistent and steady ECP data of the specimens in SCW environments. (author)

Determination of nonmetallic elements in actinide complexes by oxygen flask combustion (OFC) (Part 2). Sulphur

International Nuclear Information System (INIS)

Ruikar, P.B.; Nagar, M.S.; Subramanian, M.S.

1989-01-01

This report describes the determination of sulphur in metallic complexes by oxygen flask combustion followed by conductivity titration with standard barium acetate solution in alcoholic medium and lead electrode titration using a lead ion sensitive electrode. Various organic ligands and uranyl and plutonyl synergistic complexes have been analysed by both these methods and the precision and accuracy of the results have been found to be satisfactory. (author). 12 refs., 12 tabs

Flexible electrode belt for EIT using nanofiber web dry electrodes.

Science.gov (United States)

Oh, Tong In; Kim, Tae Eui; Yoon, Sun; Kim, Kap Jin; Woo, Eung Je; Sadleir, Rosalind J

2012-10-01

Efficient connection of multiple electrodes to the body for impedance measurement and voltage monitoring applications is of critical importance to measurement quality and practicality. Electrical impedance tomography (EIT) experiments have generally required a cumbersome procedure to attach the multiple electrodes needed in EIT. Once placed, these electrodes must then maintain good contact with the skin during measurements that may last several hours. There is usually also the need to manage the wires that run between the electrodes and the EIT system. These problems become more severe as the number of electrodes increases, and may limit the practicality and portability of this imaging method. There have been several trials describing human-electrode interfaces using configurations such as electrode belts, helmets or rings. In this paper, we describe an electrode belt we developed for long-term EIT monitoring of human lung ventilation. The belt included 16 embossed electrodes that were designed to make good contact with the skin. The electrodes were fabricated using an Ag-plated PVDF nanofiber web and metallic threads. A large contact area and padding were used behind each electrode to improve subject comfort and reduce contact impedances. The electrodes were incorporated, equally spaced, into an elasticated fabric belt. We tested the electrode belt in conjunction with the KHU Mark1 multi-frequency EIT system, and demonstrate time-difference images of phantoms and human subjects during normal breathing and running. We found that the Ag-plated PVDF nanofiber web electrodes were suitable for long-term measurement because of their flexibility and durability. Moreover, the contact impedance and stability of the Ag-plated PVDF nanofiber web electrodes were found to be comparable to similarly tested Ag/AgCl electrodes.

Oxidation of carbon monoxide, hydrogen peroxide and water at a boron doped diamond electrode: the competition for hydroxyl radicals.

Science.gov (United States)

Kisacik, Izzet; Stefanova, Ana; Ernst, Siegfried; Baltruschat, Helmut

2013-04-07

Boron doped diamond (BDD) electrodes have an extremely high over-voltage for oxygen evolution from water, which favours its use in oxidation processes of other compounds at high potentials. We used a rotating ring disc (RRDE) assembly and differential electrochemical mass spectrometry (DEMS) in order to monitor the consumption or the production of species in the course of the electrode processes. By intercepting the intermediate of the electrochemical water oxidation with chemical reactions we demonstrate clearly, albeit indirectly, that in the water oxidation process at BDD above 2.5 V the first step is the formation of ˙OH radicals. The electro-oxidation of CO to CO2 at BDD electrodes proceeds only via a first attack by ˙OH radicals followed by a further electron transfer to the electrode. At potentials below the onset of oxygen evolution from water, H2O2 is oxidised by a direct electron transfer to the BDD electrode, while at higher potentials, two different reactions paths compete for the ˙OH radicals formed in the first electron transfer from water: one, where these ˙OH radicals react with each other followed by further electron transfers leading to O2 on the one hand and one, where ˙OH radicals react with other species like H2O2 or CO with subsequent electron transfers on the other hand.

Intermediate honeycomb ordering to trigger oxygen redox chemistry in layered battery electrode.

Science.gov (United States)

Mortemard de Boisse, Benoit; Liu, Guandong; Ma, Jiangtao; Nishimura, Shin-ichi; Chung, Sai-Cheong; Kiuchi, Hisao; Harada, Yoshihisa; Kikkawa, Jun; Kobayashi, Yoshio; Okubo, Masashi; Yamada, Atsuo

2016-04-18

Sodium-ion batteries are attractive energy storage media owing to the abundance of sodium, but the low capacities of available cathode materials make them impractical. Sodium-excess metal oxides Na2MO3 (M: transition metal) are appealing cathode materials that may realize large capacities through additional oxygen redox reaction. However, the general strategies for enhancing the capacity of Na2MO3 are poorly established. Here using two polymorphs of Na2RuO3, we demonstrate the critical role of honeycomb-type cation ordering in Na2MO3. Ordered Na2RuO3 with honeycomb-ordered [Na(1/3)Ru(2/3)]O2 slabs delivers a capacity of 180 mAh g(-1) (1.3-electron reaction), whereas disordered Na2RuO3 only delivers 135 mAh g(-1) (1.0-electron reaction). We clarify that the large extra capacity of ordered Na2RuO3 is enabled by a spontaneously ordered intermediate Na1RuO3 phase with ilmenite O1 structure, which induces frontier orbital reorganization to trigger the oxygen redox reaction, unveiling a general requisite for the stable oxygen redox reaction in high-capacity Na2MO3 cathodes.

Computer Simulations of Composite Electrodes in Solid-Oxide Fuel-Cells

Energy Technology Data Exchange (ETDEWEB)

Sunde, Svein

1999-07-01

Fuel cells are devices for converting the combined chemical (free) energy of fuels and oxygen (air) directly to electrical energy without relying on the dynamic action of steam heated by reacting fuel-oxygen mixtures, like in steam turbines, or of the reacting gas mixtures themselves, like in gas turbines. The basic rationale for fuel cells is their high efficiencies as compared to indirect-conversion methods. Fuel cells are currently being considered for a number of applications, among them de-centralised power supply. Fuel cells come in five basic types and are usually classified according to the type of electrolyte used, which in turn to a significant degree limits the options for anode and cathode materials. The solid-oxide fuel-cell (SOFC) , with which this thesis is concerned, is thus named after its oxide electrolyte, typically the oxide-ion conducting material yttria-stabilised zirconia (YSZ). While the cathode of an SOFC is often uniform in chemical composition (or at least intended to be), various problems of delamination, cracking etc. associated with the use of metallic anode electrocatalysts led to the development of composite SOFC anodes. Porous anodes consisting of Ni and YSZ particles in roughly 50/50 wt-% mixtures are now almost standard with any SOFC-development programme. The designer of composite SOFC electrodes is faced with at least three, interrelated questions: (1) What will be the optimum microstructure and composition of the composite electrode? (2) If the structure changes during operation, as is often observed, what will be the consequences for the internal losses in the cell? (3) How do we interpret electrochemical and conductivity measurements with regard to structure and composition? It is the primary purpose of this thesis to provide a framework for modelling the electrochemical and transport properties of composite electrodes for SOFC, and to arrive at some new insights that cannot be offered by experiment alone. Emphasis is put on

Evaluation of LSF based SOFC Cathodes using Cone-shaped Electrodes

DEFF Research Database (Denmark)

Kammer Hansen, Kent; Mogensen, Mogens Bjerg

2008-01-01

Seven La1-xSrxFeO3-delta (x = 0, 0.05, 0.15, 0.25, 0.35, 0.50, 0.70) based perovskites were synthesized using the glycine-nitrate method. The La1-xSrxFeO3-delta compounds were characterized with powder X-ray diffraction and electrochemical impedance spectroscopy on cone-shaped electrodes using a Ce......(III) is the catalytic active specie towards the electrochemical reduction of oxygen in a solid oxide fuel cell on La1-xSrxFeO3-delta compounds. The results also show that oxide ion vacancies in the perovskite structure are important for the electrochemical reduction of oxygen. However, the effect of ordering of oxide...

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.

Adsorption of asparagine on the gold electrode and air/solution interface

International Nuclear Information System (INIS)

Slojkowska, R.; Palys, B.; Jurkiewicz-Herbich, M.

2004-01-01

The adsorption of asparagine (Asn) on a gold electrode from 0.1 M LiClO 4 aqueous solutions was investigated. The experimental data obtained from ac impedance measurements were analyzed to determine the dependence of adsorption parameters, i.e. the standard Gibbs energy of adsorption (ΔG 0 ), maximal value of surface excess concentration (Γ max ) of Asn and parameter of interactions in the adsorbed layer (A) on the electrode potential. The relatively large value of Gibbs energy of adsorption (∼ -47 kJ mol -1 ) gives the evidence of a very strong adsorption of Asn at the polycrystalline Au electrode. The comparison of the adsorption behavior of Asn at the air/solution and the Au/solution interfaces points out to the significant electronic interactions of adsorbate molecules with the Au electrode, since the adsorption of Asn on a free surface (from the same solutions) is very week. The analysis of the electrochemical data as well as the infrared reflection absorption spectroscopy (IRAS) results reveal that Asn molecules are anchored to the Au surface through oxygen atoms of the carboxylate group COO - and through the amide carbonyl group

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%.

Anodic oxidation

CERN Document Server

Ross, Sidney D; Rudd, Eric J; Blomquist, Alfred T; Wasserman, Harry H

2013-01-01

Anodic Oxidation covers the application of the concept, principles, and methods of electrochemistry to organic reactions. This book is composed of two parts encompassing 12 chapters that consider the mechanism of anodic oxidation. Part I surveys the theory and methods of electrochemistry as applied to organic reactions. These parts also present the mathematical equations to describe the kinetics of electrode reactions using both polarographic and steady-state conditions. Part II examines the anodic oxidation of organic substrates by the functional group initially attacked. This part particular

High performance electrodes for low pressure H{sub 2}-air PEM fuel cell

Energy Technology Data Exchange (ETDEWEB)

Besse, S; Bronoel, G; Fauvarque, J F [Laboratoires SORAPEC (France)

1998-12-31

Proton exchange membrane fuel cells (PEMFCs) were first developed for space applications in the 1960s. Currently, they are being manufactured for terrestrial portable power applications. One of the challenges is to develop a low pressure H{sub 2}/Air PEMFC in order to minimize the cathodic mass transport overpotentials. The hydrogen oxidation reaction is considered to be sufficiently rapid. Hydrogen transport limitations are very low even at high current densities. The different applications considered for hydrogen/air PEMFC need to work at atmospheric pressure. An optimization of the structure of the oxygen electrode and the membrane electrode assembly (MEA) are essential in order to decrease mass transport limitations and to obtain good water management even at low pressures. Efforts have been made to produce electrodes and MEA for PEMFC with low platinum loading. The electrode structure was developed to ensure a good diffusion of reactants and an effective charge collection. It has also been optimized for low pressure restrictions. It was concluded that high performances can be achieved even at low pressures by improving the electrode gas diffusion layer (PTFE content) and by improving the catalyst. 12 refs., 7 figs.

Quantitative measurements of ground state atomic oxygen in atmospheric pressure surface micro-discharge array

Science.gov (United States)

Li, D.; Kong, M. G.; Britun, N.; Snyders, R.; Leys, C.; Nikiforov, A.

2017-06-01

The generation of atomic oxygen in an array of surface micro-discharge, working in atmospheric pressure He/O2 or Ar/O2 mixtures, is investigated. The absolute atomic oxygen density and its temporal and spatial dynamics are studied by means of two-photon absorption laser-induced fluorescence. A high density of atomic oxygen is detected in the He/O2 mixture with up to 10% O2 content in the feed gas, whereas the atomic oxygen concentration in the Ar/O2 mixture stays below the detection limit of 1013 cm-3. The measured O density near the electrode under the optimal conditions in He/1.75% O2 gas is 4.26  ×  1015 cm-3. The existence of the ground state O (2p 4 3 P) species has been proven in the discharge at a distance up to 12 mm away from the electrodes. Dissociative reactions of the singlet O2 with O3 and deep vacuum ultraviolet radiation, including the radiation of excimer \\text{He}2\\ast , are proposed to be responsible for O (2p 4 3 P) production in the far afterglow. A capability of the surface micro-discharge array delivering atomic oxygen to long distances over a large area is considered very interesting for various biomedical applications.

Surface modification of positive electrode materials for lithium-ion batteries

Energy Technology Data Exchange (ETDEWEB)

Julien, C.M., E-mail: Christian.Julien@upmc.fr [Sorbonne Universités, UPMC Univ. Paris 6, Physicochimie des Electrolytes et Nanosystèmes Interfaciaux (PHENIX), UMR 8234, 75005 Paris (France); Mauger, A. [Institut de Minéralogie de Physique des Matériaux et de Cosmochimie (IMPMC), UPMC Univ. Paris 6, 4 place Jussieu, 75005 Paris (France); Groult, H. [Sorbonne Universités, UPMC Univ. Paris 6, Physicochimie des Electrolytes et Nanosystèmes Interfaciaux (PHENIX), UMR 8234, 75005 Paris (France); Zaghib, K. [Energy Storage and Conversion, Research Institute of Hydro-Québec, Varennes, Québec J3X 1S1 (Canada)

2014-12-01

The advanced lithium-ion batteries are critically important for a wide range of applications, from portable electronics to electric vehicles. The research on their electrodes aims to increase the energy density and the power density, improve the calendar and the cycling life, without sacrificing the safety issues. A constant progress through the years has been obtained owing to the surface treatment of the particles, in particular the coating of the nanoparticles with a layer that protects the core region from side reactions with the electrolyte, prevents the loss of oxygen, and the dissolution of the metal ions in the electrolyte, or simply improve the conductivity of the powder. The purpose of the present work is to present the different surface modifications that have been tried for three families of positive electrodes: layered, spinel and olivine frameworks that are currently considered as promising materials. The role of the different coats used to improve either the surface conductivity, or the thermal stability, or the structural integrity is discussed. - Highlights: • Report the various surface modifications tried for the positive electrodes of Li-ion batteries. • The role of different coats used to improve the conductivity, or the thermal stability, or the structural integrity. • Improvement of electrochemical properties of electrodes after coating or surface treatment.

Towards forming-free resistive switching in oxygen engineered HfO{sub 2−x}

Energy Technology Data Exchange (ETDEWEB)

Sharath, S. U., E-mail: sharath@oxide.tu-darmstadt.de; Kurian, J.; Hildebrandt, E.; Alff, L. [Institute of Materials Science, Technische Universität Darmstadt, Alarich-Weiss-Strasse 2, 64287 Darmstadt (Germany); Bertaud, T.; Walczyk, C.; Calka, P.; Zaumseil, P.; Sowinska, M.; Walczyk, D. [IHP, Im Technologiepark 25, 15236 Frankfurt Oder (Germany); Gloskovskii, A. [Deutsches Elektronen-Synchrotron DESY, Notkestrasse 85, 22607 Hamburg (Germany); Schroeder, T. [IHP, Im Technologiepark 25, 15236 Frankfurt Oder (Germany); Brandenburgische Technische Universität, Konrad-Zuse-Strasse 1, 03046 Cottbus (Germany)

2014-02-10

We have investigated the resistive switching behavior in stoichiometric HfO{sub 2} and oxygen-deficient HfO{sub 2−x} thin films grown on TiN electrodes using reactive molecular beam epitaxy. Oxygen defect states were controlled by the flow of oxygen radicals during thin film growth. Hard X-ray photoelectron spectroscopy confirmed the presence of sub-stoichiometric hafnium oxide and defect states near the Fermi level. The oxygen deficient HfO{sub 2−x} thin films show bipolar switching with an electroforming occurring at low voltages and low operating currents, paving the way for almost forming-free devices for low-power applications.

Method of preparation of carbon materials for use as electrodes in rechargeable batteries

Science.gov (United States)

Doddapaneni, Narayan; Wang, James C. F.; Crocker, Robert W.; Ingersoll, David; Firsich, David W.

1999-01-01

A method of producing carbon materials for use as electrodes in rechargeable batteries. Electrodes prepared from these carbon materials exhibit intercalation efficiencies of .apprxeq.80% for lithium, low irreversible loss of lithium, long cycle life, are capable of sustaining a high rates of discharge and are cheap and easy to manufacture. The method comprises a novel two-step stabilization process in which polymeric precursor materials are stabilized by first heating in an inert atmosphere and subsequently heating in air. During the stabilization process, the polymeric precursor material can be agitated to reduce particle fusion and promote mass transfer of oxygen and water vapor. The stabilized, polymeric precursor materials can then be converted to a synthetic carbon, suitable for fabricating electrodes for use in rechargeable batteries, by heating to a high temperature in a flowing inert atmosphere.

Pyroelectric response of perovskite heterostructures incorporating conductive oxide electrodes

Science.gov (United States)

Tipton, Charles Wesley, IV

2000-10-01

The use of imaging technologies has become pervasive in many applications as the demand for situational awareness information has increased over the last decade. No better example of the integration of these technologies can be found than that of infrared or thermal imaging. This dissertation, in the field of thermal imaging, has been motivated by the desire to advance the technology of uncooled, thin-film pyroelectric sensors and focuses on the materials and structures from which the detector elements will be built. This work provides a detailed study of the pyroelectric response of the La-Sr-Co-O/Pb-La-Zr-Ti-O/La-Sr-Co-O (LPL) structure. The LPL structure was chosen based on the needs of thin film detectors, the unique properties of the conductive oxide La-Sr-Co-O (LSCO), and the broad applicability of the Pb-La-Zr-Ti-O (PLZT) material system. Epitaxial heterostructures were grown by pulsed laser deposition on single-crystal oxide substrates. Using the oxygen pressure during cooling and heating of the LSCO layer as a key variable, we have been able to produce structures that have a pronounced internal field in the as-grown state. In these capacitors, where the bottom electrode has a large concentration of oxygen vacancies, we have discovered very large pyroelectric responses that are 10 to 30 times larger than expected of PLZT-based pyroelectric materials (typical values are 20 to 40 nCcm-2K -1). The enhanced pyroelectric responses are very repeatable, stable over time, and distinctly different from responses attributed to thermally stimulated currents. Detailed positron annihilation spectroscopy measurements reveal that there is indeed an oxygen concentration gradient across the capacitor. Based on the results of this study, I will present an analysis of the enhanced pyroelectric response. Although the enhanced response has been correlated with high concentrations of oxygen vacancies in the PLZT film and LSCO electrodes, the mechanism by which the large

Reduced oxygen enhancement ratio at low doses

International Nuclear Information System (INIS)

Palcic, B.; Skarsgard, L.D.

1984-01-01

The oxygen depletion rate in cell suspensions was measured using a Clark electrode. It was found that under experimental conditions used in this laboratory for hypoxic irradiations, the oxygen levels before the start of irradiation are always below 0.1μm, the levels which could give any significant enhancement to radiation inactivation by x-rays. The measured O/sub 2/ depletion rates were comparable to those reported in the literature. Chinese hamster cells (CHO) were made hypoxic by gas exchange, combined with metabolic consumption of oxygen by cells at 37 0 C. Full survival curves were determined in the dose range 0 to 3Gy using the low dose survival assay. The results confirmed the authors' earlier finding that the OER decreases at low doses. The authors therefore believe that the dose-dependent OER is a true radiobiological phenomenon and not an artifact of the experimental method used in the low dose survival assay

Brain Tissue Oxygen: In Vivo Monitoring with Carbon Paste Electrodes

Directory of Open Access Journals (Sweden)

John P. Lowry

2005-11-01

Full Text Available In this communication we review selected experiments involving the use ofcarbon paste electrodes (CPEs to monitor and measure brain tissue O2 levels in awakefreely-moving animals. Simultaneous measurements of rCBF were performed using the H2clearance technique. Voltammetric techniques used include both differential pulse (O2 andconstant potential amperometry (rCBF. Mild hypoxia and hyperoxia produced rapidchanges (decrease and increase respectively in the in vivo O2 signal. Neuronal activation(tail pinch and stimulated grooming produced similar increases in both O2 and rCBFindicating that CPE O2 currents provide an index of increases in rCBF when such increasesexceed O2 utilization. Saline injection produced a transient increase in the O2 signal whilechloral hydrate produced slower more long-lasting changes that accompanied the behavioralchanges associated with anaesthesia. Acetazolamide increased O2 levels through an increasein rCBF.

Sulfur-doped porous reduced graphene oxide hollow nanosphere frameworks as metal-free electrocatalysts for oxygen reduction reaction and as supercapacitor electrode materials.

Science.gov (United States)

Chen, Xi'an; Chen, Xiaohua; Xu, Xin; Yang, Zhi; Liu, Zheng; Zhang, Lijie; Xu, Xiangju; Chen, Ying; Huang, Shaoming

2014-11-21

Chemical doping with foreign atoms is an effective approach to significantly enhance the electrochemical performance of the carbon materials. Herein, sulfur-doped three-dimensional (3D) porous reduced graphene oxide (RGO) hollow nanosphere frameworks (S-PGHS) are fabricated by directly annealing graphene oxide (GO)-encapsulated amino-modified SiO2 nanoparticles with dibenzyl disulfide (DBDS), followed by hydrofluoric acid etching. The XPS and Raman spectra confirmed that sulfur atoms were successfully introduced into the PGHS framework via covalent bonds. The as-prepared S-PGHS has been demonstrated to be an efficient metal-free electrocatalyst for oxygen reduction reaction (ORR) with the activity comparable to that of commercial Pt/C (40%) and much better methanol tolerance and durability, and to be a supercapacitor electrode material with a high specific capacitance of 343 F g(-1), good rate capability and excellent cycling stability in aqueous electrolytes. The impressive performance for ORR and supercapacitors is believed to be due to the synergistic effect caused by sulfur-doping enhancing the electrochemical activity and 3D porous hollow nanosphere framework structures facilitating ion diffusion and electronic transfer.

Chitin based heteroatom-doped porous carbon as electrode materials for supercapacitors.

Science.gov (United States)

Zhou, Jie; Bao, Li; Wu, Shengji; Yang, Wei; Wang, Hui

2017-10-01

Chitin biomass has received much attention as an amino-functional polysaccharide precursor for synthesis of carbon materials. Rich nitrogen and oxygen dual-doped porous carbon derived from cicada slough (CS), a renewable biomass mainly composed of chitin, was synthesized and employed as electrode materials for electrochemical capacitors, for the first time ever. The cicada slough-derived carbon (CSC) was prepared by a facile process via pre-carbonization in air, followed by KOH activation. The weight ratio of KOH and char plays an important role in fabricating the microporous structure and tuning the surface chemistry of CSC. The obtained CSC had a large specific surface area (1243-2217m 2 g -1 ), fairly high oxygen content (28.95-33.78 at%) and moderate nitrogen content (1.47-4.35 at%). The electrochemical performance of the CS char and CSC as electrodes for capacitors was evaluated in a three-electrode cell configuration with 6M KOH as the electrolyte. Electrochemical studies showed that the as-prepared CSC activated at the KOH-to-char weight ratio of 2 exhibited the highest specific capacitance (266.5Fg -1 at a current density of 0.5Ag -1 ) and excellent rate capability (196.2Fg -1 remained at 20Ag -1 ) and cycle durability. In addition, the CSC-2-based symmetrical device possessed the desirable energy density and power density of about 15.97Whkg -1 and 5000Wkg -1 at 5Ag -1 , respectively. Copyright © 2017 Elsevier Ltd. All rights reserved.

Catoptric electrodes: transparent metal electrodes using shaped surfaces.

Science.gov (United States)

Kik, Pieter G

2014-09-01

An optical electrode design is presented that theoretically allows 100% optical transmission through an interdigitated metallic electrode at 50% metal areal coverage. This is achieved by redirection of light incident on embedded metal electrode lines to an angle beyond that required for total internal reflection. Full-field electromagnetic simulations using realistic material parameters demonstrate 84% frequency-averaged transmission for unpolarized illumination across the entire visible spectral range using a silver interdigitated electrode at 50% areal coverage. The redirection is achieved through specular reflection, making it nonresonant and arbitrarily broadband, provided the electrode width exceeds the optical wavelength. These findings could significantly improve the performance of photovoltaic devices and optical detectors that require high-conductivity top contacts.

Kinetic investigation of vanadium (V)/(IV) redox couple on electrochemically oxidized graphite electrodes