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Sample records for cerium oxides

  1. Cerium Oxide and Cerium Compounds

    Integrated Risk Information System (IRIS)

    EPA / 635 / R - 08 / 002F www.epa.gov / iris TOXICOLOGICAL REVIEW OF Cerium Oxide and Cerium Compounds ( CAS No . 1306 - 38 - 3 ) In Support of Summary Information on the Integrated Risk Information System ( IRIS ) September 2009 U.S . Environmental Protection Agency Washington , DC ii DISCLAIMER Th

  2. Nanoparticle cerium oxide and mixed cerium oxides for improved fuel cell lifetime

    NASA Astrophysics Data System (ADS)

    Stewart, Stephen Michael

    While there is a rich body of literature concerning of properties of bulk cerium oxide and cerium cations in solution, the discussion has been inappropriately applied to nanoscale cerium oxide resulting in many unexpected or unexplained results. In particular, there is very limited understanding about the properties of cerium oxide and its potential use as a radical scavenger, and how the catalytic properties of cerium oxide change as the particle size approaches the nanoscale. For example, the involvement of Ce+4 and Ce+3 cations in reactions such as hydrogen peroxide decomposition have been investigated for both cerium cations and bulk cerium oxide. However, while both are assumed to decompose hydrogen peroxide through the same mechanism, whereby Ce+4 is involved in peroxide decomposition while Ce +3 is involved in radical scavenging, there has been very little done to address how the selectivity and activity of these reactions are affected by changing the majority cation population, as cerium cations in solution are predominantly in the +3 oxidation state while cerium cations are predominantly in the +4 oxidation state in cerium oxide. This matter is further complicated in cerium oxide nanoparticles where the surface concentration of Ce +3 cations is increased due to particle curvature effects. Due to the potential of controlling the surface cerium oxidation state using particle size and using this control to change the catalytic properties, this project investigated the effect of particle size and composition and the activity and selectivity of cerium oxide nanoparticles, and has served to expand the understanding of the properties of pure and mixed nanoparticle cerium oxide. This work explains the metric developed for measuring the catalytic properties of pure and mixed cerium oxide nanoparticles, which is also good at predicting the immediate and long-term behavior of nanoparticles in hydrogen fuel cells. This work also directly demonstrates praseodymium

  3. Formulation and method for preparing gels comprising hydrous cerium oxide

    DOEpatents

    Collins, Jack L; Chi, Anthony

    2013-05-07

    Formulations useful for preparing hydrous cerium oxide gels contain a metal salt including cerium, an organic base, and a complexing agent. Methods for preparing gels containing hydrous cerium oxide include heating a formulation to a temperature sufficient to induce gel formation, where the formulation contains a metal salt including cerium, an organic base, and a complexing agent.

  4. IRIS Toxicological Review of Cerium Oxide and Cerium Compounds (External Review Draft)

    EPA Science Inventory

    EPA conducted a peer review of the scientific basis supporting the human health hazard and dose-response assessment of cerium oxide and cerium compounds that will appear on the Integrated Risk Information System (IRIS) database.

  5. Nanocrystalline cerium oxide materials for solid fuel cell systems

    SciTech Connect

    Brinkman, Kyle S

    2015-05-05

    Disclosed are solid fuel cells, including solid oxide fuel cells and PEM fuel cells that include nanocrystalline cerium oxide materials as a component of the fuel cells. A solid oxide fuel cell can include nanocrystalline cerium oxide as a cathode component and microcrystalline cerium oxide as an electrolyte component, which can prevent mechanical failure and interdiffusion common in other fuel cells. A solid oxide fuel cell can also include nanocrystalline cerium oxide in the anode. A PEM fuel cell can include cerium oxide as a catalyst support in the cathode and optionally also in the anode.

  6. Photodissociation of Cerium Oxide Nanocluster Cations.

    PubMed

    Akin, S T; Ard, S G; Dye, B E; Schaefer, H F; Duncan, M A

    2016-04-21

    Cerium oxide cluster cations, CexOy(+), are produced via laser vaporization in a pulsed nozzle source and detected with time-of-flight mass spectrometry. The mass spectrum displays a strongly preferred oxide stoichiometry for each cluster with a specific number of metal atoms x, with x ≤ y. Specifically, the most prominent clusters correspond to the formula CeO(CeO2)n(+). The cluster cations are mass selected and photodissociated with a Nd:YAG laser at either 532 or 355 nm. The prominent clusters dissociate to produce smaller species also having a similar CeO(CeO2)n(+) formula, always with apparent leaving groups of (CeO2). The production of CeO(CeO2)n(+) from the dissociation of many cluster sizes establishes the relative stability of these clusters. Furthermore, the consistent loss of neutral CeO2 shows that the smallest neutral clusters adopt the same oxidation state (IV) as the most common form of bulk cerium oxide. Clusters with higher oxygen content than the CeO(CeO2)n(+) masses are present with much lower abundance. These species dissociate by the loss of O2, leaving surviving clusters with the CeO(CeO2)n(+) formula. Density functional theory calculations on these clusters suggest structures composed of stable CeO(CeO2)n(+) cores with excess oxygen bound to the surface as a superoxide unit (O2(-)). PMID:27035210

  7. The surface chemistry of cerium oxide

    SciTech Connect

    Mullins, David R.

    2015-01-29

    Our review covers the structure of, and chemical reactions on, well-defined cerium oxide surfaces. Ceria, or mixed oxides containing ceria, are critical components in automotive three-way catalysts due to their well-known oxygen storage capacity. Ceria is also emerging as an important material in a number of other catalytic processes, particularly those involving organic oxygenates and the water–gas shift reaction. Ceria's acid–base properties, and thus its catalytic behavior, are closely related to its surface structure where different oxygen anion and cerium cation environments are present on the low-index structural faces. The actual structure of these various faces has been the focus of a number of theoretical and experimental investigations. Ceria is also easily reducible from CeO2 to CeO2-X. The presence of oxygen vacancies on the surface often dramatically alters the adsorption and subsequent reactions of various adsorbates, either on a clean surface or on metal particles supported on the surface. We conducted surface science studies on the surfaces of thin-films rather than on the surfaces of bulk single crystal oxides. The growth, characterization and properties of these thin-films are also examined.

  8. The surface chemistry of cerium oxide

    DOE PAGESBeta

    Mullins, David R.

    2015-01-29

    Our review covers the structure of, and chemical reactions on, well-defined cerium oxide surfaces. Ceria, or mixed oxides containing ceria, are critical components in automotive three-way catalysts due to their well-known oxygen storage capacity. Ceria is also emerging as an important material in a number of other catalytic processes, particularly those involving organic oxygenates and the water–gas shift reaction. Ceria's acid–base properties, and thus its catalytic behavior, are closely related to its surface structure where different oxygen anion and cerium cation environments are present on the low-index structural faces. The actual structure of these various faces has been the focusmore » of a number of theoretical and experimental investigations. Ceria is also easily reducible from CeO2 to CeO2-X. The presence of oxygen vacancies on the surface often dramatically alters the adsorption and subsequent reactions of various adsorbates, either on a clean surface or on metal particles supported on the surface. We conducted surface science studies on the surfaces of thin-films rather than on the surfaces of bulk single crystal oxides. The growth, characterization and properties of these thin-films are also examined.« less

  9. The surface chemistry of cerium oxide

    NASA Astrophysics Data System (ADS)

    Mullins, David R.

    2015-03-01

    This review covers the structure of, and chemical reactions on, well-defined cerium oxide surfaces. Ceria, or mixed oxides containing ceria, are critical components in automotive three-way catalysts due to their well-known oxygen storage capacity. Ceria is also emerging as an important material in a number of other catalytic processes, particularly those involving organic oxygenates and the water-gas shift reaction. Ceria's acid-base properties, and thus its catalytic behavior, are closely related to its surface structure where different oxygen anion and cerium cation environments are present on the low-index structural faces. The actual structure of these various faces has been the focus of a number of theoretical and experimental investigations. Ceria is also easily reducible from CeO2 to CeO2-X. The presence of oxygen vacancies on the surface often dramatically alters the adsorption and subsequent reactions of various adsorbates, either on a clean surface or on metal particles supported on the surface. Most surface science studies have been conducted on the surfaces of thin-films rather than on the surfaces of bulk single crystal oxides. The growth, characterization and properties of these thin-films are also examined.

  10. Liquid-phase oxidation of cyclohexanone over cerium oxide catalyst

    SciTech Connect

    Shen, H.C. ); Weng, H.S. )

    1990-05-01

    Catalytic oxidation of cyclohexanone in the liquid phase with glacial acetic acid as the solvent over cerium oxide was studied between 5 and 15 atm and 98 and 118 {degrees} C in a batch reactor. The products were adipic acid, glutaric acid, succinic acid, caprolactone, carbon oxides, etc. The reaction undergoes a short induction period prior to a rapid reaction regime. In both regimes, the reaction is independent of oxygen pressure when the system pressure is above 10 atm. The induction period is inversely proportional to both of the catalyst weight and cyclohexanone concentration.During the rapid reaction regime, the reaction rate was found to be proportional to the 0.5 power of the catalyst weight and to the 1.5 power of the cyclohexanone concentration. Reaction mechanisms and rate expressions are proposed. The carbon oxides produced in this study were much lower than those previously reported. The cerium oxide catalyst is stable during the reaction.

  11. An investigation of the continuum resonance effect in cerium and cerium oxide

    NASA Astrophysics Data System (ADS)

    Roberts, Mark W.

    1998-10-01

    Large x-ray emission resonances associated with the M shell in cerium and cerium oxide were investigated. The device used in this investigation consisted of an energy dispersive x-ray detector and a double-pass cylindrical mirror electron analyzer within an ultra-high vacuum system. Observations were made of the x-ray and electron emissions from samples bombarded by mono-energetic electrons from an electron gun. The x-ray and electron data were recorded with the system pressure in the low 10-9 torr range. X-ray data were obtained using incident electron energies from 865 eV to 925 eV; the binding energies of the cerium M5 and M4 subshells and the x-ray continuum resonances are contained within this energy range. The x- ray detector was set to count x-rays in a fixed energy window 120 eV wide, centered on 900 eV. Differentiated electron spectra from the samples were recorded using a lock-in amplifier. Vacuum evaporation and condensation were used to deposit cerium metal samples onto a wheel which was then rotated to position a given sample in front of the electron gun. Cerium oxide samples were obtained by exposing cerium metal deposits to room air at atmospheric pressure and then repumping the system. The x-ray yield spectra from the cerium and cerium oxide samples show large resonances for incident electron energies near the M5 and M4 level ionization energies. There are no features in the electron spectra which correspond to the large resonances observed in the x-ray yield spectra. These findings are in agreement with results previously obtained by Chamberlain et al. and by Mason. The maxima in the x-ray resonances for cerium oxide occur at slightly lower incident electron energy than those for cerium metal. There is also a large increase in the intensity of the x-ray continuum resonance yield in cerium oxide above that in the metal. Possible explanations for these observations are presented.

  12. Optical glass surfaces polishing by cerium oxide particles

    NASA Astrophysics Data System (ADS)

    Bouzid, D.; Belkhie, N.; Aliouane, T.

    2012-02-01

    The use of powders in metallic oxides as means of grinding and polishing of the optical glass components have seen recently a large application in optical industry. In fact, cerium oxide abrasive is more used in the optical glass polishing. It is used as grains abrasive in suspension or fixed abrasive (pellets); these pellets are manufactured from a mixture made of cerium oxide abrasive and a organic binder. The cerium oxide used in the experiments is made by (Logitech USA) of 99 % purity, the average grain size of the particle is 300 nm, the density being 6,74 g /cm3 and the specific surface is 3,3042 m2/g. In this study, we are interested in the surfaces quality of the optical glass borosilicate crown (BK7) polished by particles in cerium oxide bounded by epoxy. The surfaces of the optical glass treated are characterized by the roughness, the flatness by using the microscope Zygo and the SEM.

  13. Heteroaggregation of cerium oxide nanoparticles and nanoparticles of pyrolyzed biomass

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Heteroaggregation with indigenous particles is an important process controlling the mobility of engineered nanomaterials in the environment. We studied heteroaggregation of cerium oxide nanoparticles (n-CeO2), which are widely used commercially, with nanoparticles of pyrogenic carbonaceous material ...

  14. Uptake and accumulation of bulk and nanosized cerium oxide particles and ionic cerium by radish (Raphanus sativus L.).

    PubMed

    Zhang, Weilan; Ebbs, Stephen D; Musante, Craig; White, Jason C; Gao, Cunmei; Ma, Xingmao

    2015-01-21

    The potential toxicity and accumulation of engineered nanomaterials (ENMs) in agricultural crops has become an area of great concern and intense investigation. Interestingly, although below-ground vegetables are most likely to accumulate the highest concentrations of ENMs, little work has been done investigating the potential uptake and accumulation of ENMs for this plant group. The overall objective of this study was to evaluate how different forms of cerium (bulk cerium oxide, cerium oxide nanoparticles, and the cerium ion) affected the growth of radish (Raphanus sativus L.) and accumulation of cerium in radish tissues. Ionic cerium (Ce(3+)) had a negative effect on radish growth at 10 mg CeCl3/L, whereas bulk cerium oxide (CeO2) enhanced plant biomass at the same concentration. Treatment with 10 mg/L cerium oxide nanoparticles (CeO2 NPs) had no significant effect on radish growth. Exposure to all forms of cerium resulted in the accumulation of this element in radish tissues, including the edible storage root. However, the accumulation patterns and their effect on plant growth and physiological processes varied with the characteristics of cerium. This study provides a critical frame of reference on the effects of CeO2 NPs versus their bulk and ionic counterparts on radish growth.

  15. Control of cerium oxidation state through metal complex secondary structures

    DOE PAGESBeta

    Levin, Jessica R.; Dorfner, Walter L.; Carroll, Patrick J.; Schelter, Eric J.

    2015-08-11

    A series of alkali metal cerium diphenylhydrazido complexes, Mx(py)y[Ce(PhNNPh)4], M = Li, Na, and K, x = 4 (Li and Na) or 5 (K), and y = 4 (Li), 8 (Na), or 7 (K), were synthesized to probe how a secondary coordination sphere would modulate electronic structures at a cerium cation. The resulting electronic structures of the heterobimetallic cerium diphenylhydrazido complexes were found to be strongly dependent on the identity of the alkali metal cations. When M = Li+ or Na+, the cerium(III) starting material was oxidized with concomitant reduction of 1,2-diphenylhydrazine to aniline. Reduction of 1,2-diphenylhydrazine was not observedmore » when M = K+, and the complex remained in the cerium(III) oxidation state. Oxidation of the cerium(III) diphenylhydrazido complex to the Ce(IV) diphenylhydrazido one was achieved through a simple cation exchange reaction of the alkali metals. As a result, UV-Vis spectroscopy, FTIR spectroscopy, electrochemistry, magnetic susceptibility, and DFT studies were used to probe the oxidation state and the electronic changes that occurred at the metal centre.« less

  16. Control of cerium oxidation state through metal complex secondary structures

    SciTech Connect

    Levin, Jessica R.; Dorfner, Walter L.; Carroll, Patrick J.; Schelter, Eric J.

    2015-08-11

    A series of alkali metal cerium diphenylhydrazido complexes, Mx(py)y[Ce(PhNNPh)4], M = Li, Na, and K, x = 4 (Li and Na) or 5 (K), and y = 4 (Li), 8 (Na), or 7 (K), were synthesized to probe how a secondary coordination sphere would modulate electronic structures at a cerium cation. The resulting electronic structures of the heterobimetallic cerium diphenylhydrazido complexes were found to be strongly dependent on the identity of the alkali metal cations. When M = Li+ or Na+, the cerium(III) starting material was oxidized with concomitant reduction of 1,2-diphenylhydrazine to aniline. Reduction of 1,2-diphenylhydrazine was not observed when M = K+, and the complex remained in the cerium(III) oxidation state. Oxidation of the cerium(III) diphenylhydrazido complex to the Ce(IV) diphenylhydrazido one was achieved through a simple cation exchange reaction of the alkali metals. As a result, UV-Vis spectroscopy, FTIR spectroscopy, electrochemistry, magnetic susceptibility, and DFT studies were used to probe the oxidation state and the electronic changes that occurred at the metal centre.

  17. Electrode electrolyte interlayers containing cerium oxide for electrochemical fuel cells

    DOEpatents

    Borglum, Brian P.; Bessette, Norman F.

    2000-01-01

    An electrochemical cell is made having a porous fuel electrode (16) and a porous air electrode (13), with solid oxide electrolyte (15) therebetween, where the air electrode surface opposing the electrolyte has a separate, attached, dense, continuous layer (14) of a material containing cerium oxide, and where electrolyte (16) contacts the continuous oxide layer (14), without contacting the air electrode (13).

  18. Optical and electrical studies of cerium mixed oxides

    SciTech Connect

    Sherly, T. R.; Raveendran, R.

    2014-10-15

    The fast development in nanotechnology makes enthusiastic interest in developing nanomaterials having tailor made properties. Cerium mixed oxide materials have received great attention due to their UV absorption property, high reactivity, stability at high temperature, good electrical property etc and these materials find wide applications in solid oxide fuel cells, solar control films, cosmetics, display units, gas sensors etc. In this study cerium mixed oxide compounds were prepared by co-precipitation method. All the samples were doped with Zn (II) and Fe (II). Preliminary characterizations such as XRD, SEM / EDS, TEM were done. UV - Vis, Diffuse reflectance, PL, FT-IR, Raman and ac conductivity studies of the samples were performed.

  19. The effective thermal conductivity of an adsorbent - Praseodymium cerium oxide

    NASA Technical Reports Server (NTRS)

    Secary, J. J.; Tong, T. W.

    1992-01-01

    The results of an experimental study to determine the effective thermal conductivity of praseodymium cerium oxide are reported. Praseodymium cerium oxide is an adsorbent used in the development of adsorption compressors for spaceborne refrigeration systems. A guarded-hot-plate apparatus was built for this study. Measurements were carried out for mean temperatures ranging from 300 to 600 C under a vacuum of 10 exp -5 torr. For the temperature range studied, the effective thermal conductivity increased from 0.14 to 0.76 W/m per C with increasing temperature, while displaying a cubic temperature dependency.

  20. Synthesis and characterization of magnesium doped cerium oxide for the fuel cell application

    NASA Astrophysics Data System (ADS)

    Kumar, Amit; Kumari, Monika; Kumar, Mintu; Kumar, Sacheen; Kumar, Dinesh

    2016-05-01

    Cerium oxide has attained much attentions in global nanotechnology market due to valuable application for catalytic, fuel additive, and widely as electrolyte in solid oxide fuel cell. Doped cerium oxide has large oxygen vacancies that allow for greater reactivity and faster ion transport. These properties make cerium oxide suitable material for SOFCs application. Cerium oxide electrolyte requires lower operation temperature which shows improvement in processing and the fabrication technique. In our work, we synthesized magnesium doped cerium oxide by the co-precipitation method. With the magnesium doping catalytic reactivity of CeO2 was increased. Synthesized nanoparticle were characterized by the XRD and UV absorption techniques.

  1. IRIS TOXICOLOGICAL REVIEW AND SUMMARY DOCUMENTS FOR CERIUM OXIDE (STABLE) AND COMPOUNDS

    EPA Science Inventory

    Cerium is a member of the lanthanoid series of rare earth metals. It is also the most abundant and most reactive of the rare earth metals. Cerium oxidizes at room temperature and forms a variety of salt compounds including oxides, hydroxides, sulfates and chlorides. Cerium is ...

  2. Fungus mediated synthesis of biomedically important cerium oxide nanoparticles

    SciTech Connect

    Khan, Shadab Ali; Ahmad, Absar

    2013-10-15

    Graphical abstract: - Highlights: • First time biological synthesis of cerium oxide oxide nanoparticles using fungus Humicola sp. • Complete characterization of cerium oxide nanoparticles. • Biosynthesis of naturally protein capped, luminescent and water dispersible CeO{sub 2} nanoparticles. • Biosynthesized CeO{sub 2} nanoparticles can be used for many biomedical applications. - Abstract: Nanomaterials can be synthesized by chemical, physical and the more recently discovered biological routes. The biological routes are advantageous over the chemical and physical ones as unlike these, the biological synthesis protocols occur at ambient conditions, are cheap, non-toxic and eco-friendly. Although purely biological and bioinspired methods for the synthesis of nanomaterials are environmentally benign and energy conserving processes, their true potential has not been explored yet and attempts are being made to extend the formation of technologically important nanoparticles using microorganisms like fungi. Though there have been reports on the biosynthesis of oxide nanoparticles by our group in the past, no attempts have been made to employ fungi for the synthesis of nanoparticles of rare earth metals or lanthanides. Here we report for the first time, the bio-inspired synthesis of biomedically important cerium oxide (CeO{sub 2}) nanoparticles using the thermophilic fungus Humicola sp. The fungus Humicola sp. when exposed to aqueous solutions of oxide precursor cerium (III) nitrate hexahydrate (CeN{sub 3}O{sub 9}·6H{sub 2}O) results in the extracellular formation of CeO{sub 2} nanoparticles containing Ce (III) and Ce (IV) mixed oxidation states, confirmed by X-ray Photoemission Spectroscopy (XPS). The formed nanoparticles are naturally capped by proteins secreted by the fungus and thus do not agglomerate, are highly stable, water dispersible and are highly fluorescent as well. The biosynthesized nanoparticles were characterized by UV–vis spectroscopy

  3. Fundamental aspects of regenerative cerium oxide nanoparticles and their applications in nanobiotechnology

    NASA Astrophysics Data System (ADS)

    Patil, Swanand D.

    Cerium oxide has been used extensively for various applications over the past two decades. The use of cerium oxide nanoparticles is beneficial in present applications and can open avenues for future applications. The present study utilizes the microemulsion technique to synthesize uniformly distributed cerium oxide nanoparticles. The same technique was also used to synthesize cerium oxide nanoparticles doped with trivalent elements (La and Nd). The fundamental study of cerium oxide nanoparticles identified variations in properties as a function of particle size and also due to doping with trivalent elements (La and Nd). It was found that the lattice parameter of cerium oxide nanoparticles increases with decrease in particle size. Also Raman allowed mode shift to lower energies and the peak at 464 cm-1 becomes broader and asymmetric. The size dependent changes in cerium oxide were correlated to increase in oxygen vacancy concentration in the cerium oxide lattice. The doping of cerium oxide nanoparticles with trivalent elements introduces more oxygen vacancies and expands the cerium oxide lattice further (in addition to the lattice expansion due to the size effect). The lattice expansion is greater for La-doped cerium oxide nanoparticles compared to Nd-doping due to the larger ionic radius of La compared to Nd, the lattice expansion is directly proportional to the dopant concentration. The synthesized cerium oxide nanoparticles were used to develop an electrochemical biosensor of hydrogen peroxide (H2O2). The sensor was useful to detect H2O2 concentrations as low as 1muM in water. Also the preliminary testing of the sensor on tomato stem and leaf extracts indicated that the sensor can be used in practical applications such as plant physiological studies etc. The nanomolar concentrations of cerium oxide nanoparticles were also found to be useful in decreasing ROS (reactive oxygen species) mediated cellular damages in various in vitro cell cultures. Cerium oxide

  4. Engineered cerium oxide nanoparticles: Effects on bacterial growth and viability

    SciTech Connect

    Pelletier, Dale A; Suresh, Anil K; Holton, Gregory A; McKeown, Catherine K; Wang, Wei; Gu, Baohua; Mortensen, Ninell P; Allison, David P; Joy, David Charles; Allison, Martin R; Brown, Steven D; Phelps, Tommy Joe; Doktycz, Mitchel John

    2010-01-01

    Interest in engineered nanostructures has risen in recent years due to their use in energy conservation strategies and biomedicine. To ensure prudent development and use of nanomaterials, the fate and effects of such engineered structures on the environment should be understood. Interactions of nanomaterials with environmental microorganisms are inevitable, but the general consequences of such interactions remain unclear. Further, standardized methods for assessing such interactions are lacking. Therefore, we have initiated a multianalytical approach to understand the interactions of synthesized nanoparticles with bacterial systems. These efforts are focused initially on cerium oxide nanoparticles and model bacteria in order to evaluate characterization procedures and the possible fate of such materials in the environment. In this study the effects of cerium oxide nanoparticles on the growth and viability of Gram-negative Escherichia coli and Shewanella oneidensis, a metal-reducing bacteria, and Gram-positive Bacillus subtilis were examined relative to particle size, growth media, pH, and dosage. A hydrothermal based synthesis procedure was used to prepare cerium oxide nanoparticles of defined sizes in order to eliminate complications originating from the use of organic solvents and surfactants. Bactericidal effects were determined by minimum inhibitory concentration, colony forming units, disc diffusion tests and Live/Dead assays. In growth inhibition experiments involving E. coli and B. subtilis, a clear strain and size-dependent inhibition was observed. S. oneidensis appeared to be unaffected by the cerium oxide nanoparticles. Transmission electron microscopy along with microarray-based transcriptional profiling have been used to understand the response mechanism of the bacteria. The use of multiple analytical approaches adds confidence to toxicity assessments while the use of different bacterial systems highlights the potential wide-ranging effects of

  5. Antibacterial Activity of Polymer Coated Cerium Oxide Nanoparticles

    PubMed Central

    Shah, Vishal; Shah, Shreya; Shah, Hirsh; Rispoli, Fred J.; McDonnell, Kevin T.; Workeneh, Selam; Karakoti, Ajay; Kumar, Amit; Seal, Sudipta

    2012-01-01

    Cerium oxide nanoparticles have found numerous applications in the biomedical industry due to their strong antioxidant properties. In the current study, we report the influence of nine different physical and chemical parameters: pH, aeration and, concentrations of MgSO4, CaCl2, KCl, natural organic matter, fructose, nanoparticles and Escherichia coli, on the antibacterial activity of dextran coated cerium oxide nanoparticles. A least-squares quadratic regression model was developed to understand the collective influence of the tested parameters on the anti-bacterial activity and subsequently a computer-based, interactive visualization tool was developed. The visualization allows us to elucidate the effect of each of the parameters in combination with other parameters, on the antibacterial activity of nanoparticles. The results indicate that the toxicity of CeO2 NPs depend on the physical and chemical environment; and in a majority of the possible combinations of the nine parameters, non-lethal to the bacteria. In fact, the cerium oxide nanoparticles can decrease the anti-bacterial activity exerted by magnesium and potassium salts. PMID:23110109

  6. Induction of pulmonary fibrosis by cerium oxide nanoparticles

    SciTech Connect

    Ma, Jane Y.; Mercer, Robert R.; Barger, Mark; Schwegler-Berry, Diane; Scabilloni, James; Ma, Joseph K.; Castranova, Vincent

    2012-08-01

    Cerium compounds have been used as a diesel engine catalyst to lower the mass of diesel exhaust particles, but are emitted as cerium oxide (CeO{sub 2}) nanoparticles in the diesel exhaust. In a previous study, we have demonstrated a wide range of CeO{sub 2}-induced lung responses including sustained pulmonary inflammation and cellular signaling that could lead to pulmonary fibrosis. In this study, we investigated the fibrogenic responses induced by CeO{sub 2} in a rat model at various time points up to 84 days post-exposure. Male Sprague Dawley rats were exposed to CeO{sub 2} by a single intratracheal instillation. Alveolar macrophages (AM) were isolated by bronchial alveolar lavage (BAL). AM-mediated cellular responses, osteopontin (OPN) and transform growth factor (TGF)-β1 in the fibrotic process were investigated. The results showed that CeO{sub 2} exposure significantly increased fibrotic cytokine TGF-β1 and OPN production by AM above controls. The collagen degradation enzymes, matrix metalloproteinase (MMP)-2 and -9 and the tissue inhibitor of MMP were markedly increased in the BAL fluid at 1 day- and subsequently declined at 28 days after exposure, but remained much higher than the controls. CeO{sub 2} induced elevated phospholipids in BAL fluid and increased hydroxyproline content in lung tissue in a dose- and time-dependent manner. Immunohistochemical analysis showed MMP-2, MMP-9 and MMP-10 expressions in fibrotic regions. Morphological analysis noted increased collagen fibers in the lungs exposed to a single dose of 3.5 mg/kg CeO{sub 2} and euthanized at 28 days post-exposure. Collectively, our studies show that CeO{sub 2} induced fibrotic lung injury in rats, suggesting it may cause potential health effects. -- Highlights: ► Cerium oxide exposure significantly affected the following parameters in the lung. ► Induced fibrotic cytokine OPN and TGF-β1 production and phospholipidosis. ► Caused imbalance of the MMP-9/ TIMP-1 ratio that favors fibrosis

  7. Environmental Geochemistry of Cerium: Applications and Toxicology of Cerium Oxide Nanoparticles

    PubMed Central

    Dahle, Jessica T.; Arai, Yuji

    2015-01-01

    Cerium is the most abundant of rare-earth metals found in the Earth’s crust. Several Ce-carbonate, -phosphate, -silicate, and -(hydr)oxide minerals have been historically mined and processed for pharmaceutical uses and industrial applications. Of all Ce minerals, cerium dioxide has received much attention in the global nanotechnology market due to their useful applications for catalysts, fuel cells, and fuel additives. A recent mass flow modeling study predicted that a major source of CeO2 nanoparticles from industrial processing plants (e.g., electronics and optics manufactures) is likely to reach the terrestrial environment such as landfills and soils. The environmental fate of CeO2 nanoparticles is highly dependent on its physcochemical properties in low temperature geochemical environment. Though there are needs in improving the analytical method in detecting/quantifying CeO2 nanoparticles in different environmental media, it is clear that aquatic and terrestrial organisms have been exposed to CeO2 NPs, potentially yielding in negative impact on human and ecosystem health. Interestingly, there has been contradicting reports about the toxicological effects of CeO2 nanoparticles, acting as either an antioxidant or reactive oxygen species production-inducing agent). This poses a challenge in future regulations for the CeO2 nanoparticle application and the risk assessment in the environment. PMID:25625406

  8. Synthesis and characterization of polyvinylpyrrolidone coated cerium oxide nanoparticles.

    PubMed

    Merrifield, Ruth C; Wang, Zhi Wei; Palmer, Richard E; Lead, Jamie R

    2013-01-01

    There is a pressing need for the development of standard and reference nanomaterials for environmental nanoscience and nanotoxicology. To that aim, suspensions of polyvinylpyrrolidone (PVP)-coated ceria nanoparticles (NPs) were produced. Four differently sized monodispersed samples were produced by using different PVP chain lengths. The chemical and physical properties of these NPs were characterized as prepared and in different ecotoxicology exposure media. Dynamic light scattering analysis showed that the samples were monodispersed, with an unchanged size when suspended in the different media over a 72 h period. Electron microscopy confirmed this and revealed that the larger (ca. 20 nm) particles were aggregates composed of the smaller individual particles (4-5 nm). Electron energy loss spectroscopy (EELS) showed that the smallest and largest samples were composed almost entirely of cerium(III) oxide, with only small amounts of cerium(IV) present in the largest sample. Dissolved cerium concentrations in media were low and constant, showing that the NPs did not dissolve over time. The simple synthesis of the these NPs and their physical and chemical stability in different environmental conditions make them potentially suitable for use as reference materials for (eco)toxicology and surface water environmental studies.

  9. Superconductive articles including cerium oxide layer

    DOEpatents

    Wu, Xin D.; Muenchausen, Ross E.

    1993-01-01

    A ceramic superconductor comprising a metal oxide substrate, a ceramic high temperature superconductive material, and a intermediate layer of a material having a cubic crystal structure, said layer situated between the substrate and the superconductive material is provided, and a structure for supporting a ceramic superconducting material is provided, said structure comprising a metal oxide substrate, and a layer situated over the surface of the substrate to substantially inhibit interdiffusion between the substrate and a ceramic superconducting material deposited upon said structure.

  10. Redox reactivity of cerium oxide nanoparticles against dopamine.

    PubMed

    Hayat, Akhtar; Andreescu, Daniel; Bulbul, Gonca; Andreescu, Silvana

    2014-03-15

    The interaction between dopamine and the redox active cerium oxide nanoparticles, or nanoceria was studied using a suite of spectroscopic and surface characterization methods. Changes in the chemical reactivity and concentration of dopamine upon exposure to nanoceria was assessed in aqueous solutions and a human physiological fluid--human serum. The results indicate strong attachment of dopamine to the nanoparticle surface through oxidation followed by chemisorption of the oxidative product with formation of a charge transfer complex. Such oxidation/surface adsorption processes between nanoceria and dopamine lead to a reduction of the concentration of free dopamine in aqueous environments. These findings suggest that the redox reactivity of nanoceria may alter dopamine levels in biological systems exposed to these particles and indicate the need for a comprehensive assessment of the potential neurological consequences that might result from intended or unintended exposure to these particles. PMID:24461841

  11. Role of nanocrystalline cerium oxide coatings on austenitic stainless steels

    NASA Astrophysics Data System (ADS)

    Zhang, Haiying

    Protective nanocrystalline cerium oxide coating has been applied to ASTM grade 304L and 304 austenitic stainless steels to improve its oxidation resistance at elevated temperatures. Experimentally, the selected alloy was exposed to 800°C/1000°C under dry air conditions. Weight changes (DeltaW/A) were monitored as a function of time and the results were compared with uncoated alloys tested under similar conditions. It was found that the oxidation resistances of 304L and 304 stainless steels were significantly improved. A comparison of the oxidation rates indicated that the nanocrystalline cerium oxide coating reduced the rate of oxidation by more than two orders of magnitude. Nevertheless, a comprehensive understanding of the mechanisms responsible for the reduction in the oxidation rate is not clear. Consequently, this work is aimed at investigating the mechanisms involved during scale growth in the presence or absence of nanocrystalline coatings. For this purpose, density functional theory was carried out in order to predict oxygen and iron diffusion microscopic activation energies and reveal the intrinsic characteristics of nanocrystalline coatings. A numerical simulation of corrosion process has also been conducted to predict the corrosion rates of alloys with and without coatings. Hence, the results from simulations are compared with the experimental outcome, and possible explanations are given to account for the reduction in the exhibited oxidation rates. The simulation results will provide a highly valuable tool for the realization of functional nanostructures and architectures "by design", particularly in the development of novel coatings, and a new approach of life assessment.

  12. Pilot demonstration of cerium oxide coated anodes

    SciTech Connect

    Gregg, J.S.; Frederick, M.S.; Shingler, M.J.; Alcorn, T.R.

    1992-10-01

    Cu cermet anodes were tested for 213 to 614 hours with an in-situ deposited CEROX coating in a pilot cell operated by Reynolds Manufacturing Technology Laboratory. At high bath ratio ([approximately]1.5) and low current density (0.5 A/cm[sup 2]), a [ge]1 mm thick dense CEROX coating was deposited on the anodes. At lower bath ratios and higher current density, the CEROX coating was thinner and less dense, but no change in corrosion rate was noted. Regions of low current density on the anodes and sides adjacent to the carbon anode sometimes had thin or absent CEROX coatings. Problems with cracking and oxidation of the cermet substrates led to higher corrosion rates in a pilot cell than would be anticipated from lab scale results.

  13. Altering properties of cerium oxide thin films by Rh doping

    SciTech Connect

    Ševčíková, Klára; Nehasil, Václav; Vorokhta, Mykhailo; Haviar, Stanislav; Matolín, Vladimír; and others

    2015-07-15

    Highlights: • Thin films of ceria doped by rhodium deposited by RF magnetron sputtering. • Concentration of rhodium has great impact on properties of Rh–CeO{sub x} thin films. • Intensive oxygen migration in films with low concentration of rhodium. • Oxygen migration suppressed in films with high amount of Rh dopants. - Abstract: Ceria containing highly dispersed ions of rhodium is a promising material for catalytic applications. The Rh–CeO{sub x} thin films with different concentrations of rhodium were deposited by RF magnetron sputtering and were studied by soft and hard X-ray photoelectron spectroscopies, Temperature programmed reaction and X-ray powder diffraction techniques. The sputtered films consist of rhodium–cerium mixed oxide where cerium exhibits a mixed valency of Ce{sup 4+} and Ce{sup 3+} and rhodium occurs in two oxidation states, Rh{sup 3+} and Rh{sup n+}. We show that the concentration of rhodium has a great influence on the chemical composition, structure and reducibility of the Rh–CeO{sub x} thin films. The films with low concentrations of rhodium are polycrystalline, while the films with higher amount of Rh dopants are amorphous. The morphology of the films strongly influences the mobility of oxygen in the material. Therefore, varying the concentration of rhodium in Rh–CeO{sub x} thin films leads to preparing materials with different properties.

  14. Fabrication of Cerium Oxide and Uranium Oxide Microspheres for Space Nuclear Power Applications

    SciTech Connect

    Jeffrey A. Katalenich; Michael R. Hartman; Robert C. O'Brien

    2013-02-01

    Cerium oxide and uranium oxide microspheres are being produced via an internal gelation sol-gel method to investigate alternative fabrication routes for space nuclear fuels. Depleted uranium and non-radioactive cerium are being utilized as surrogates for plutonium-238 (Pu-238) used in radioisotope thermoelectric generators and for enriched uranium required by nuclear thermal rockets. While current methods used to produce Pu-238 fuels at Los Alamos National Laboratory (LANL) involve the generation of fine powders that pose a respiratory hazard and have a propensity to contaminate glove boxes, the sol-gel route allows for the generation of oxide microsphere fuels through an aqueous route. The sol-gel method does not generate fine powders and may require fewer processing steps than the LANL method with less operator handling. High-quality cerium dioxide microspheres have been fabricated in the desired size range and equipment is being prepared to establish a uranium dioxide microsphere production capability.

  15. Green synthesized cerium oxide nanoparticle: A prospective drug against oxidative harm.

    PubMed

    Dutta, Debanjan; Mukherjee, Riya; Patra, Mousumi; Banik, Milon; Dasgupta, Rakhi; Mukherjee, Manabendra; Basu, Tarakdas

    2016-11-01

    Cerium oxide nanoparticle (CeONP) of size 2-3nm was synthesized by a new, simple and green method at ambient temperature, using cerium nitrate as prime precursor and Aloe vera leaf extract as stabilizing agent. Of the two oxidation states (+3) and (+4) of cerium, it was dominantly present in (+3) state in CeONP and cyclic conversion of Ce(III)O→Ce(IV)O→Ce(III)O by reaction with H2O2 implied uninterrupted antioxidant property of CeONP. Moreover, the higher oxygen defect in the crystal lattice produced particles with higher antioxidant activity. CeONP was found to neutralize the deleterious effects of H2O2 viz., cell death, generation of intracellular reactive oxygen species and loss of connectivity in mouse neural cells. Therefore, CeONP might have potential use in future as an anti-oxidant drug.

  16. Green synthesized cerium oxide nanoparticle: A prospective drug against oxidative harm.

    PubMed

    Dutta, Debanjan; Mukherjee, Riya; Patra, Mousumi; Banik, Milon; Dasgupta, Rakhi; Mukherjee, Manabendra; Basu, Tarakdas

    2016-11-01

    Cerium oxide nanoparticle (CeONP) of size 2-3nm was synthesized by a new, simple and green method at ambient temperature, using cerium nitrate as prime precursor and Aloe vera leaf extract as stabilizing agent. Of the two oxidation states (+3) and (+4) of cerium, it was dominantly present in (+3) state in CeONP and cyclic conversion of Ce(III)O→Ce(IV)O→Ce(III)O by reaction with H2O2 implied uninterrupted antioxidant property of CeONP. Moreover, the higher oxygen defect in the crystal lattice produced particles with higher antioxidant activity. CeONP was found to neutralize the deleterious effects of H2O2 viz., cell death, generation of intracellular reactive oxygen species and loss of connectivity in mouse neural cells. Therefore, CeONP might have potential use in future as an anti-oxidant drug. PMID:27478962

  17. Toxicity of Cerium Oxide Nanoparticles in Human Lung Cancer Cells

    SciTech Connect

    Weisheng, Lin; Huang, Yue-wern; Zhou, Xiao Dong; Ma, Yinfa

    2006-12-31

    With the fast development of nanotechnology, the nanomaterials start to cause people's attention for potential toxic effect. In this paper, the cytotoxicity and oxidative stress caused by 20-nm cerium oxide (CeO2) nanoparticles in cultured human lung cancer cells was investigated. The sulforhodamine B method was employed to assess cell viability after exposure to 3.5, 10.5, and 23.3 μg/ml of CeO2 nanoparticles for 24, 48, and 72 h. Cell viability decreased significantly as a function of nanoparticle dose and exposure time. Indicators of oxidative stress and cytotoxicity, including total reactive oxygen species, glutathione, malondialdehyde, α-tocopherol, and lactate dehydrogenase, were quantitatively assessed. It is concluded from the results that free radicals generated by exposure to 3.5 to 23.3 μg/ml CeO2 nanoparticles produce significant oxidative stress in the cells, as reflected by reduced glutathione and α-tocopherol levels; the toxic effects of CeO2 nanoparticles are dose dependent and time dependent; elevated oxidative stress increases the production of malondialdehyde and lactate dehydrogenase, which are indicators of lipid peroxidation and cell membrane damage, respectively.

  18. Recent advances (2010-2015) in studies of cerium oxide nanoparticles' health effects.

    PubMed

    Li, Yan; Li, Peng; Yu, Hua; Bian, Ying

    2016-06-01

    Cerium oxide nanoparticles, widespread applied in our life, have attracted much concern for their human health effects. However, most of the works addressing cerium oxide nanoparticles toxicity have only used in vitro models or in vivo intratracheal instillation methods. The toxicity studies have varied results and not all are conclusive. The information about risk assessments derived from epidemiology studies is severely lacking. The knowledge of occupational safety and health (OSH) for exposed workers is very little. Thus this review focuses on recent advances in studies of toxicokinetics, antioxidant activity and toxicity. Additionally, aim to extend previous health effects assessments of cerium oxide nanoparticles, we summarize the epidemiology studies of engineered cerium oxide nanoparticles used as automotive diesel fuel additive, aerosol particulate matter in air pollution, other industrial ultrafine and nanoparticles (e.g., fumes particles generated in welding and flame cutting processes). PMID:27088851

  19. Direct growth of cerium oxide nanorods on diverse substrates for superhydrophobicity and corrosion resistance

    NASA Astrophysics Data System (ADS)

    Cho, Young Jun; Jang, Hanmin; Lee, Kwan-Soo; Kim, Dong Rip

    2015-06-01

    Superhydrophobic surfaces with anti-corrosion properties have attracted great interest in many industrial fields, particularly to enhance the thermal performance of offshore applications such as heat exchangers, pipelines, power plants, and platform structures. Nanostructures with hydrophobic materials have been widely utilized to realize superhydrophobicity of surfaces, and cerium oxide has been highlighted due to its good corrosion resistive and intrinsically hydrophobic properties. However, few studies of direct growth of cerium oxide nanostructures on diverse substrates have been reported. Herein we report a facile hydrothermal method to directly grow cerium oxide nanorods on diverse substrates, such as aluminum alloy, stainless steel, titanium, and silicon. Diverse substrates with cerium oxide nanorods exhibited superhydrophobicity with no hydrophobic modifiers on their surfaces, and showed good corrosion resistive properties in corrosive medium. We believe our method could pave the way for realization of scalable and sustainable corrosion resistive superhydrophobic surfaces in many industrial fields.

  20. Inhaled Diesel Emissions Generated with Cerium Oxide Nanoparticle Fuel Additive Induce Adverse Pulmonary and Systemic Effects

    EPA Science Inventory

    Diesel exhaust (DE) exposure induces adverse cardiopulmonary effects. Cerium oxide nanoparticles added to diesel fuel (DECe) increases fuel burning efficiency but leads to altered emission characteristics and potentially altered health effects. Here, we evaluated whether DECe res...

  1. Effects of uncoated and citric acid coated cerium oxide nanoparticles, bulk cerium oxide, cerium acetate, and citric acid on tomato plants.

    PubMed

    Barrios, Ana Cecilia; Rico, Cyren M; Trujillo-Reyes, Jesica; Medina-Velo, Illya A; Peralta-Videa, Jose R; Gardea-Torresdey, Jorge L

    2016-09-01

    Little is known about the physiological and biochemical responses of plants exposed to surface modified nanomaterials. In this study, tomato (Solanum lycopersicum L.) plants were cultivated for 210days in potting soil amended with uncoated and citric acid coated cerium oxide nanoparticles (nCeO2, CA+nCeO2) bulk cerium oxide (bCeO2), and cerium acetate (CeAc). Millipore water (MPW), and citric acid (CA) were used as controls. Physiological and biochemical parameters were measured. At 500mg/kg, both the uncoated and CA+nCeO2 increased shoot length by ~9 and ~13%, respectively, while bCeO2 and CeAc decreased shoot length by ~48 and ~26%, respectively, compared with MPW (p≤0.05). Total chlorophyll, chlo-a, and chlo-b were significantly increased by CA+nCeO2 at 250mg/kg, but reduced by bCeO2 at 62.5mg/kg, compared with MPW. At 250 and 500mg/kg, nCeO2 increased Ce in roots by 10 and 7 times, compared to CA+nCeO2, but none of the treatments affected the Ce concentration in above ground tissues. Neither nCeO2 nor CA+nCeO2 affected the homeostasis of nutrient elements in roots, stems, and leaves or catalase and ascorbate peroxidase in leaves. CeAc at 62.5 and 125mg/kg increased B (81%) and Fe (174%) in roots, while at 250 and 500mg/kg, increased Ca in stems (84% and 86%, respectively). On the other hand, bCeO2 at 62.5 increased Zn (152%) but reduced P (80%) in stems. Only nCeO2 at 62.5mg/kg produced higher total number of tomatoes, compared with control and the rest of the treatments. The surface coating reduced Ce uptake by roots but did not affect its translocation to the aboveground organs. In addition, there was no clear effect of surface coating on fruit production. To our knowledge, this is the first study comparing the effects of coated and uncoated nCeO2 on tomato plants.

  2. Effects of uncoated and citric acid coated cerium oxide nanoparticles, bulk cerium oxide, cerium acetate, and citric acid on tomato plants.

    PubMed

    Barrios, Ana Cecilia; Rico, Cyren M; Trujillo-Reyes, Jesica; Medina-Velo, Illya A; Peralta-Videa, Jose R; Gardea-Torresdey, Jorge L

    2016-09-01

    Little is known about the physiological and biochemical responses of plants exposed to surface modified nanomaterials. In this study, tomato (Solanum lycopersicum L.) plants were cultivated for 210days in potting soil amended with uncoated and citric acid coated cerium oxide nanoparticles (nCeO2, CA+nCeO2) bulk cerium oxide (bCeO2), and cerium acetate (CeAc). Millipore water (MPW), and citric acid (CA) were used as controls. Physiological and biochemical parameters were measured. At 500mg/kg, both the uncoated and CA+nCeO2 increased shoot length by ~9 and ~13%, respectively, while bCeO2 and CeAc decreased shoot length by ~48 and ~26%, respectively, compared with MPW (p≤0.05). Total chlorophyll, chlo-a, and chlo-b were significantly increased by CA+nCeO2 at 250mg/kg, but reduced by bCeO2 at 62.5mg/kg, compared with MPW. At 250 and 500mg/kg, nCeO2 increased Ce in roots by 10 and 7 times, compared to CA+nCeO2, but none of the treatments affected the Ce concentration in above ground tissues. Neither nCeO2 nor CA+nCeO2 affected the homeostasis of nutrient elements in roots, stems, and leaves or catalase and ascorbate peroxidase in leaves. CeAc at 62.5 and 125mg/kg increased B (81%) and Fe (174%) in roots, while at 250 and 500mg/kg, increased Ca in stems (84% and 86%, respectively). On the other hand, bCeO2 at 62.5 increased Zn (152%) but reduced P (80%) in stems. Only nCeO2 at 62.5mg/kg produced higher total number of tomatoes, compared with control and the rest of the treatments. The surface coating reduced Ce uptake by roots but did not affect its translocation to the aboveground organs. In addition, there was no clear effect of surface coating on fruit production. To our knowledge, this is the first study comparing the effects of coated and uncoated nCeO2 on tomato plants. PMID:26672385

  3. Induction of pulmonary fibrosis by cerium oxide nanoparticles

    PubMed Central

    Ma, Jane Y.; Mercer, Robert R.; Barger, Mark; Schwegler-Berry, Diane; Scabilloni, James; Ma, Joseph K.; Castranova, Vincent

    2015-01-01

    Cerium compounds have been used as a diesel engine catalyst to lower the mass of diesel exhaust particles, but are emitted as cerium oxide (CeO2) nanoparticles in the diesel exhaust. In a previous study, we have demonstrated a wide range of CeO2-induced lung responses including sustained pulmonary inflammation and cellular signaling that could lead to pulmonary fibrosis. In this study, we investigated the fibrogenic responses induced by CeO2 in a rat model at various time points up to 84 days post-exposure. Male Sprague Dawley rats were exposed to CeO2 by a single intratracheal instillation. Alveolar macrophages (AM) were isolated by bronchial alveolar lavage (BAL). AM-mediated cellular responses, osteopontin (OPN) and transform growth factor (TGF)-β1 in the fibrotic process were investigated. The results showed that CeO2 exposure significantly increased fibrotic cytokine TGF-β1 and OPN production by AM above controls. The collagen degradation enzymes, matrix metalloproteinase (MMP)-2 and -9 and the tissue inhibitor of MMP were markedly increased in the BAL fluid at 1 day- and subsequently declined at 28 days after exposure, but remained much higher than the controls. CeO2 induced elevated phospholipids in BAL fluid and increased hydroxyproline content in lung tissue in a dose- and time-dependent manner. Immunohistochemical analysis showed MMP-2, MMP-9 and MMP-10 expressions in fibrotic regions. Morphological analysis noted increased collagen fibers in the lungs exposed to a single dose of 3.5 mg/kg CeO2 and euthanized at 28 days post-exposure. Collectively, our studies show that CeO2 induced fibrotic lung injury in rats, suggesting it may cause potential health effects. PMID:22613087

  4. Pits confined in ultrathin cerium(IV) oxide for studying catalytic centers in carbon monoxide oxidation

    NASA Astrophysics Data System (ADS)

    Sun, Yongfu; Liu, Qinghua; Gao, Shan; Cheng, Hao; Lei, Fengcai; Sun, Zhihu; Jiang, Yong; Su, Haibin; Wei, Shiqiang; Xie, Yi

    2013-11-01

    Finding ideal material models for studying the role of catalytic active sites remains a great challenge. Here we propose pits confined in an atomically thin sheet as a platform to evaluate carbon monoxide catalytic oxidation at various sites. The artificial three-atomic-layer thin cerium(IV) oxide sheet with approximately 20% pits occupancy possesses abundant pit-surrounding cerium sites having average coordination numbers of 4.6 as revealed by X-ray absorption spectroscopy. Density-functional calculations disclose that the four- and five-fold coordinated pit-surrounding cerium sites assume their respective role in carbon monoxide adsorption and oxygen activation, which lowers the activation barrier and avoids catalytic poisoning. Moreover, the presence of coordination-unsaturated cerium sites increases the carrier density and facilitates carbon monoxide diffusion along the two-dimensional conducting channels of surface pits. The atomically thin sheet with surface-confined pits exhibits lower apparent activation energy than the bulk material (61.7 versus 122.9 kJ mol-1), leading to reduced conversion temperature and enhanced carbon monoxide catalytic ability.

  5. Pits confined in ultrathin cerium(IV) oxide for studying catalytic centers in carbon monoxide oxidation.

    PubMed

    Sun, Yongfu; Liu, Qinghua; Gao, Shan; Cheng, Hao; Lei, Fengcai; Sun, Zhihu; Jiang, Yong; Su, Haibin; Wei, Shiqiang; Xie, Yi

    2013-01-01

    Finding ideal material models for studying the role of catalytic active sites remains a great challenge. Here we propose pits confined in an atomically thin sheet as a platform to evaluate carbon monoxide catalytic oxidation at various sites. The artificial three-atomic-layer thin cerium(IV) oxide sheet with approximately 20% pits occupancy possesses abundant pit-surrounding cerium sites having average coordination numbers of 4.6 as revealed by X-ray absorption spectroscopy. Density-functional calculations disclose that the four- and five-fold coordinated pit-surrounding cerium sites assume their respective role in carbon monoxide adsorption and oxygen activation, which lowers the activation barrier and avoids catalytic poisoning. Moreover, the presence of coordination-unsaturated cerium sites increases the carrier density and facilitates carbon monoxide diffusion along the two-dimensional conducting channels of surface pits. The atomically thin sheet with surface-confined pits exhibits lower apparent activation energy than the bulk material (61.7 versus 122.9 kJ mol(-1)), leading to reduced conversion temperature and enhanced carbon monoxide catalytic ability.

  6. Antioxidant Cerium Oxide Nanoparticles in Biology and Medicine

    PubMed Central

    Nelson, Bryant C.; Johnson, Monique E.; Walker, Marlon L.; Riley, Kathryn R.; Sims, Christopher M.

    2016-01-01

    Previously, catalytic cerium oxide nanoparticles (CNPs, nanoceria, CeO2-x NPs) have been widely utilized for chemical mechanical planarization in the semiconductor industry and for reducing harmful emissions and improving fuel combustion efficiency in the automobile industry. Researchers are now harnessing the catalytic repertoire of CNPs to develop potential new treatment modalities for both oxidative- and nitrosative-stress induced disorders and diseases. In order to reach the point where our experimental understanding of the antioxidant activity of CNPs can be translated into useful therapeutics in the clinic, it is necessary to evaluate the most current evidence that supports CNP antioxidant activity in biological systems. Accordingly, the aims of this review are three-fold: (1) To describe the putative reaction mechanisms and physicochemical surface properties that enable CNPs to both scavenge reactive oxygen species (ROS) and to act as antioxidant enzyme-like mimetics in solution; (2) To provide an overview, with commentary, regarding the most robust design and synthesis pathways for preparing CNPs with catalytic antioxidant activity; (3) To provide the reader with the most up-to-date in vitro and in vivo experimental evidence supporting the ROS-scavenging potential of CNPs in biology and medicine. PMID:27196936

  7. Antioxidant Cerium Oxide Nanoparticles in Biology and Medicine.

    PubMed

    Nelson, Bryant C; Johnson, Monique E; Walker, Marlon L; Riley, Kathryn R; Sims, Christopher M

    2016-05-17

    Previously, catalytic cerium oxide nanoparticles (CNPs, nanoceria, CeO2-x NPs) have been widely utilized for chemical mechanical planarization in the semiconductor industry and for reducing harmful emissions and improving fuel combustion efficiency in the automobile industry. Researchers are now harnessing the catalytic repertoire of CNPs to develop potential new treatment modalities for both oxidative- and nitrosative-stress induced disorders and diseases. In order to reach the point where our experimental understanding of the antioxidant activity of CNPs can be translated into useful therapeutics in the clinic, it is necessary to evaluate the most current evidence that supports CNP antioxidant activity in biological systems. Accordingly, the aims of this review are three-fold: (1) To describe the putative reaction mechanisms and physicochemical surface properties that enable CNPs to both scavenge reactive oxygen species (ROS) and to act as antioxidant enzyme-like mimetics in solution; (2) To provide an overview, with commentary, regarding the most robust design and synthesis pathways for preparing CNPs with catalytic antioxidant activity; (3) To provide the reader with the most up-to-date in vitro and in vivo experimental evidence supporting the ROS-scavenging potential of CNPs in biology and medicine.

  8. Antioxidant cerium oxide nanoparticle hydrogels for cellular encapsulation.

    PubMed

    Weaver, Jessica D; Stabler, Cherie L

    2015-04-01

    Oxidative stress and the resulting radical by-products cause significant toxicity and graft loss in cellular transplantation. Here, the engineering of an auto-catalytic, antioxidant, self-renewing cerium oxide nanoparticle (CONP)-composite hydrogel is reported. This enzyme-mimetic material ubiquitously scavenges ambient free radicals, with the potential to provide indefinite antioxidant protection. The potential of this system to enhance the protection of encapsulated beta cells was evaluated. Co-incubation of CONPs free in solution with beta cells demonstrated potent cytoprotection from superoxide exposure; however, phagocytosis of the CONPs by the beta cells resulted in cytotoxicity at concentrations as low as 1mM. When CONPs were embedded within alginate hydrogels, the composite hydrogel provided cytoprotection to encapsulated beta cells from free radical attack without cytotoxicity, even up to 10mM. This nanocomposite hydrogel has wide applicability in cellular transplantation, with the unique advantage of localization of these potent antioxidant CONPs and their capacity for sustained, long-term scavenging. PMID:25620795

  9. Antioxidant Cerium Oxide Nanoparticle Hydrogels for Cellular Encapsulation

    PubMed Central

    Weaver, Jessica D; Stabler, Cherie L

    2015-01-01

    Oxidative stress and the resulting radical by-products cause significant toxicity and graft loss in cellular transplantation. Here, the engineering of an auto-catalytic, antioxidant, self-renewing cerium oxide nanoparticle (CONP)-composite hydrogel is reported. This enzyme-mimetic material ubiquitously scavenges ambient free radicals, with the potential to provide indefinite antioxidant protection. Here, we evaluated the potential of this system to enhance the protection of encapsulated beta cells. Co-incubation of CONPs, free in solution with beta cells, demonstrated potent cytoprotection from superoxide exposure; however, phagocytosis of the CONPs by the beta cells resulted in cytotoxicity at concentrations as low as 1 mM. When CONPs were embedded within alginate hydrogels, the composite hydrogel provided cytoprotection to encapsulated beta cells from free radical attack without cytotoxicity, even up to 10 mM concentrations. This nanocomposite hydrogel has wide applicability in cellular transplantation, with the unique advantage of localization of these potent antioxidant CONPs and their capacity for sustained, long-term scavenging. PMID:25620795

  10. Catalytic Properties and Biomedical Applications of Cerium Oxide Nanoparticles

    PubMed Central

    Walkey, Carl; Das, Soumen; Seal, Sudipta; Erlichman, Joseph; Heckman, Karin; Ghibelli, Lina; Traversa, Enrico; McGinnis, James F.; Self, William T.

    2014-01-01

    Cerium oxide nanoparticles (Nanoceria) have shown promise as catalytic antioxidants in the test tube, cell culture models and animal models of disease. However given the reactivity that is well established at the surface of these nanoparticles, the biological utilization of Nanoceria as a therapeutic still poses many challenges. Moreover the form that these particles take in a biological environment, such as the changes that can occur due to a protein corona, are not well established. This review aims to summarize the existing literature on biological use of Nanoceria, and to raise questions about what further study is needed to apply this interesting catalytic material to biomedical applications. These questions include: 1) How does preparation, exposure dose, route and experimental model influence the reported effects of Nanoceria in animal studies? 2) What are the considerations to develop Nanoceria as a therapeutic agent in regards to these parameters? 3) What biological targets of reactive oxygen species (ROS) and reactive nitrogen species (RNS) are relevant to this targeting, and how do these properties also influence the safety of these nanomaterials? PMID:26207185

  11. Antioxidant properties of cerium oxide nanocrystals as a function of nanocrystal diameter and surface coating.

    PubMed

    Lee, Seung Soo; Song, Wensi; Cho, Minjung; Puppala, Hema L; Nguyen, Phuc; Zhu, Huiguang; Segatori, Laura; Colvin, Vicki L

    2013-11-26

    This work examines the effect of nanocrystal diameter and surface coating on the reactivity of cerium oxide nanocrystals with H2O2 both in chemical solutions and in cells. Monodisperse nanocrystals were formed in organic solvents from the decomposition of cerium precursors, and subsequently phase transferred into water using amphiphiles as nanoparticle coatings. Quantitative analysis of the antioxidant capacity of CeO2-x using gas chromatography and a luminol test revealed that 2 mol of H2O2 reacted with every mole of cerium(III), suggesting that the reaction proceeds via a Fenton-type mechanism. Smaller diameter nanocrystals containing more cerium(III) were found to be more reactive toward H2O2. Additionally, the presence of a surface coating did not preclude the reaction between the nanocrystal surface cerium(III) and hydrogen peroxide. Taken together, the most reactive nanoparticles were the smallest (e.g., 3.8 nm diameter) with the thinnest surface coating (e.g., oleic acid). Moreover, a benchmark test of their antioxidant capacity revealed these materials were 9 times more reactive than commercial antioxidants such as Trolox. A unique feature of these antioxidant nanocrystals is that they can be applied multiple times: over weeks, cerium(IV) rich particles slowly return to their starting cerium(III) content. In nearly all cases, the particles remain colloidally stable (e.g., nonaggregated) and could be applied multiple times as antioxidants. These chemical properties were also observed in cell culture, where the materials were able to reduce oxidative stress in human dermal fibroblasts exposed to H2O2 with efficiency comparable to their solution phase reactivity. These data suggest that organic coatings on cerium oxide nanocrystals do not limit the antioxidant behavior of the nanocrystals, and that their redox cycling behavior can be preserved even when stabilized. PMID:24079896

  12. Variations in Reactivity on Different Crystallographic Orientations of Cerium Oxide

    SciTech Connect

    Mullins, David R; Albrecht, Peter M; Calaza, Florencia C

    2013-01-01

    Cerium oxide is a principal component in many heterogeneous catalytic processes. One of its key characteristics is the ability to provide or remove oxygen in chemical reactions. The different crystallographic faces of ceria present significantly different surface structures and compositions that may alter the catalytic reactivity. The structure and composition determine the number of coordination vacancies surrounding surface atoms, the availability of adsorption sites, the spacing between adsorption sites and the ability to remove O from the surface. To investigate the role of surface orientation on reactivity, CeO2 films were grown with two different orientations. CeO2(100) films were grown ex situ by pulsed laser deposition on Nb-doped SrTiO3(100). CeO2(111) films were grown in situ by thermal deposition of Ce metal onto Ru(0001) in an oxygen atmosphere. The chemical reactivity was characterized by the adsorption and decomposition of various molecules such as alcohols, aldehydes and organic acids. In general the CeO2(100) surface was found to be more active, i.e. molecules adsorbed more readily and reacted to form new products, especially on a fully oxidized substrate. However the CeO2(100) surface was less selective with a greater propensity to produce CO, CO2 and water as products. The differences in chemical reactivity are discussed in light of possible structural terminations of the two surfaces. Recently nanocubes and nano-octahedra have been synthesized that display CeO2(100) and CeO2(111) faces, respectively. These nanoparticles enable us to correlate reactions on high surface area model catalysts at atmospheric pressure with model single crystal films in a UHV environment.

  13. Precipitation-Redispersion of Cerium Oxide Nanoparticles with Poly(acrylic acid): Toward Stable Dispersions

    SciTech Connect

    Sehgal,A.; Lalatonne, Y.; Berret, J.; Morvan, M.

    2005-01-01

    We exploit a precipitation-redispersion mechanism for complexation of short chain polyelectrolytes with cerium oxide nanoparticles to extend their stability ranges. As synthesized, cerium oxide sols at pH 1.4 consist of monodisperse cationic nanocrystalline particles having a hydrodynamic diameter of 10 nm and a molecular weight of 400 000 g mol{sup -1}. We show that short chain uncharged poly(acrylic acid) at low pH when added to a cerium oxide sols leads to macroscopic precipitation. As the pH is increased, the solution spontaneously redisperses into a clear solution of single particles with an anionic poly(acrylic acid) corona. The structure and dynamics of cerium oxide nanosols and their hybrid polymer-inorganic complexes in solution are investigated by static and dynamic light scattering, X-ray scattering, and chemical analysis. Quantitative analysis of the redispersed sol gives rise to an estimate of 40-50 polymer chains per particle for stable suspension. This amount represents 20% of the mass of the polymer-nanoparticle complexes. This complexation adds utility to the otherwise unstable cerium oxide dispersions by extending the range of stability of the sols in terms of pH, ionic strength, and concentration.

  14. Soil organic matter influences cerium translocation and physiological processes in kidney bean plants exposed to cerium oxide nanoparticles.

    PubMed

    Majumdar, Sanghamitra; Peralta-Videa, Jose R; Trujillo-Reyes, Jesica; Sun, Youping; Barrios, Ana C; Niu, Genhua; Margez, Juan P Flores-; Gardea-Torresdey, Jorge L

    2016-11-01

    Soil organic matter plays a major role in determining the fate of the engineered nanomaterials (ENMs) in the soil matrix and effects on the residing plants. In this study, kidney bean plants were grown in soils varying in organic matter content and amended with 0-500mg/kg cerium oxide nanoparticles (nano-CeO2) under greenhouse condition. After 52days of exposure, cerium accumulation in tissues, plant growth and physiological parameters including photosynthetic pigments (chlorophylls and carotenoids), net photosynthesis rate, transpiration rate, and stomatal conductance were recorded. Additionally, catalase and ascorbate peroxidase activities were measured to evaluate oxidative stress in the tissues. The translocation factor of cerium in the nano-CeO2 exposed plants grown in organic matter enriched soil (OMES) was twice as the plants grown in low organic matter soil (LOMS). Although the leaf cover area increased by 65-111% with increasing nano-CeO2 concentration in LOMS, the effect on the physiological processes were inconsequential. In OMES leaves, exposure to 62.5-250mg/kg nano-CeO2 led to an enhancement in the transpiration rate and stomatal conductance, but to a simultaneous decrease in carotenoid contents by 25-28%. Chlorophyll a in the OMES leaves also decreased by 27 and 18% on exposure to 125 and 250mg/kg nano-CeO2. In addition, catalase activity increased in LOMS stems, and ascorbate peroxidase increased in OMES leaves of nano-CeO2 exposed plants, with respect to control. Thus, this study provides clear evidence that the properties of the complex soil matrix play decisive roles in determining the fate, bioavailability, and biological transport of ENMs in the environment.

  15. Soil organic matter influences cerium translocation and physiological processes in kidney bean plants exposed to cerium oxide nanoparticles.

    PubMed

    Majumdar, Sanghamitra; Peralta-Videa, Jose R; Trujillo-Reyes, Jesica; Sun, Youping; Barrios, Ana C; Niu, Genhua; Margez, Juan P Flores-; Gardea-Torresdey, Jorge L

    2016-11-01

    Soil organic matter plays a major role in determining the fate of the engineered nanomaterials (ENMs) in the soil matrix and effects on the residing plants. In this study, kidney bean plants were grown in soils varying in organic matter content and amended with 0-500mg/kg cerium oxide nanoparticles (nano-CeO2) under greenhouse condition. After 52days of exposure, cerium accumulation in tissues, plant growth and physiological parameters including photosynthetic pigments (chlorophylls and carotenoids), net photosynthesis rate, transpiration rate, and stomatal conductance were recorded. Additionally, catalase and ascorbate peroxidase activities were measured to evaluate oxidative stress in the tissues. The translocation factor of cerium in the nano-CeO2 exposed plants grown in organic matter enriched soil (OMES) was twice as the plants grown in low organic matter soil (LOMS). Although the leaf cover area increased by 65-111% with increasing nano-CeO2 concentration in LOMS, the effect on the physiological processes were inconsequential. In OMES leaves, exposure to 62.5-250mg/kg nano-CeO2 led to an enhancement in the transpiration rate and stomatal conductance, but to a simultaneous decrease in carotenoid contents by 25-28%. Chlorophyll a in the OMES leaves also decreased by 27 and 18% on exposure to 125 and 250mg/kg nano-CeO2. In addition, catalase activity increased in LOMS stems, and ascorbate peroxidase increased in OMES leaves of nano-CeO2 exposed plants, with respect to control. Thus, this study provides clear evidence that the properties of the complex soil matrix play decisive roles in determining the fate, bioavailability, and biological transport of ENMs in the environment. PMID:27343939

  16. A new class of homogeneous visible-light photocatalysts: molecular cerium vanadium oxide clusters.

    PubMed

    Seliverstov, Andrey; Streb, Carsten

    2014-07-28

    The first systematic access to molecular cerium vanadium oxides is presented. A family of structurally related, di-cerium-functionalized vanadium oxide clusters and their use as visible-light-driven photooxidation catalysts is reported. Comparative analyses show that photocatalytic activity is controlled by the cluster architecture. Increased photoreactivity of the cerium vanadium oxides in the visible range compared with nonfunctionalized vanadates is observed. Based on the recent discovery of the first molecular cerium vanadate cluster, (nBu4 N)2 [(Ce(dmso)3 )2 V12 O33 Cl]⋅2 DMSO (1), two new di-cerium-containing vanadium oxide clusters [(Ce(dmso)4 )2 V11 O30 Cl]⋅DMSO (2) and [(Ce(nmp)4 )2 V12 O32 Cl]⋅NMP⋅Me2 CO (3; NMP=N-methyl-2-pyrrolidone) were obtained by using a novel fragmentation and reassembly route. Pentagonal building units {(V)M5 } (M=V, Ce) reminiscent of "Müller-type" pentagons are observed in 2 and 3. Compounds 1-3 feature high visible-light photooxidative activity, and quantum efficiencies >10 % for indigo photooxidation are observed. Photocatalytic performance increases in the order 1<3<2. Mechanistic studies show that the irradiation wavelength and the presence of oxygen strongly affect photoreactivity. Initial findings suggest that the photooxidation mechanism proceeds by intermediate formation of hydroxyl radicals. The findings open new avenues for the bottom-up design of sunlight-driven photocatalysts.

  17. Effect of cerium oxide nanoparticles on intestinal serotonin in zebrafish

    PubMed Central

    Özel, Rıfat Emrah; Hayat, Akhtar; Wallace, Kenneth N.; Andreescu, Silvana

    2013-01-01

    Cerium oxide nanoparticles or nanoceria are emerging as a new and promising class of nanoparticle technology for biomedical applications. The safe implementation of these particles in clinical applications requires evaluation of their redox properties and reactivity that might cause neurotoxic effects by interacting with redox components of the physiological environment. We report in vitro and in vivo studies to evaluate the impact of nanoceria exposure on serotonin (5-HT), an important neurotransmitter that plays a critical role in various physiological processes including motility and secretion in the digestive system. In vitro studies of 5-HT in the presence of nanoceria using spectroscopic, electrochemical and surface characterization methods demonstrate that nanoceria interacts with 5-HT and forms a surface adsorbed 5-HT-nanoceria complex. Further in vivo studies in live zebrafish embryos indicate depletion of the 5-HT level in the intestine for exposure periods longer than three days. Intestinal 5-HT was assessed quantitatively in live embryos using implantable carbon fiber microelectrodes and the results were compared to immunohistochemistry of the dissected intestine. 20 and 50 ppm nanoparticle exposure decreased the 5-HT level to 20.5 (±1.3) and 5.3 (±1.5) nM respectively as compared to 30.8 (±3.4) nM for unexposed control embryos. The results suggest that internalized nanoceria particles can concentrate 5-HT at the nanoparticle accumulation site depleting it from the surrounding tissue. This finding might have long term implications in the neurophysiology and functional development of organisms exposed to these particles through intended or unintended exposure. PMID:24015353

  18. Cerium oxide nanoparticle treatment ameliorates peritonitis-induced diaphragm dysfunction

    PubMed Central

    Asano, Shinichi; Arvapalli, Ravikumar; Manne, Nandini DPK; Maheshwari, Mani; Ma, Bing; Rice, Kevin M; Selvaraj, Vellaisamy; Blough, Eric R

    2015-01-01

    The severe inflammation observed during sepsis is thought to cause diaphragm dysfunction, which is associated with poor patient prognosis. Cerium oxide (CeO2) nanoparticles have been posited to exhibit anti-inflammatory and antioxidative activities suggesting that these particles may be of potential use for the treatment of inflammatory disorders. To investigate this possibility, Sprague Dawley rats were randomly assigned to the following groups: sham control, CeO2 nanoparticle treatment only (0.5 mg/kg iv), sepsis, and sepsis+CeO2 nanoparticles. Sepsis was induced by the introduction of cecal material (600 mg/kg) directly into the peritoneal cavity. Nanoparticle treatment decreased sepsis-associated impairments in diaphragmatic contractile (Po) function (sham: 25.6±1.6 N/cm2 vs CeO2: 23.4±0.8 N/cm2 vs Sep: 15.9±1.0 N/cm2 vs Sep+CeO2: 20.0±1.0 N/cm2, P<0.05). These improvements in diaphragm contractile function were accompanied by a normalization of protein translation signaling (Akt, FOXO-1, and 4EBP1), diminished proteolysis (caspase 8 and ubiquitin levels), and decreased inflammatory signaling (Stat3 and iNOS). Histological analysis suggested that nanoparticle treatment was associated with diminished sarcolemma damage and diminished inflammatory cell infiltration. These data indicate CeO2 nanoparticles may improve diaphragmatic function in the septic laboratory rat. PMID:26491293

  19. Effect of cerium oxide nanoparticles on intestinal serotonin in zebrafish.

    PubMed

    Ozel, Rıfat Emrah; Hayat, Akhtar; Wallace, Kenneth N; Andreescu, Silvana

    2013-09-21

    Cerium oxide nanoparticles or nanoceria are emerging as a new and promising class of nanoparticle technology for biomedical applications. The safe implementation of these particles in clinical applications requires evaluation of their redox properties and reactivity that might cause neurotoxic effects by interacting with redox components of the physiological environment. We report in vitro and in vivo studies to evaluate the impact of nanoceria exposure on serotonin (5-HT), an important neurotransmitter that plays a critical role in various physiological processes including motility and secretion in the digestive system. In vitro studies of 5-HT in the presence of nanoceria using spectroscopic, electrochemical and surface characterization methods demonstrate that nanoceria interacts with 5-HT and forms a surface adsorbed 5-HT-nanoceria complex. Further in vivo studies in live zebrafish embryos indicate depletion of the 5-HT level in the intestine for exposure periods longer than three days. Intestinal 5-HT was assessed quantitatively in live embryos using implantable carbon fiber microelectrodes and the results were compared to immunohistochemistry of the dissected intestine. 20 and 50 ppm nanoparticle exposure decreased the 5-HT level to 20.5 (±1.3) and 5.3 (±1.5) nM respectively as compared to 30.8 (±3.4) nM for unexposed control embryos. The results suggest that internalized nanoceria particles can concentrate 5-HT at the nanoparticle accumulation site depleting it from the surrounding tissue. This finding might have long term implications in the neurophysiology and functional development of organisms exposed to these particles through intended or unintended exposure. PMID:24015353

  20. Effects of Cerium Oxide Nanoparticles on Sorghum Plant Traits

    NASA Astrophysics Data System (ADS)

    Mu, L.; Chen, Y.; Darnault, C. J. G.; Rauh, B.; Kresovich, S.; Korte, C.

    2015-12-01

    Nanotechnology and nanomaterials are considered as the development of the modern science. However, besides with that wide application, nanoparticles arouse to the side effects on the environment and human health. As the catalyst of ceramics and fuel industry, Cerium (IV) oxide nanoparticles (CeO2 NPs) can be found in the environment following their use and life-cycle. Therefore, it is critical to assess the potential effects that CeO2 NPs found in soils may have on plants. In this study, CeO2 NPs were analyzed for the potential influence on the sorghum [Sorghum bicolor (L.) Moench] (Reg. no. 126) (PI 154844) growth and traits. The objectives of this research were to determine whether CeO2 NPs impact the sorghum germination and growth characteristics. The sorghum was grown in the greenhouse located at Biosystems Research Complex, Clemson University under different CeO2 NPs treatments (0mg; 100mg; 500mg; 1000mg CeO2 NPs/Kg soil) and harvested around each month. At the end of the each growing period, above ground vegetative tissue was air-dried, ground to 2mm particle size and compositional traits estimated using near-infrared spectroscopy. Also, the NPK value of the sorghum tissue was tested by Clemson Agriculture Center. After the first harvest, the result showed that the height of above ground biomass under the nanoparticles stress was higher than that of control group. This difference between the control and the nanoparticles treatments was significant (F>F0.05; LSD). Our results also indicated that some of the compositional traits were impacted by the different treatments, including the presence and/or concentrations of the nanoparticles.

  1. THERMAL EFFECTS ON MASS AND SPATIAL RESOLUTION DURING LASER PULSE ATOM PROBE TOMOGRAPHY OF CERIUM OXIDE

    SciTech Connect

    Rita Kirchhofer; Melissa C. Teague; Brian P. Gorman

    2013-05-01

    Cerium oxide (CeO2) is an ideal surrogate material for trans-uranic elements and fission products found in nuclear fuels due to similarities in their thermal properties; therefore, cerium oxide was used to determine the best run condition for atom probe tomography (APT). Laser pulse APT is a technique that allows for spatial resolution in the nm scale and isotopic/elemental chemical identification. A systematic study of the impact of laser pulse energy and specimen base temperature on the mass resolution, measurement of stoichiometry, multiples, and evaporation mechanisms are reported in this paper. It was demonstrated that using laser pulse APT stoichiometric field evaporation of cerium oxide was achieved at 1 pJ laser pulse energy and 20 K specimen base temperature.

  2. Photoemission of the Oxidation of Cerium Overlayers on GaSb(110) Surface

    NASA Astrophysics Data System (ADS)

    Liang, Qi; Wu, Jian-xin; Ji, Ming-rong; Ma, Mao-sheng; Liu, Xian-ming; Zhang, Yu-heng

    1997-10-01

    We have used x-ray photoelectron spectroscopy to study the oxidation of cerium overlayers on a semiconductor GaSb(110) surface. A GaSb(110) sample covered with 10 monolayers Ce was used to adsorb oxygen. When the exposure of O2 was up to 50 L, the oxide of cerium, Ce2O3, began to change into unstable CeO2. The dissociation of CeO2 resulted in strong oxidation of the substrate. The main products are Ga2O3, Sb2O3, and then Sb2O5. After annealing, a part of the oxygen atoms transferred from cerium dioxide toward Ga and Sb.

  3. Development of graphene-nanometre-sized cerium oxide-incorporated aluminium and its electrochemical evaluation

    NASA Astrophysics Data System (ADS)

    Ashraf, P. Muhamed; Thomas, Saly N.; Edwin, Leela

    2016-02-01

    Graphene-nanometre-sized cerium oxide-incorporated aluminium was prepared and its electrochemical and surface morphological characteristics were studied. The atomic force micrographs and scanning electron micrographs evaluation highlighted that the graphene and nanometre-sized cerium oxide in aluminium had decreased the surface roughness and improved the surface morphological characteristics. The graphene: nanometre-sized cerium oxide (ratios 1:2 or 2:1) with lesser amounts of particle in the matrix showed excellent corrosion resistance in the marine environment as evidenced by linear polarization, electrochemical impedance and weight loss studies. Introduction of graphene in the aluminium matrix showed a barrier separation between the outermost layer and inner layer, increased roughness and increased corrosion. The material is found to be a potential candidate for use in marine environment.

  4. Synthesis and catalytic properties of microemulsion-derived cerium oxide nanoparticles

    SciTech Connect

    Kockrick, Emanuel; Schrage, Christian; Grigas, Anett; Geiger, Dorin; Kaskel, Stefan

    2008-07-15

    The synthesis of cerium dioxide nanoparticles using an inverse microemulsion technique and precipitation method was investigated. Cerium hydroxide nanoparticles were synthesized by adding diluted ammonia to n-heptane-surfactant-cerium nitrate system. The micelle and particle size in the range of 5-12 nm were controlled by varying the molar water to surfactant ratio and analyzed by dynamic light scattering (DLS), small angle X-ray scattering (SAXS) and high-resolution transmission electron microscopy (HRTEM). Cerium hydroxide nanoparticles were isolated and subsequently treated at 100-600 deg. C to obtain nanoscale ceria. Crystallite sizes of cerium dioxide in the range of 6-16 nm were estimated by Scherrer analysis by X-ray diffraction (XRD) and HRTEM. The catalytic activity of particles annealed at 400 and 600 deg. C in soot combustion reactions was characterized by temperature-programmed oxidation (TPO) indicating a size-dependant activity. Crystallite sizes and catalytic stability of elevated ceria systems were tested in second combustion cycles. - Graphical abstract: The synthesis of cerium dioxide nanoparticles using an inverse microemulsion technique and precipitation method was investigated using small angle X-ray scattering, dynamic light scattering and high-resolution transmission electron microscopy. Catalytic activity of ceria nanoparticles was tested in soot combustion reaction indicating size-dependent reactivity.

  5. Cerium Oxide Nanoparticles and Bulk Cerium Oxide Leading to Different Physiological and Biochemical Responses in Brassica rapa.

    PubMed

    Ma, Xingmao; Wang, Qiang; Rossi, Lorenzo; Zhang, Weilan

    2016-07-01

    Cerium oxide nanoparticles (CeO2NPs) have been incorporated into many commercial products, and their potential release into the environment through the use and disposal of these products has caused serious concerns. Despite the previous efforts and rapid progress on elucidating the environmental impact of CeO2NPs, the long-term impact of CeO2NPs to plants, a key component of the ecosystem, is still not well understood. The potentially different impact of CeO2NPs and their bulk counterparts to plants is also unclear. The main objectives of this study were (1) to investigate whether continued irrigation with solutions containing different concentrations of CeO2NPs (0, 10, and 100 mg/L) would induce physiological and biochemical adjustments in Brassica rapa in soil growing conditions and (2) to determine whether CeO2NPs and bulk CeO2 particles exert different impacts on plants. The results indicated that bulk CeO2 at 10 and 100 mg/L enhanced plant biomass by 28% and 35%, respectively, while CeO2NPs at equivalent concentrations did not. While the bulk CeO2 treatment resulted in significantly higher concentrations of hydrogen peroxide (H2O2) in plant tissues at the vegetative stage, CeO2NPs led to significantly higher H2O2 levels in plant tissues at the floral stage. The activity of superoxide dismutase (SOD) in Brassica rapa also displayed a growth-stage dependent response to different sizes of CeO2 while catalase (CAT) activity was not affected by either size of CeO2 throughout the life cycle of Brassica rapa. Altogether, the results demonstrated that plant responses to CeO2 exposure varied with the particle sizes and the growth stages of plants.

  6. Cerium Oxide Nanoparticles and Bulk Cerium Oxide Leading to Different Physiological and Biochemical Responses in Brassica rapa.

    PubMed

    Ma, Xingmao; Wang, Qiang; Rossi, Lorenzo; Zhang, Weilan

    2016-07-01

    Cerium oxide nanoparticles (CeO2NPs) have been incorporated into many commercial products, and their potential release into the environment through the use and disposal of these products has caused serious concerns. Despite the previous efforts and rapid progress on elucidating the environmental impact of CeO2NPs, the long-term impact of CeO2NPs to plants, a key component of the ecosystem, is still not well understood. The potentially different impact of CeO2NPs and their bulk counterparts to plants is also unclear. The main objectives of this study were (1) to investigate whether continued irrigation with solutions containing different concentrations of CeO2NPs (0, 10, and 100 mg/L) would induce physiological and biochemical adjustments in Brassica rapa in soil growing conditions and (2) to determine whether CeO2NPs and bulk CeO2 particles exert different impacts on plants. The results indicated that bulk CeO2 at 10 and 100 mg/L enhanced plant biomass by 28% and 35%, respectively, while CeO2NPs at equivalent concentrations did not. While the bulk CeO2 treatment resulted in significantly higher concentrations of hydrogen peroxide (H2O2) in plant tissues at the vegetative stage, CeO2NPs led to significantly higher H2O2 levels in plant tissues at the floral stage. The activity of superoxide dismutase (SOD) in Brassica rapa also displayed a growth-stage dependent response to different sizes of CeO2 while catalase (CAT) activity was not affected by either size of CeO2 throughout the life cycle of Brassica rapa. Altogether, the results demonstrated that plant responses to CeO2 exposure varied with the particle sizes and the growth stages of plants. PMID:26691446

  7. Hydrothermal preparation of fractal dendrites: Cerium carbonate hydroxide and cerium oxide

    SciTech Connect

    Wu Mingzai; Zhang Qihua; Liu Yanmei; Fang Qingqing; Liu Xiansong

    2009-06-03

    The surfactant-assisted hydrothermal route was used to prepare fractal dendrite cerium carbonate hydroxide (CeOHCO{sub 3}) microstructures. After annealing at 600 deg. C for 4 h, the products were transformed to CeO{sub 2}. The crystal structures of the two compounds were determined by X-ray diffraction (XRD). The morphologies and microstructures were characterized by field emission scanning electron microscopy (FESEM) and high-resolution transmission electron microscopy (HRTEM). Room temperature photoluminescence (PL) showed that a strong ultraviolet emission at 336 nm was observed for CeOHCO{sub 3}, and that centered at 415 nm for CeO{sub 2} microstructures. Both of these emission peaks are different from those reported for CeOHCO{sub 3} and CeO{sub 2} with other shapes. In addition, the possible growth mechanism of dendrite CeOHCO{sub 3} microstructures and the role of surfactant polyvinyl pyrrolidone (PVP) were also investigated in this paper.

  8. Studies of Solution Deposited Cerium Oxide Thin Films on Textured Ni-Alloy Substractes for YBCO Superconductor

    SciTech Connect

    Stewart, Erin L; Bhuiyan, Md S; Sathyamurthy, Srivatsan; Paranthaman, Mariappan Parans

    2006-01-01

    Cerium oxide (CeO2) buffer layers play an important role for the development of YBa2Cu3O7-x (YBCO) based superconducting tapes using the rolling assisted biaxially textured substrates (RABiTS) approach. The chemical solution deposition (CSD) approach has been used to grow epitaxial CeO2 films on textured Ni-3 a 4% W alloy substrates with various starting precursors of ceria. Precursors such as cerium acetate, cerium acetylacetonate, cerium 2-ethylhexanoate, cerium nitrate, and cerium trifluoroacetate were prepared in suitable solvents. The optimum growth conditions for these cerium precursors were Ar-4% H2 gas processing atmosphere, solution concentration levels of 0.2-0.5 M, a dwell time of 15 min, and a process temperature range of 1050-1150 degrees C. X-ray diffraction, AFM, SEM, and optical microscopy were used to characterize the CeO2 films. Highly textured CeO2 layers were obtained on Ni-W substrates with both cerium acetate and cerium acetylacetonate as starting precursors. YBCO films with a Jc of 1.5 MA/cm2 were obtained on cerium acetylacetonate-based CeO2 films with sputtered YSZ and CeO2 cap layers.

  9. Phenotypic and genomic responses to titanium dioxide and cerium oxide nanoparticles in Arabidopsis germinants

    EPA Science Inventory

    The effects of exposure to two nanoparticles (NPs) -titanium dioxide (nano-titania) and cerium oxide (nano-ceria) at 500 mg NPs L-1 on gene expression and growth in Arabidopsis thaliana germinants were studied using microarrays and phenotype studies. After 12 days post treatment,...

  10. Exposure of cerium oxide nanoparticles to kidney bean shows disturbance in the plant defense mechanisms.

    PubMed

    Majumdar, Sanghamitra; Peralta-Videa, Jose R; Bandyopadhyay, Susmita; Castillo-Michel, Hiram; Hernandez-Viezcas, Jose-Angel; Sahi, Shivendra; Gardea-Torresdey, Jorge L

    2014-08-15

    Overwhelming use of engineered nanoparticles demands rapid assessment of their environmental impacts. The transport of cerium oxide nanoparticles (nCeO2) in plants and their impact on cellular homeostasis as a function of exposure duration is not well understood. In this study, kidney bean plants were exposed to suspensions of ∼ 8 ± 1 nm nCeO2 (62.5 to 500 mg/L) for 15 days in hydroponic conditions. Plant parts were analyzed for cerium accumulation after one, seven, and 15 days of nCeO2 exposure. The primary indicators of stress like lipid peroxidation, antioxidant enzyme activities, total soluble protein and chlorophyll contents were studied. Cerium in tissues was localized using scanning electron microscopy and synchrotron μ-XRF mapping, and the chemical forms were identified using μ-XANES. In the root epidermis, cerium was primarily shown to exist as nCeO2, although a small fraction (12%) was biotransformed to Ce(III) compound. Cerium was found to reach the root vascular tissues and translocate to aerial parts with time. Upon prolonged exposure to 500 mg nCeO2/L, the root antioxidant enzyme activities were significantly reduced, simultaneously increasing the root soluble protein by 204%. In addition, leaf's guaiacol peroxidase activity was enhanced with nCeO2 exposure in order to maintain cellular homeostasis. PMID:24981679

  11. Exposure, Health and Ecological Effects Review of Engineered Nanoscale Cerium and Cerium Oxide Associated with its Use as a Fuel Additive

    EPA Science Inventory

    Advances of nanoscale science have produced nanomaterials with unique physical and chemical properties at commercial levels which are now incorporated into over 1000 products. Nanoscale cerium (di) oxide (CeO(2)) has recently gained a wide range of applications which includes coa...

  12. Antiapoptotic effects of cerium oxide and yttrium oxide nanoparticles in isolated rat pancreatic islets.

    PubMed

    Hosseini, A; Baeeri, M; Rahimifard, M; Navaei-Nigjeh, M; Mohammadirad, A; Pourkhalili, N; Hassani, S; Kamali, M; Abdollahi, M

    2013-05-01

    Type I diabetes mellitus is a metabolic disease caused by the impairment of pancreatic β-cells mainly mediated through oxidative stress and related apoptosis. Islets transplantation seems a promising treatment for these patients, but during islets transplant, various types of stresses related to the isolation and transplantation procedure compromise the function and viability of islets. We recently hypothesized that the combination of cerium oxide (CeO2) and yttrium oxide (Y2O3) nanoparticles with a potential free radical scavenger behavior should be useful to make isolated islets survive until transplanted. In the present study, oxidative stress-induced apoptosis in isolated rat pancreatic islets exposed to hydrogen peroxide (H2O2) and the protective effects of CeO2 and Y2O3 nanoparticles were investigated. Exposure of islets to H2O2 (50 µm, 2 h) increased intracellular oxidant formation such as reactive oxygen species and subsequently apoptosis and decreased viability, glucose-induced adenosine triphosphate (ATP) production and glucose-stimulated insulin secretion. Pretreatment with CeO2 and/or Y2O3 nanoparticles reduced the oxidant formation and apoptosis and increased viability, glucose-induced ATP production and glucose-stimulated insulin secretion. These results suggest that this combination may protect β-cell apoptosis by improving the oxidative stress-mediated apoptotic pathway.

  13. Shifts in oxidation states of cerium oxide nanoparticles detected inside intact hydrated cells and organelles

    PubMed Central

    Szymanski, Craig J.; Munusamy, Prabhakaran; Mihai, Cosmin; Xie, Yumei; Hu, Dehong; Gilles, Mary K.; Tyliszczak, Tolek; Thevuthasan, Suntharampillai; Baer, Donald R.; Orr, Galya

    2015-01-01

    Cerium oxide nanoparticles (CNPs) have been shown to induce diverse biological effects, ranging from toxic to beneficial. The beneficial effects have been attributed to the potential antioxidant activity of CNPs via certain redox reactions, depending on their oxidation state or Ce3+/Ce4+ ratio. However, this ratio is strongly dependent on the environment and age of the nanoparticles and it is unclear whether and how the complex intracellular environment impacts this ratio and the possible redox reactions of CNPs. To identify any changes in the oxidation state of CNPs in the intracellular environment and better understand their intracellular reactions, we directly quantified the oxidation states of CNPs outside and inside intact hydrated cells and organelles using correlated scanning transmission x-ray and super resolution fluorescence microscopies. By analyzing hundreds of small CNP aggregates, we detected a shift to a higher Ce3+/Ce4+ ratio in CNPs inside versus outside the cells, indicating a net reduction of CNPs in the intracellular environment. We further found a similar ratio in the cytoplasm and in the lysosomes, indicating that the net reduction occurs earlier in the internalization pathway. Together with oxidative stress and toxicity measurements, our observations identify a net reduction of CNPs in the intracellular environment, which is consistent with their involvement in potentially beneficial oxidation reactions, but also point to interactions that can negatively impact the health of cells. PMID:26056725

  14. Shifts in oxidation states of cerium oxide nanoparticles detected inside intact hydrated cells and organelles

    SciTech Connect

    Szymanski, Craig J.; Munusamy, Prabhakaran; Mihai, Cosmin; Xie, Yumei; Hu, Dehong; Gilles, Marry K.; Tyliszczak, T.; Thevuthasan, Suntharampillai; Baer, Donald R.; Orr, Galya

    2015-09-01

    Cerium oxide nanoparticles (CNPs) have been shown to induce diverse biological effects, ranging from toxic to beneficial. The beneficial effects have been attributed to the potential antioxidant activity of CNPs via certain redox reactions, depending on their oxidation state or Ce3+/Ce4+ ratio. However, this ratio is strongly dependent on the environment and age of the nanoparticles and it is unclear whether and how the complex intracellular environment impacts this ratio and the possible redox reactions of CNPs. To identify any changes in the oxidation state of CNPs in the intracellular environment and better understand their intracellular reactions, we directly quantified the oxidation states of CNPs outside and inside intact hydrated cells and organelles using correlated scanning transmission x-ray and super resolution fluorescence microscopies. By analyzing hundreds of small CNP aggregates, we detected a shift to a higher Ce3+/Ce4+ ratio in CNPs inside versus outside the cells, indicating a net reduction of CNPs in the intracellular environment. We further found a similar ratio in the cytoplasm and in the lysosomes, indicating that the net reduction occurs earlier in the internalization pathway. Together with oxidative stress and toxicity measurements, our observations identify a net reduction of CNPs in the intracellular environment, which is consistent with their involvement in potentially beneficial oxidation reactions, but also point to interactions that can negatively impact the health of cells.

  15. Shifts in oxidation states of cerium oxide nanoparticles detected inside intact hydrated cells and organelles.

    PubMed

    Szymanski, Craig J; Munusamy, Prabhakaran; Mihai, Cosmin; Xie, Yumei; Hu, Dehong; Gilles, Mary K; Tyliszczak, Tolek; Thevuthasan, Suntharampillai; Baer, Donald R; Orr, Galya

    2015-09-01

    Cerium oxide nanoparticles (CNPs) have been shown to induce diverse biological effects, ranging from toxic to beneficial. The beneficial effects have been attributed to the potential antioxidant activity of CNPs via certain redox reactions, depending on their oxidation state or Ce(3+)/Ce(4+) ratio. However, this ratio is strongly dependent on the environment and age of the nanoparticles and it is unclear whether and how the complex intracellular environment impacts this ratio and the possible redox reactions of CNPs. To identify any changes in the oxidation state of CNPs in the intracellular environment and better understand their intracellular reactions, we directly quantified the oxidation states of CNPs outside and inside intact hydrated cells and organelles using correlated scanning transmission x-ray and super resolution fluorescence microscopies. By analyzing hundreds of small CNP aggregates, we detected a shift to a higher Ce(3+)/Ce(4+) ratio in CNPs inside versus outside the cells, indicating a net reduction of CNPs in the intracellular environment. We further found a similar ratio in the cytoplasm and in the lysosomes, indicating that the net reduction occurs earlier in the internalization pathway. Together with oxidative stress and toxicity measurements, our observations identify a net reduction of CNPs in the intracellular environment, which is consistent with their involvement in potentially beneficial oxidation reactions, but also point to interactions that can negatively impact the health of the cells.

  16. Stability and morphology of cerium oxide surfaces in an oxidizing environment: A first-principles investigation

    NASA Astrophysics Data System (ADS)

    Fronzi, Marco; Soon, Aloysius; Delley, Bernard; Traversa, Enrico; Stampfl, Catherine

    2009-09-01

    We present density functional theory investigations of the bulk properties of cerium oxides (CeO2 and Ce2O3) and the three low index surfaces of CeO2, namely, (100), (110), and (111). For the surfaces, we consider various terminations including surface defects. Using the approach of "ab initio atomistic thermodynamics," we find that the most stable surface structure considered is the stoichiometric (111) surface under "oxygen-rich" conditions, while for a more reducing environment, the same (111) surface, but with subsurface oxygen vacancies, is found to be the most stable one, and for a highly reducing environment, the (111) Ce-terminated surface becomes energetically favored. Interestingly, this latter surface exhibits a significant reconstruction in that it becomes oxygen terminated and the upper layers resemble the Ce2O3(0001) surface. This structure could represent a precursor to the phase transition of CeO2 to Ce2O3.

  17. Phosphate ester hydrolysis of biologically relevant molecules by cerium oxide nanoparticles.

    PubMed

    Kuchma, Melissa Hirsch; Komanski, Christopher B; Colon, Jimmie; Teblum, Andrew; Masunov, Artëm E; Alvarado, Beatrice; Babu, Suresh; Seal, Sudipta; Summy, Justin; Baker, Cheryl H

    2010-12-01

    In an effort to characterize the interaction of cerium oxide nanoparticles (CNPs) in biological systems, we explored the reactivity of CNPs with the phosphate ester bonds of p-nitrophenylphosphate (pNPP), ATP, o-phospho-l-tyrosine, and DNA. The activity of the bond cleavage for pNPP at pH 7 is calculated to be 0.860 ± 0.010 nmol p-nitrophenol/min/μg CNPs. Interestingly, when CNPs bind to plasmid DNA, no cleavage products are detected. While cerium(IV) complexes generally exhibit the ability to break phosphorus-oxygen bonds, the reactions we report appear to be dependent on the availability of cerium(III) sites, not cerium(IV) sites. We investigated the dephosphorylation mechanism from the first principles and find the reaction proceeds through inversion of the phosphate group similar to an S(N)2 mechanism. The ability of CNPs to interact with phosphate ester bonds of biologically relevant molecules has important implications for their use as potential therapeutics.

  18. Cerium Oxide Nanoparticles Reduce Microglial Activation and Neurodegenerative Events in Light Damaged Retina

    PubMed Central

    Fiorani, Lavinia; Passacantando, Maurizio; Santucci, Sandro; Di Marco, Stefano; Bisti, Silvia; Maccarone, Rita

    2015-01-01

    The first target of any therapy for retinal neurodegeneration is to slow down the progression of the disease and to maintain visual function. Cerium oxide or ceria nanoparticles reduce oxidative stress, which is known to play a pivotal role in neurodegeneration. Our aim was to investigate whether cerium oxide nanoparticles were able to mitigate neurodegeneration including microglial activation and related inflammatory processes induced by exposure to high intensity light. Cerium oxide nanoparticles were injected intravitreally or intraveinously in albino Sprague-Dawley rats three weeks before exposing them to light damage of 1000 lux for 24 h. Electroretinographic recordings were performed a week after light damage. The progression of retinal degeneration was evaluated by measuring outer nuclear layer thickness and TUNEL staining to quantify photoreceptors death. Immunohistochemical analysis was used to evaluate retinal stress, neuroinflammatory cytokines and microglial activation. Only intravitreally injected ceria nanoparticles were detected at the level of photoreceptor outer segments 3 weeks after the light damage and electoretinographic recordings showed that ceria nanoparticles maintained visual response. Moreover, this treatment reduced neuronal death and “hot spot” extension preserving the outer nuclear layer morphology. It is noteworthy that in this work we demonstrated, for the first time, the ability of ceria nanoparticles to reduce microglial activation and their migration toward outer nuclear layer. All these evidences support ceria nanoparticles as a powerful therapeutic agent in retinal neurodegenerative processes. PMID:26469804

  19. Unveiling the mechanism of uptake and sub-cellular distribution of cerium oxide nanoparticles†

    PubMed Central

    Singh, Sanjay; Kumar, Amit; Karakoti, Ajay; Seal, Sudipta; Self, William T.

    2011-01-01

    Cerium oxide nanoparticles (CNPs) have been recently studied for their potent superoxide scavenging properties in both cell and animal model systems. Data from these model systems have shown that exposure of cells to CNPs results in the protection against reactive oxygen species (ROS). Despite these exciting findings, very little is known regarding the uptake or subcellular distribution of these nanomaterials inside cells. In this study we utilized fluorophore (carboxyfluorescein) conjugated cerium oxide NPs (CCNPs) to study the mechanism of uptake and to elucidate the subcellular localization of CNPs using a keratinocyte model system. We observed rapid uptake (within 3 h) of CCNPs that was governed by energy-dependent, clathrin-mediated and caveolae-mediated endocytic pathways. We found CCNPs co-localized with mitochondria, lysosomes and endoplasmic reticulum as well as being abundant in the cytoplasm and the nucleus. Given the radical scavenging properties of cerium oxide and the widespread cellular disposition we observed, CNPs likely act as cellular antioxidants in multiple compartments of the cell imparting protection against a variety of oxidant injuries. PMID:20697616

  20. Aqueous Co-precipitation of Pd-doped Cerium Oxide Nanoparticles: Chemistry Structure and Particle Growth

    SciTech Connect

    Liang H.; Zhang L.; Raitano J.M.; He G.; Akey A.J.; Herman I.P.; Chan S.-W.

    2012-01-01

    Nanoparticles of palladium-doped cerium oxide (Pd-CeO{sub 2}) have been prepared by aqueous co-precipitation resulting in a single phase cubic structure after calcination according to X-ray diffraction (XRD). Inhomogeneous strain, calculated using the Williamson-Hall method, was found to increase with palladium content, and the lattice contracts slightly, relative to nano-cerium oxide, as palladium content is increased. Moreover, high resolution transmission electron microscopy reveals some instances of defective microstructure. These factors combined imply that palladium is in solid solution with CeO{sub 2} in these nanoparticles, but palladium (II) oxide (PdO) peaks in the Raman spectra indicate that solid solution formation is partial and that highly dispersed PdO is present as well as the solid solution. Nevertheless, the addition of palladium to the CeO{sub 2} lattice inhibits the growth of the 6% Pd-CeO{sub 2} particles compared to pure CeO{sub 2} between 600 and 850 C. Activation energies for grain growth of 54 {+-} 7 and 79 {+-} 8 kJ/mol were determined for 6% Pd-CeO{sub 2} and pure CeO{sub 2}, respectively, along with pre-exponential Arrhenius factors of 10 for the doped sample and 600 for pure cerium oxide.

  1. Cerium oxide nanoparticles protect endothelial cells from apoptosis induced by oxidative stress.

    PubMed

    Chen, Shizhu; Hou, Yingjian; Cheng, Gong; Zhang, Cuimiao; Wang, Shuxiang; Zhang, Jinchao

    2013-07-01

    Oxidative stress is well documented to cause injury to endothelial cells (ECs), which in turn trigger cardiovascular diseases. Previous studies revealed that cerium oxide nanoparticles (nanoceria) had antioxidant property, but the protective effect of nanoceria on ROS injury to ECs and cardiovascular diseases has not been reported. In the current study, we investigated the protective effect and underlying mechanisms of nanoceria on oxidative injury to ECs. The cell viability, lactate dehydrogenase release, cellular uptake, intracellular localization and reactive oxygen species (ROS) levels, endocytosis mechanism, cell apoptosis, and mitochondrial membrane potential were performed. The results indicated that nanoceria had no cytotoxicity on ECs but had the ability to prevent injury by H2O2. Nanoceria could be uptaken into ECs through caveolae- and clathrin-mediated endocytosis and distributed throughout the cytoplasma. The internalized nanoceria effectively attenuated ROS overproduction induced by H2O2. Apoptosis was also alleviated greatly by nanoceria pretreatment. These results may be helpful for more rational application of nanoceria in biomedical fields in the future.

  2. Cerium and yttrium oxide nanoparticles against lead-induced oxidative stress and apoptosis in rat hippocampus.

    PubMed

    Hosseini, Asieh; Sharifi, Ali Mohammad; Abdollahi, Mohammad; Najafi, Rezvan; Baeeri, Maryam; Rayegan, Samira; Cheshmehnour, Jamshid; Hassani, Shokoufeh; Bayrami, Zahra; Safa, Majid

    2015-03-01

    Due to numerous industrial applications, lead has caused widespread pollution in the environment; it seems that the central nervous system (CNS) is the main target for lead in the human body. Oxidative stress and programmed cell death in the CNS have been assumed as two mechanisms related to neurotoxicity of lead. Cerium oxide (CeO2) and yttrium oxide (Y2O3) nanoparticles have recently shown antioxidant effects, particularly when used together, through scavenging the amount of reactive oxygen species (ROS) required for cell apoptosis. We looked into the neuroprotective effects of the combinations of these nanoparticles against acute lead-induced neurotoxicity in rat hippocampus. We used five groups in this study: control, lead, CeO2 nanoparticles + lead, Y2O3 nanoparticles + lead, and CeO2 and Y2O3 nanoparticles + lead. Nanoparticles of CeO2 (1000 mg/kg) and Y2O3 (230 mg/kg) were administered intraperitoneally during 2 days prior to intraperitoneal injection of the lead (25 mg/kg for 3 days). At the end of the treatments, oxidative stress markers, antioxidant enzymes activity, and apoptosis indexes were investigated. The results demonstrated that pretreatments with CeO2 and/or Y2O3 nanoparticles recovered lead-caused oxidative stress markers (ROS, lipid peroxidation, and total thiol molecules) and apoptosis indexes (Bax/Bcl-2 and caspase-3 protein expression). Besides, these nanoparticles reduced the activities of lead-induced superoxide dismutase and catalase as well as the ADP/ATP ratio. Interestingly, the best recovery resulted from the compound of these nanoparticles. Based on these outcomes, it appears that this combination may potentially be beneficial for protection against lead-caused acute toxicity in the brain through improving the oxidative stress-mediated programmed cell death pathway.

  3. High temperature stability of a 316 austenitic stainless steel coated with cerium oxide nanoparticles

    NASA Astrophysics Data System (ADS)

    Mendoza Del Angel, Humberto

    Cerium oxide (CeO2-x) nanoparticles were used for coating protection on a 316 Austenitic Stainless Steel (Aust. SS) to enhance the thermal stability of the oxide films formed at high temperatures. Three simple coating methods were used, dipping, spraying and spinning in order to explore the coating film morphology, nanoparticle distribution and its effect on thermal stability of the steel substrates. Experimentally, the selected steel was exposed to 800°C/1000°C under dry air conditions. Weight changes (DeltaW/A) were monitored as a function of time and the results were compared with uncoated alloys tested under similar conditions. The cerium oxide nanoparticles used on the three methods were synthesized in the laboratory obtaining nanoparticles in the range of 3.5 to 6.2 nanometers. It was found that cerium oxide particle size is affected by temperature. In this case, the activation energy for particle growth was estimated to be around 21,1 kJ/mol. Characterization of the film morphologies before and after oxidation were carried out using Atomic Force Microscopy (AFM), Surface Profilometry, Scanning Electron Microscopy (SEM) and X-ray Diffraction (XRD). A comparison of the three coating methods was carried out for the particular case of the 316 Aust. SS coupons. In addition, the oxidation kinetics was experimentally investigated for the coated samples. For this purpose thermal gravimetric determinations were made at 800°C, 900°C, and 1000°C and oxidation rate constants were calculated at each temperature.

  4. Oxidation behaviour and electrical properties of cobalt/cerium oxide composite coatings for solid oxide fuel cell interconnects

    NASA Astrophysics Data System (ADS)

    Harthøj, Anders; Holt, Tobias; Møller, Per

    2015-05-01

    This work evaluates the performance of cobalt/cerium oxide (Co/CeO2) composite coatings and pure Co coatings to be used for solid oxide fuel cell (SOFC) interconnects. The coatings are electroplated on the ferritic stainless steels Crofer 22 APU and Crofer 22H. Coated and uncoated samples are exposed in air at 800 °C for 3000 h and oxidation rates are measured and oxide scale microstructures are investigated. Area-specific resistances (ASR) in air at 850 °C of coated and uncoated samples are also measured. A dual layered oxide scale formed on all coated samples. The outer layer consisted of Co, Mn, Fe and Cr oxide and the inner layer consisted of Cr oxide. The CeO2 was present as discrete particles in the outer oxide layer after exposure. The Cr oxide layer thicknesses and oxidations rates were significantly reduced for Co/CeO2 coated samples compared to for Co coated and uncoated samples. The ASR of all Crofer 22H samples increased significantly faster than of Crofer 22 APU samples which was likely due to the presence of SiO2 in the oxide/metal interface of Crofer 22H.

  5. Long-term testing of in-situ cerium oxide coated anodes for aluminum electrowinning

    SciTech Connect

    King, H.L.

    1989-10-01

    The ELTECH Anode Phase 2 Project (Contract Number AC07-86ID12655), as supported by the Department of Energy (DOE) from December 1988 through April 1989, focused on long-term testing of in-situ anodically deposited cerium oxide (CEROX) coatings on nickel ferrite/Cu cermets. The specific objective of this research was to determine the effectiveness of the CEROX coating in reducing the transfer of cermet components to the produced aluminum. A dosing regimen was first established for the minimum addition of cerium to the cell necessary to produce targeted CEROX coatings on the cermet anode and the periodic additions necessary to maintain coating thicknesses. The effects of the addition of CeF{sub 3} on CEROX coating formation was evaluated for targeted coating thicknesses at three different current densities. Analytical procedures were identified for determining alumina concentrations and the cryolite bath ratio for quasi-commercial baths.

  6. Controlling the physics and chemistry of binary and ternary praseodymium and cerium oxide systems.

    PubMed

    Niu, Gang; Zoellner, Marvin Hartwig; Schroeder, Thomas; Schaefer, Andreas; Jhang, Jin-Hao; Zielasek, Volkmar; Bäumer, Marcus; Wilkens, Henrik; Wollschläger, Joachim; Olbrich, Reinhard; Lammers, Christian; Reichling, Michael

    2015-10-14

    Rare earth praseodymium and cerium oxides have attracted intense research interest in the last few decades, due to their intriguing chemical and physical characteristics. An understanding of the correlation between structure and properties, in particular the surface chemistry, is urgently required for their application in microelectronics, catalysis, optics and other fields. Such an understanding is, however, hampered by the complexity of rare earth oxide materials and experimental methods for their characterisation. Here, we report recent progress in studying high-quality, single crystalline, praseodymium and cerium oxide films as well as ternary alloys grown on Si(111) substrates. Using these well-defined systems and based on a systematic multi-technique surface science approach, the corresponding physical and chemical properties, such as the surface structure, the surface morphology, the bulk-surface interaction and the oxygen storage/release capability, are explored in detail. We show that specifically the crystalline structure and the oxygen stoichiometry of the oxide thin films can be well controlled by the film preparation method. This work leads to a comprehensive understanding of the properties of rare earth oxides and highlights the applications of these versatile materials. Furthermore, methanol adsorption studies are performed on binary and ternary rare earth oxide thin films, demonstrating the feasibility of employing such systems for model catalytic studies. Specifically for ceria systems, we find considerable stability against normal environmental conditions so that they can be considered as a "materials bridge" between surface science models and real catalysts.

  7. Controlling the physics and chemistry of binary and ternary praseodymium and cerium oxide systems.

    PubMed

    Niu, Gang; Zoellner, Marvin Hartwig; Schroeder, Thomas; Schaefer, Andreas; Jhang, Jin-Hao; Zielasek, Volkmar; Bäumer, Marcus; Wilkens, Henrik; Wollschläger, Joachim; Olbrich, Reinhard; Lammers, Christian; Reichling, Michael

    2015-10-14

    Rare earth praseodymium and cerium oxides have attracted intense research interest in the last few decades, due to their intriguing chemical and physical characteristics. An understanding of the correlation between structure and properties, in particular the surface chemistry, is urgently required for their application in microelectronics, catalysis, optics and other fields. Such an understanding is, however, hampered by the complexity of rare earth oxide materials and experimental methods for their characterisation. Here, we report recent progress in studying high-quality, single crystalline, praseodymium and cerium oxide films as well as ternary alloys grown on Si(111) substrates. Using these well-defined systems and based on a systematic multi-technique surface science approach, the corresponding physical and chemical properties, such as the surface structure, the surface morphology, the bulk-surface interaction and the oxygen storage/release capability, are explored in detail. We show that specifically the crystalline structure and the oxygen stoichiometry of the oxide thin films can be well controlled by the film preparation method. This work leads to a comprehensive understanding of the properties of rare earth oxides and highlights the applications of these versatile materials. Furthermore, methanol adsorption studies are performed on binary and ternary rare earth oxide thin films, demonstrating the feasibility of employing such systems for model catalytic studies. Specifically for ceria systems, we find considerable stability against normal environmental conditions so that they can be considered as a "materials bridge" between surface science models and real catalysts. PMID:26355535

  8. Neuroprotective mechanisms of cerium oxide nanoparticles in a mouse hippocampal brain slice model of ischemia.

    PubMed

    Estevez, A Y; Pritchard, S; Harper, K; Aston, J W; Lynch, A; Lucky, J J; Ludington, J S; Chatani, P; Mosenthal, W P; Leiter, J C; Andreescu, S; Erlichman, J S

    2011-09-15

    Cerium oxide nanoparticles (nanoceria) are widely used as catalysts in industrial applications because of their potent free radical-scavenging properties. Given that free radicals play a prominent role in the pathology of many neurological diseases, we explored the use of nanoceria as a potential therapeutic agent for stroke. Using a mouse hippocampal brain slice model of cerebral ischemia, we show here that ceria nanoparticles reduce ischemic cell death by approximately 50%. The neuroprotective effects of nanoceria were due to a modest reduction in reactive oxygen species, in general, and ~15% reductions in the concentrations of superoxide (O(2)(•-)) and nitric oxide, specifically. Moreover, treatment with nanoceria markedly decreased (~70% reduction) the levels of ischemia-induced 3-nitrotyrosine, a modification to tyrosine residues in proteins induced by the peroxynitrite radical. These findings suggest that scavenging of peroxynitrite may be an important mechanism by which cerium oxide nanoparticles mitigate ischemic brain injury. Peroxynitrite plays a pivotal role in the dissemination of oxidative injury in biological tissues. Therefore, nanoceria may be useful as a therapeutic intervention to reduce oxidative and nitrosative damage after a stroke. PMID:21704154

  9. The effect of lanthanum(III) and cerium(III) ions between layers of manganese oxide on water oxidation.

    PubMed

    Najafpour, Mohammad Mahdi; Isaloo, Mohsen Abbasi; Hołyńska, Małgorzata; Shen, Jian-Ren; Allakhverdiev, Suleyman I; Allakhverdiev, Suleyman

    2015-12-01

    Manganese oxide structure with lanthanum(III) or cerium(III) ions between the layers was synthesized by a simple method. The ratio of Mn to Ce or La in samples was 0.00, 0.04, 0.08, 0.16, 0.32, 0.5, 0.82, or 1.62. The compounds were characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction studies, and atomic absorption spectroscopy. The compounds show efficient catalytic activity of water oxidation in the presence of cerium(IV) ammonium nitrate with a turnover frequency of 1.6 mmol O2/mol Mn.s. In contrast to the water-oxidizing complex in Photosystem II, calcium(II) has no specific role to enhance the water-oxidizing activity of the layered manganese oxides and other cations can be replaced without any significant decrease in water-oxidizing activities of these layered Mn oxides. Based on this and previously reported results from oxygen evolution in the presence of H 2 (18) O, we discuss the mechanism and the important factors influencing the water-oxidizing activities of the manganese oxides. PMID:25701552

  10. Custom cerium oxide nanoparticles protect against a free radical mediated autoimmune degenerative disease in the brain.

    PubMed

    Heckman, Karin L; DeCoteau, William; Estevez, Ana; Reed, Kenneth J; Costanzo, Wendi; Sanford, David; Leiter, James C; Clauss, Jennifer; Knapp, Kylie; Gomez, Carlos; Mullen, Patrick; Rathbun, Elle; Prime, Kelly; Marini, Jessica; Patchefsky, Jamie; Patchefsky, Arthur S; Hailstone, Richard K; Erlichman, Joseph S

    2013-12-23

    Cerium oxide nanoparticles are potent antioxidants, based on their ability to either donate or receive electrons as they alternate between the +3 and +4 valence states. The dual oxidation state of ceria has made it an ideal catalyst in industrial applications, and more recently, nanoceria's efficacy in neutralizing biologically generated free radicals has been explored in biological applications. Here, we report the in vivo characteristics of custom-synthesized cerium oxide nanoparticles (CeNPs) in an animal model of immunological and free-radical mediated oxidative injury leading to neurodegenerative disease. The CeNPs are 2.9 nm in diameter, monodispersed and have a -23.5 mV zeta potential when stabilized with citrate/EDTA. This stabilizer coating resists being 'washed' off in physiological salt solutions, and the CeNPs remain monodispersed for long durations in high ionic strength saline. The plasma half-life of the CeNPs is ∼4.0 h, far longer than previously described, stabilized ceria nanoparticles. When administered intravenously to mice, the CeNPs were well tolerated and taken up by the liver and spleen much less than previous nanoceria formulations. The CeNPs were also able to penetrate the brain, reduce reactive oxygen species levels, and alleviate clinical symptoms and motor deficits in mice with a murine model of multiple sclerosis. Thus, CeNPs may be useful in mitigating tissue damage arising from free radical accumulation in biological systems.

  11. Adsorption and dissociation of methanol on the fully oxidized and partially reduced (111) cerium oxide surface: dependence on the configuration of the cerium 4f electrons

    SciTech Connect

    Beste, Ariana; Mullins, David R; Overbury, Steven {Steve} H; Harrison, Robert J

    2008-01-01

    The adsorption and dissociation of methanol on the fully oxidized and partially reduced (111) cerium oxide surface is studied using the PW91 functional as well as the PW91+U scheme. We investigate the influence of the detailed electronic structure of the Ce 4f band on the chemistry of methanol on the surface. For the partially reduced surface we obtain a spin delocalized, a ferromagnetic, and an anti-ferromagnetic solution. We find that the qualitative conclusions are independent of the surface type used. Methanol adsorption is exothermic on the fully oxidized as well as on the partially reduced surface. Also dissociation of methanol on the surface is exothermic but strongly enhanced by the presence of a vacancy. We localize an on-top methoxy species as a dissociation product on the fully oxidized surface and a triply bridged methoxy species on the partially reduced surface where the methoxy oxygen partly fills the oxygen vacancy in the surface. Adsorption energies are influenced by the introduction of the repulsive Hubbard (U) term. On the other hand, relative surface stabilities like dissociation energies are less sensitive.

  12. Surface structures of cerium oxide nanocrystalline particles from the size dependence of the lattice parameters

    NASA Astrophysics Data System (ADS)

    Tsunekawa, S.; Ito, S.; Kawazoe, Y.

    2004-10-01

    Cerium oxide nanocrystalline particles are synthesized and monodispersed in the size range from 2 to 8nm in diameter. The dependence of the lattice parameters on particle size is obtained by x-ray and electron diffraction analyses. The size dependence well coincides with the estimation based on the assumption that the surface is composed of one layer of Ce2O3 and the inside consists of CeO2. The effect of particle size on lattice parameters is discussed from the differences in the fabrication method and the surface structure.

  13. Silicate-free growth of high-quality ultrathin cerium oxide films on Si(111)

    SciTech Connect

    Flege, Jan Ingo; Kaemena, Bjoern; Wilkens, Torsten; Schmidt, Thomas; Falta, Jens; Gevers, Sebastian; Bruns, Daniel; Wollschlaeger, Joachim; Bertram, Florian; Baetjer, Jan

    2011-12-15

    Ultrathin Ce{sub 2}O{sub 3} layers have been grown on Si(111) by reactive metal deposition in an oxygen background and characterized by x-ray standing waves, x-ray diffraction, x-ray photoelectron spectroscopy, and low-energy electron diffraction to elucidate and quantify both atomic structure and chemical composition. It is demonstrated that highly ordered, mostly B-oriented, epitaxial ceria films can be achieved by preadsorption of a monolayer of atomic chlorine, effectively passivating the substrate and thereby suppressing cerium silicate and silicon oxide formation at the interface.

  14. Electrochemical & Thermochemical Behavior of Cerium(IV) Oxide delta

    NASA Astrophysics Data System (ADS)

    Chueh, William C.

    The mixed-valent nature of nonstoichiometric ceria (CeO2-delta ) gives rise to a wide range of intriguing properties, such as mixed ionic and electronic conduction and oxygen storage. Surface and transport behavior in rare-earth (samaria) doped and undoped ceria were investigated, with particular emphasis on applications in electrochemical and thermochemical energy conversion processes such as fuel cells and solar fuel production. The electrochemical responses of bulk-processed ceria with porous Pt and Au electrodes were analyzed using 1-D and 2-D transport models to decouple surface reactions, near-surface transport and bulk transport. Combined experimental and numerical results indicate that hydrogen electro-oxidation and hydrolysis near open-circuit conditions occur preferentially over the ceria | gas interface rather than over the ceria | gas | metal interface, with the rate-limiting step likely to be either surface reaction or transport through the surface oxygen vacancy depletion layer. In addition, epitaxial thin films of ceria were grown on zirconia substrates using pulsed-laser deposition to examine electrocatalysis over well-defined microstructures. Physical models were derived to analyze the electrochemical impedance response. By varying the film thickness, interfacial and chemical capacitance were decoupled, with the latter shown to be proportional to the small polaron densities. The geometry of microfabricated metal current collectors (metal = Pt, Ni) was also systematically varied to investigate the relative activity of the ceria | gas and the ceria | metal | gas interfaces. The data suggests that the electrochemical activity of the metal-ceria composite is only weakly dependent on the metal due to the relatively high activity of the ceria | gas interface. In addition to electrochemical experiments, thermochemical reduction-oxidation studies were performed on ceria. It was shown that thermally-reduced ceria, upon exposure to H 2O and/or CO2, can be

  15. Cerium-based binary and ternary oxides in the transesterification of dimethylcarbonate with phenol.

    PubMed

    Dibenedetto, Angela; Angelini, Antonella; di Bitonto, Luigi; De Giglio, Elvira; Cometa, Stefania; Aresta, Michele

    2014-04-01

    Diphenyl carbonate (DPC) plays a key role in phosgene-free carbonylation processes. It can be produced by transesterification of dimethyl carbonate (DMC) with phenol in the presence of catalysts. Methyl phenyl carbonate (MPC) is first produced that is then converted into DPC by either disproportionation or further transesterification with phenol. Cerium-based bimetallic oxides (with the heterometal being niobium, iron, palladium, or aluminum) are used as catalysts in the transesterification of DMC to synthesize MPC. The catalytic activity is affected by the type and concentration of the heterometal. XPS, IR and elementary analyses are employed to characterize the new catalysts. Differently from pure oxides, the mixed oxides produce a significant increase of the conversion and selectivity towards MPC. PMID:24616260

  16. Cerium oxide-chitosan based nanobiocomposite for food borne mycotoxin detection

    NASA Astrophysics Data System (ADS)

    Kaushik, Ajeet; Solanki, Pratima R.; Pandey, M. K.; Ahmad, Sharif; Malhotra, Bansi D.

    2009-10-01

    Cerium oxide nanoparticles (NanoCeO2) and chitosan (CH) based nanobiocomposite film deposited onto indium-tin-oxide coated glass substrate has been used to coimmobilize rabbit immunoglobin (r-IgGs) and bovine serum albumin (BSA) for food borne mycotoxin [ochratoxin-A (OTA)] detection. Electrochemical studies reveal that presence of NanoCeO2 increases effective electro-active surface area of CH-NanoCeO2/indium tin oxide (ITO) nanobiocomposite resulting in high loading of r-IgGs. BSA/r-IgGs/CH-NanoCeO2/ITO immunoelectrode exhibits improved linearity (0.25-6.0 ng/dl), detection limit (0.25 ng/dl), response time (25 s), sensitivity (18 μA/ng dl-1 cm-2), and regression coefficient (r2˜0.997).

  17. Determination of Ideal Broth Formulations Needed to Prepare Hydrous Cerium Oxide Microspheres via the Internal Gelation Process

    SciTech Connect

    Collins, Jack Lee; Chi, Anthony

    2009-02-01

    A simple test tube methodology was used to determine optimum process parameters for preparing hydrous cerium oxide microspheres via the internal gelation process.1 Broth formulations of cerium ammonium nitrate [(NH4)2Ce(NO3)6], hexamethylenetetramine, and urea were found that can be used to prepare hydrous cerium oxide gel spheres in the temperature range of 60 to 90 C. A few gel-forming runs were made in which microspheres were prepared with some of these formulations to be able to equate the test-tube gelation times to actual gelation times. These preparations confirmed that the test-tube methodology is reliable for determining the ideal broth formulations.

  18. Cyanex 923 as the extractant in a rare earth element impurity analysis of high-purity cerium oxide.

    PubMed

    Duan, Taicheng; Li, Hongfei; Kang, JianZhen; Chen, Hangting

    2004-06-01

    In this work, the feasibility of employing Cyanex 923 as an extractant into the non-cerium REE (rare earth elements) impurity analysis of high-purity cerium oxide was investigated. Through investigations on the choice of the extraction medium, the optimium extraction acidity, matrix Ce4+ effect on the non-cerium REE ion extraction, the optimium extractant concentration and suitable extracting time, and oscillation strengh, it was found that when the phase ratio was at 1:1 and the acicidity was about 2% H2SO4, by gently shaking by hand for about 2 min, 10 mL of 30% Cyanex 923 could not extract even for a 20 ng amount of non-cerium REE3+ ions. However, the extraction efficiency for Ce4+ of 100 mg total amount under the same conditions was about 96%, indicating that a 25-fold preconcentration factor could be achieved. Thus, it was concluded that Cyanex 923 could be used in a REE impurity analysis of 99.9999% or so pure cerium oxide for primary sepapation to elimilate matrix-induced interferences encountered in an ICP-MS (inductively coupled plasma mass spectroscopy) determination.

  19. Cerium oxide for the destruction of chemical warfare agents: A comparison of synthetic routes.

    PubMed

    Janoš, Pavel; Henych, Jiří; Pelant, Ondřej; Pilařová, Věra; Vrtoch, Luboš; Kormunda, Martin; Mazanec, Karel; Štengl, Václav

    2016-03-01

    Four different synthetic routes were used to prepare active forms of cerium oxide that are capable of destroying toxic organophosphates: a sol-gel process (via a citrate precursor), homogeneous hydrolysis and a precipitation/calcination procedure (via carbonate and oxalate precursors). The samples prepared via homogeneous hydrolysis with urea and the samples prepared via precipitation with ammonium bicarbonate (with subsequent calcination at 500°C in both cases) exhibited the highest degradation efficiencies towards the extremely dangerous nerve agents soman (O-pinacolyl methylphosphonofluoridate) and VX (O-ethyl S-[2-(diisopropylamino)ethyl] methylphosphonothioate) and the organophosphate pesticide parathion methyl. These samples were able to destroy more than 90% of the toxic compounds in less than 10 min. The high degradation efficiency of cerium oxide is related to its complex surface chemistry (presence of surface OH groups and surface non-stoichiometry) and to its nanocrystalline nature, which promotes the formation of crystal defects on which the decomposition of organophosphates proceeds through a nucleophilic substitution mechanism that is not dissimilar to the mechanism of enzymatic hydrolysis of organic phosphates by phosphotriesterase. PMID:26561750

  20. Cerium oxide for the destruction of chemical warfare agents: A comparison of synthetic routes.

    PubMed

    Janoš, Pavel; Henych, Jiří; Pelant, Ondřej; Pilařová, Věra; Vrtoch, Luboš; Kormunda, Martin; Mazanec, Karel; Štengl, Václav

    2016-03-01

    Four different synthetic routes were used to prepare active forms of cerium oxide that are capable of destroying toxic organophosphates: a sol-gel process (via a citrate precursor), homogeneous hydrolysis and a precipitation/calcination procedure (via carbonate and oxalate precursors). The samples prepared via homogeneous hydrolysis with urea and the samples prepared via precipitation with ammonium bicarbonate (with subsequent calcination at 500°C in both cases) exhibited the highest degradation efficiencies towards the extremely dangerous nerve agents soman (O-pinacolyl methylphosphonofluoridate) and VX (O-ethyl S-[2-(diisopropylamino)ethyl] methylphosphonothioate) and the organophosphate pesticide parathion methyl. These samples were able to destroy more than 90% of the toxic compounds in less than 10 min. The high degradation efficiency of cerium oxide is related to its complex surface chemistry (presence of surface OH groups and surface non-stoichiometry) and to its nanocrystalline nature, which promotes the formation of crystal defects on which the decomposition of organophosphates proceeds through a nucleophilic substitution mechanism that is not dissimilar to the mechanism of enzymatic hydrolysis of organic phosphates by phosphotriesterase.

  1. Phenotypic and genomic responses to titanium dioxide and cerium oxide nanoparticles in Arabidopsis germinants.

    PubMed

    Tumburu, Laxminath; Andersen, Christian P; Rygiewicz, Paul T; Reichman, Jay R

    2015-01-01

    The effects of exposure to nanoparticles of titanium dioxide (nano-titanium) and cerium oxide (nano-cerium) on gene expression and growth in Arabidopsis thaliana germinants were studied by using microarrays and quantitative real-time polymerase chain reaction (qPCR), and by evaluating germinant phenotypic plasticity. Exposure to 12 d of either nano-titania or nano-ceria altered the regulation of 204 and 142 genes, respectively. Genes induced by the nanoparticles mainly include ontology groups annotated as stimuli responsive, including both abiotic (oxidative stress, salt stress, water transport) and biotic (respiratory burst as a defense against pathogens) stimuli. Further analysis of the differentially expressed genes indicates that both nanoparticles affected a range of metabolic processes (deoxyribonucleic acid [DNA] metabolism, hormone metabolism, tetrapyrrole synthesis, and photosynthesis). Individual exposures to the nanoparticles increased percentages of seeds with emergent radicles, early development of hypocotyls and cotyledons, and those with fully grown leaves. Although there were distinct differences between the nanoparticles in their affect on molecular mechanisms attributable to enhancing germinant growth, both particles altered similar suites of genes related to various pathways and processes related to enhanced growth.

  2. Phenotypic and genomic responses to titanium dioxide and cerium oxide nanoparticles in Arabidopsis germinants.

    PubMed

    Tumburu, Laxminath; Andersen, Christian P; Rygiewicz, Paul T; Reichman, Jay R

    2015-01-01

    The effects of exposure to nanoparticles of titanium dioxide (nano-titanium) and cerium oxide (nano-cerium) on gene expression and growth in Arabidopsis thaliana germinants were studied by using microarrays and quantitative real-time polymerase chain reaction (qPCR), and by evaluating germinant phenotypic plasticity. Exposure to 12 d of either nano-titania or nano-ceria altered the regulation of 204 and 142 genes, respectively. Genes induced by the nanoparticles mainly include ontology groups annotated as stimuli responsive, including both abiotic (oxidative stress, salt stress, water transport) and biotic (respiratory burst as a defense against pathogens) stimuli. Further analysis of the differentially expressed genes indicates that both nanoparticles affected a range of metabolic processes (deoxyribonucleic acid [DNA] metabolism, hormone metabolism, tetrapyrrole synthesis, and photosynthesis). Individual exposures to the nanoparticles increased percentages of seeds with emergent radicles, early development of hypocotyls and cotyledons, and those with fully grown leaves. Although there were distinct differences between the nanoparticles in their affect on molecular mechanisms attributable to enhancing germinant growth, both particles altered similar suites of genes related to various pathways and processes related to enhanced growth. PMID:25242526

  3. Low Temperature Constrained Sintering of Cerium Gadolinium OxideFilms for Solid Oxide Fuel Cell Applications

    SciTech Connect

    Nicholas, Jason Dale

    2007-01-01

    Cerium gadolinium oxide (CGO) has been identified as an acceptable solid oxide fuel cell (SOFC) electrolyte at temperatures (500-700 C) where cheap, rigid, stainless steel interconnect substrates can be used. Unfortunately, both the high sintering temperature of pure CGO, >1200 C, and the fact that constraint during sintering often results in cracked, low density ceramic films, have complicated development of metal supported CGO SOFCs. The aim of this work was to find new sintering aids for Ce0.9Gd0.1O1.95, and to evaluate whether they could be used to produce dense, constrained Ce0.9Gd0.1O1.95 films at temperatures below 1000 C. To find the optimal sintering aid, Ce0.9Gd0.1O1.95 was doped with a variety of elements, of which lithium was found to be the most effective. Dilatometric studies indicated that by doping CGO with 3mol% lithium nitrate, it was possible to sinter pellets to a relative density of 98.5% at 800 C--a full one hundred degrees below the previous low temperature sintering record for CGO. Further, it was also found that a sintering aid's effectiveness could be explained in terms of its size, charge and high temperature mobility. A closer examination of lithium doped Ce0.9Gd0.1O1.95 indicated that lithium affects sintering by producing a Li2O-Gd2O3-CeO2 liquid at the CGO grain boundaries. Due to this liquid phase sintering, it was possible to produce dense, crack-free constrained films of CGO at the record low temperature of 950 C using cheap, colloidal spray deposition processes. This is the first time dense constrained CGO films have been produced below 1000 C and could help commercialize metal supported ceria based solid oxide fuel cells.

  4. Physical and chemical characterization of cerium(IV) oxide nanoparticles.

    PubMed

    Cepriá, Gemma; Córdova, Walvin R; Céspedes, Oscar; Sánchez-García, Laura; Ferrer, Pilar; Gianolio, Diego; Castillo, Juan R

    2016-09-01

    Chemical composition, size and structure of the nanoparticle are required to describe nanoceria. Nanoparticles of similar size and Ce(III) content might exhibit different chemical behaviour due to their differences in structure. A simple and direct procedure based on affordable techniques for all the laboratories is presented in this paper. The combination of Raman and UV-vis spectroscopy and particle impact coulometry (PIC) allows the characterization of nanoceria of small size from 4 to 65 nm at a concentration from micromolar to nanomolar, a concentration range suitable for the analysis of lab-prepared or commercial nanoparticle suspensions, but too high for most analytical purposes aimed at nanoparticle monitoring. While the PIC limits of size detection are too high to observe small nanoparticles unless catalytic amplification is used, the method provides a simple means to study aggregation of nanoparticles in the media they are needed to be dispersed for each application. Raman spectroscopy provided information about structure of the nanoparticle, and UV-vis about their chemical behaviour against some common reducing and oxidizing agents. Graphical Abstract To characterize nanoceria it is necessary to provide information about the shape, size and structure of the nanoparticles as well as the chemical composition.

  5. Heteroaggregation of Cerium Oxide Nanoparticles and Nanoparticles of Pyrolyzed Biomass.

    PubMed

    Yi, Peng; Pignatello, Joseph J; Uchimiya, Minori; White, Jason C

    2015-11-17

    Heteroaggregation with indigenous particles is critical to the environmental mobility of engineered nanomaterials (ENM). We studied heteroaggregation of ceria nanoparticles (n-CeO2), as a model for metal oxide ENM, with nanoparticles of pyrogenic carbonaceous material (n-PCM) derived from pecan shell biochar, a model for natural chars and human-made chars used in soil remediation and agriculture. The TEM and STEM images of n-PCM identify both hard and soft particles, both C-rich and C,O,Ca-containing particles (with CaCO3 crystals), both amorphous and "onion-skin" C-rich particles, and traces of nanotubes. Heteroaggregation was evaluated at constant n-CeO2, variable n-PCM concentration by monitoring hydrodynamic diameter by dynamic light scattering and ζ-potential under conditions where n-PCM is "invisible". At pH 5.3, where n-CeO2 and n-PCM are positively and negatively charged, respectively, and each stable to homoaggregation, heteroaggregation is favorable and occurs by a charge neutralization-charge reversal mechanism (CNCR): in this mechanism, primary heteroaggregates that form in the initial stage are stable at low or high n-PCM concentration due to electrostatic repulsion, but unstable at intermediate n-PCM concentration, leading to secondary heteroaggregation. The greatest instability coincides with full charge neutralization. At pH 7.1, where n-CeO2 is neutral and unstable alone, and n-PCM is negative and stable alone, heteroaggregation occurs by a charge-accumulation, core-shell stabilization (CACS) mechanism: n-PCM binds to and forms a negatively charged shell on the neutral surface of the nascent n-CeO2 core, stabilizing the core-shell heteraggregate at a size that decreases with n-PCM concentration. The CNCR and CACS mechanisms give fundamental insight into heteroaggregation between oppositely charged, and between neutral and charged nanoparticles. PMID:26461459

  6. Inhaled Diesel Emissions Generated with Cerium Oxide Nanoparticle Fuel Additive Induce Adverse Pulmonary and Systemic Effects

    PubMed Central

    Snow, Samantha J.; McGee, John; Miller, Desinia B.; Bass, Virginia; Schladweiler, Mette C.; Thomas, Ronald F.; Krantz, Todd; King, Charly; Ledbetter, Allen D.; Richards, Judy; Weinstein, Jason P.; Conner, Teri; Willis, Robert; Linak, William P.; Nash, David; Wood, Charles E.; Elmore, Susan A.; Morrison, James P.; Johnson, Crystal L.; Gilmour, Matthew Ian; Kodavanti, Urmila P.

    2014-01-01

    Diesel exhaust (DE) exposure induces adverse cardiopulmonary effects. Cerium oxide nanoparticles added to diesel fuel (DECe) increases fuel burning efficiency but leads to altered emission characteristics and potentially altered health effects. Here, we evaluated whether DECe results in greater adverse pulmonary effects compared with DE. Male Sprague Dawley rats were exposed to filtered air, DE, or DECe for 5 h/day for 2 days. N-acetyl glucosaminidase activity was increased in bronchial alveolar lavage fluid (BALF) of rats exposed to DECe but not DE. There were also marginal but insignificant increases in several other lung injury biomarkers in both exposure groups (DECe > DE for all). To further characterize DECe toxicity, rats in a second study were exposed to filtered air or DECe for 5 h/day for 2 days or 4 weeks. Tissue analysis indicated a concentration- and time-dependent accumulation of lung and liver cerium followed by a delayed clearance. The gas-phase and high concentration of DECe increased lung inflammation at the 2-day time point, indicating that gas-phase components, in addition to particles, contribute to pulmonary toxicity. This effect was reduced at 4 weeks except for a sustained increase in BALF γ-glutamyl transferase activity. Histopathology and transmission electron microscopy revealed increased alveolar septa thickness due to edema and increased numbers of pigmented macrophages after DECe exposure. Collectively, these findings indicate that DECe induces more adverse pulmonary effects on a mass basis than DE. In addition, lung accumulation of cerium, systemic translocation to the liver, and delayed clearance are added concerns to existing health effects of DECe. PMID:25239632

  7. Inhaled diesel emissions generated with cerium oxide nanoparticle fuel additive induce adverse pulmonary and systemic effects.

    PubMed

    Snow, Samantha J; McGee, John; Miller, Desinia B; Bass, Virginia; Schladweiler, Mette C; Thomas, Ronald F; Krantz, Todd; King, Charly; Ledbetter, Allen D; Richards, Judy; Weinstein, Jason P; Conner, Teri; Willis, Robert; Linak, William P; Nash, David; Wood, Charles E; Elmore, Susan A; Morrison, James P; Johnson, Crystal L; Gilmour, Matthew Ian; Kodavanti, Urmila P

    2014-12-01

    Diesel exhaust (DE) exposure induces adverse cardiopulmonary effects. Cerium oxide nanoparticles added to diesel fuel (DECe) increases fuel burning efficiency but leads to altered emission characteristics and potentially altered health effects. Here, we evaluated whether DECe results in greater adverse pulmonary effects compared with DE. Male Sprague Dawley rats were exposed to filtered air, DE, or DECe for 5 h/day for 2 days. N-acetyl glucosaminidase activity was increased in bronchial alveolar lavage fluid (BALF) of rats exposed to DECe but not DE. There were also marginal but insignificant increases in several other lung injury biomarkers in both exposure groups (DECe > DE for all). To further characterize DECe toxicity, rats in a second study were exposed to filtered air or DECe for 5 h/day for 2 days or 4 weeks. Tissue analysis indicated a concentration- and time-dependent accumulation of lung and liver cerium followed by a delayed clearance. The gas-phase and high concentration of DECe increased lung inflammation at the 2-day time point, indicating that gas-phase components, in addition to particles, contribute to pulmonary toxicity. This effect was reduced at 4 weeks except for a sustained increase in BALF γ-glutamyl transferase activity. Histopathology and transmission electron microscopy revealed increased alveolar septa thickness due to edema and increased numbers of pigmented macrophages after DECe exposure. Collectively, these findings indicate that DECe induces more adverse pulmonary effects on a mass basis than DE. In addition, lung accumulation of cerium, systemic translocation to the liver, and delayed clearance are added concerns to existing health effects of DECe.

  8. Cerium-modified doped strontium titanate compositions for solid oxide fuel cell anodes and electrodes for other electrochemical devices

    SciTech Connect

    Marina, Olga A; Stevenson, Jeffry W

    2010-11-23

    The present invention provides novel compositions that find advantageous use in making electrodes for electrochemical cells and electrochemical devices such as solid oxide fuel cells, electrolyzers, sensors, pumps and the like, the compositions comprising cerium-modified doped strontium titanate. The invention also provides novel methods for making and using anode material compositions and solid oxide fuel cells and solid oxide fuel cell assemblies having anodes comprising the compositions.

  9. Cerium-modified doped strontium titanate compositions for solid oxide fuel cell anodes and electrodes for other electrochemical devices

    DOEpatents

    Marina, Olga A [Richland, WA; Stevenson, Jeffry W [Richland, WA

    2010-03-02

    The present invention provides novel compositions that find advantageous use in making electrodes for electrochemical cells and electrochemical devices such as solid oxide fuel cells, electrolyzers, sensors, pumps and the like, the compositions comprising cerium-modified doped strontium titanate. The invention also provides novel methods for making and using anode material compositions and solid oxide fuel cells and solid oxide fuel cell assemblies having anodes comprising the compositions.

  10. Germination and early plant development of ten plant species exposed to titanium dioxide and cerium oxide nanoparticles

    EPA Science Inventory

    Ten agronomic plant species were exposed to different concentrations of nano titanium dioxide (nTiO2) or nano cerium oxide (nCeO2) (0, 250, 500 and 1000 mg/L) to examine potential effects on germination and early seedling development. We modified a standard test protocol develop...

  11. Air, aqueous and thermal stabilities of Ce3+ ions in cerium oxide nanoparticle layers with substrates.

    PubMed

    Naganuma, Tamaki; Traversa, Enrico

    2014-06-21

    Abundant oxygen vacancies coexisting with Ce(3+) ions in fluorite cerium oxide nanoparticles (CNPs) have the potential to enhance catalytic ability, but the ratio of unstable Ce(3+) ions in CNPs is typically low. Our recent work, however, demonstrated that the abundant Ce(3+) ions created in cerium oxide nanoparticle layers (CNPLs) by Ar ion irradiation were stable in air at room temperature. Ce valence states in CNPs correlate with the catalytic ability that involves redox reactions between Ce(3+) and Ce(4+) ions in given application environments (e.g. high temperature in carbon monoxide gas conversion and immersion conditions in biomedical applications). To better understand the mechanism by which Ce(3+) ions achieve stability in CNPLs, we examined (i) extra-long air-stability, (ii) thermal stability up to 500 °C, and (iii) aqueous stability of Ce(3+) ions in water, buffer solution and cell culture medium. It is noteworthy that air-stability of Ce(3+) ions in CNPLs persisted for more than 1 year. Thermal stability results showed that oxidation of Ce(3+) to Ce(4+) occurred at 350 °C in air. Highly concentrated Ce(3+) ions in ultra-thin CNPLs slowly oxidized in water within 1 day, but stability was improved in the cell culture medium. Ce(3+) stability of CNPLs immersed in the medium was associated with phosphorus adsorption on the Ce(3+) sites. This study also illuminates the potential interaction mechanisms of stable Ce(3+) ions in CNPLs. These findings could be utilized to understand catalytic mechanisms of CNPs with abundant oxygen vacancies in their application environments.

  12. Corrosion resistance of flaky aluminum pigment coated with cerium oxides/hydroxides in chloride and acidic electrolytes

    NASA Astrophysics Data System (ADS)

    Niroumandrad, S.; Rostami, M.; Ramezanzadeh, B.

    2015-12-01

    The objective of this study was to enhance the corrosion resistance of lamellar aluminum pigment through surface treatment by cerium oxides/hydroxides. The surface composition of the pigments was studied by energy-dispersive spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS). The corrosion resistance of the pigment was evaluated by conventional hydrogen evolution measurements in acidic solution and electrochemical impedance spectroscopy (EIS) in 3.5% NaCl solution. Results showed that the Ce-rich coating composed of Ce2O3 and CeO2 was precipitated on the pigment surface after immersion in the cerium solution. The corrosion resistance of pigment was significantly enhanced after modification with cerium layer.

  13. Freshwater dispersion stability of PAA-stabilised cerium oxide nanoparticles and toxicity towards Pseudokirchneriella subcapitata.

    PubMed

    Booth, Andy; Størseth, Trond; Altin, Dag; Fornara, Andrea; Ahniyaz, Anwar; Jungnickel, Harald; Laux, Peter; Luch, Andreas; Sørensen, Lisbet

    2015-02-01

    An aqueous dispersion of poly (acrylic acid)-stabilised cerium oxide (CeO₂) nanoparticles (PAA-CeO₂) was evaluated for its stability in a range of freshwater ecotoxicity media (MHRW, TG 201 and M7), with and without natural organic matter (NOM). In a 15 day dispersion stability study, PAA-CeO₂ did not undergo significant aggregation in any media type. Zeta potential varied between media types and was influenced by PAA-CeO₂ concentration, but remained constant over 15 days. NOM had no influence on PAA-CeO₂ aggregation or zeta potential. The ecotoxicity of the PAA-CeO₂ dispersion was investigated in 72 h algal growth inhibition tests using the freshwater microalgae Pseudokirchneriella subcapitata. PAA-CeO₂ EC₅₀ values for growth inhibition (GI; 0.024 mg/L) were 2-3 orders of magnitude lower than pristine CeO₂ EC₅₀ values reported in the literature. The concentration of dissolved cerium (Ce(3+)/Ce(4+)) in PAA-CeO₂ exposure suspensions was very low, ranging between 0.5 and 5.6 μg/L. Free PAA concentration in the exposure solutions (0.0096-0.0384 mg/L) was significantly lower than the EC10 growth inhibition (47.7 mg/L) value of pure PAA, indicating that free PAA did not contribute to the observed toxicity. Elemental analysis indicated that up to 38% of the total Cerium becomes directly associated with the algal cells during the 72 h exposure. TOF-SIMS analysis of algal cell wall compounds indicated three different modes of action, including a significant oxidative stress response to PAA-CeO₂ exposure. In contrast to pristine CeO₂ nanoparticles, which rapidly aggregate in standard ecotoxicity media, PAA-stabilised CeO₂ nanoparticles remain dispersed and available to water column species. Interaction of PAA with cell wall components, which could be responsible for the observed biomarker alterations, could not be excluded. This study indicates that the increased dispersion stability of PAA-CeO₂ leads to an increase in toxicity compared to

  14. The induction of angiogenesis by cerium oxide nanoparticles through the modulation of oxygen in intracellular environments

    PubMed Central

    Das, Soumen; Singh, Sanjay; Dowding, Janet M.; Oommen, Saji; Kumar, Amit; Sayle, Thi X. T.; Saraf, Shashank; Patra, Chitta Ranjan; Vlahakis, Nicholas E.; Sayle, Dean C.; Self, William T.; Seal, Sudipta

    2012-01-01

    Angiogenesis is the formation of new blood vessels from existing blood vessels and is critical for many physiological and pathophysiological processes. In this study we have shown the unique property of cerium oxide nanoparticle (CNPs) to induce angiogenesis, observed using both in vitro and in vivo model systems. In particular, CNPs trigger angiogenesis by modulating the intracellular oxygen environment and stabilizing hypoxia inducing factor 1α endogenously. Furthermore, correlations between angiogenesis induction and CNPs physicochemical properties including: surface Ce3+/Ce4+ ratio, surface charge, size, and shape were also explored. High surface area and increased Ce3+/Ce4+ ratio make CNPs more catalytically active towards regulating intracellular oxygen, which in turn led to more robust induction of angiogenesis. Atomistic simulation was also used, in partnership with in vitro and in vivo experimentation, to reveal that the surface reactivity of CNPs and facile oxygen transport promotes pro-angiogenesis. PMID:22858004

  15. Sensitization of Pancreatic Cancer Cells to Radiation by Cerium Oxide Nanoparticle-Induced ROS Production

    PubMed Central

    Wason, Melissa S.; Colon, Jimmie; Das, Soumen; Seal, Sudipta; Turkson, James; Zhao, Jihe; Baker, Cheryl H.

    2012-01-01

    Side effect of radiation therapy (RT) remains the most challenging issue for pancreatic cancer treatment. In this report we determined whether and how cerium oxide nanoparticles (CONPs) sensitize pancreatic cancer cells to RT. CONP pretreatment enhanced radiation-induced reactive oxygen species (ROS) production preferentially in acidic cell-free solutions as well as acidic human pancreatic cancer cells. In acidic environments, CONPs favor the scavenging of superoxide radical over the hydroxyl peroxide resulting in accumulation of the latter whereas in neutral pH CONPs scavenge both. CONP treatment prior to RT markedly potentiated the cancer cell apoptosis both in culture and in tumors and the inhibition of the pancreatic tumor growth without harming the normal tissues or host mice. Taken together, these results identify CONPs as a potentially novel RT-sensitizer as well as protectant for improving pancreatic cancer treatment. PMID:23178284

  16. Catalytic ozonation of oxalate with a cerium supported palladium oxide: an efficient degradation not relying on hydroxyl radical oxidation.

    PubMed

    Zhang, Tao; Li, Weiwei; Croué, Jean-Philippe

    2011-11-01

    The cerium supported palladium oxide (PdO/CeO(2)) at a low palladium loading was found very effective in catalytic ozonation of oxalate, a probe compound that is difficult to be efficiently degraded in water with hydroxyl radical oxidation and one of the major byproducts in ozonation of organic matter. The oxalate was degraded into CO(2) during the catalytic ozonation. The molar ratio of oxalate degraded to ozone consumption increased with increasing catalyst dose and decreasing ozone dosage and pH under the conditions of this study. The maximum molar ratio reached around 1, meaning that the catalyst was highly active and selective for oxalate degradation in water. The catalytic ozonation, which showed relatively stable activity, does not promote hydroxyl radical generation from ozone. Analysis with ATR-FTIR and in situ Raman spectroscopy revealed that 1) oxalate was adsorbed on CeO(2) of the catalyst forming surface complexes, and 2) O(3) was adsorbed on PdO of the catalyst and further decomposed to surface atomic oxygen (*O), surface peroxide (*O(2)), and O(2) gas in sequence. The results indicate that the high activity of the catalyst is related to the synergetic function of PdO and CeO(2) in that the surface atomic oxygen readily reacts with the surface cerium-oxalate complex. This kind of catalytic ozonation would be potentially effective for the degradation of polar refractory organic pollutants and hydrophilic natural organic matter.

  17. Catalyst support of mixed cerium zirconium titanium oxide, including use and method of making

    DOEpatents

    Willigan, Rhonda R.; Vanderspurt, Thomas Henry; Tulyani, Sonia; Radhakrishnan, Rakesh; Opalka, Susanne Marie; Emerson, Sean C.

    2011-01-18

    A durable catalyst support/catalyst is capable of extended water gas shift operation under conditions of high temperature, pressure, and sulfur levels. The support is a homogeneous, nanocrystalline, mixed metal oxide of at least three metals, the first being cerium, the second being Zr, and/or Hf, and the third importantly being Ti, the three metals comprising at least 80% of the metal constituents of the mixed metal oxide and the Ti being present in a range of 5% to 45% by metals-only atomic percent of the mixed metal oxide. The mixed metal oxide has an average crystallite size less than 6 nm and forms a skeletal structure with pores whose diameters are in the range of 4-9 nm and normally greater than the average crystallite size. The surface area of the skeletal structure per volume of the material of the structure is greater than about 240 m.sup.2/cm.sup.3. The method of making and use are also described.

  18. Potential of using cerium oxide nanoparticles for protecting healthy tissue during accelerated partial breast irradiation (APBI)

    PubMed Central

    Ouyang, Zi; Mainali, Madan Kumar; Sinha, Neeharika; Strack, Guinevere; Altundal, Yucel; Hao, Yao; Winningham, Thomas Andrew; Sajo, Erno; Celli, Jonathan; Ngwa, Wilfred

    2016-01-01

    The purpose of this study is to investigate the feasibility of using cerium oxide nanoparticles (CONPs) as radical scavengers during accelerated partial breast irradiation (APBI) to protect normal tissue. We hypothesize that CONPs can be slowly released from the routinely used APBI balloon applicators—via a degradable coating—and protect the normal tissue on the border of the lumpectomy cavity over the duration of APBI. To assess the feasibility of this approach, we analytically calculated the initial concentration of CONPs required to protect normal breast tissue from reactive oxygen species (ROS) and the time required for the particles to diffuse to various distances from the lumpectomy wall. Given that cerium has a high atomic number, we took into account the possible inadvertent dose enhancement that could occur due to the photoelectric interactions with radiotherapy photons. To protect against a typical MammoSite treatment fraction of 3.4 Gy, 5 ng-g−1 of CONPs is required to scavenge hydroxyl radicals and hydrogen peroxide. Using 2 nm sized NPs, with an initial concentration of 1 mg-g−1, we found that 2–10 days of diffusion is required to obtain desired concentrations of CONPs in regions 1–2 cm away from the lumpectomy wall. The resultant dose enhancement factor (DEF) is less than 1.01 under such conditions. Our results predict that CONPs can be employed for radioprotection during APBI using a new design in which balloon applicators are coated with the NPs for sustained/controlled in-situ release from within the lumpectomy cavity. PMID:27053452

  19. Interactive effects of cerium oxide and diesel exhaust nanoparticles on inducing pulmonary fibrosis

    PubMed Central

    Ma, Jane Y.C.; Young, Shih-Houng; Mercer, Robert R.; Barger, Mark; Schwegler-Berry, Diane; Ma, Joseph K.; Castranova, Vincent

    2015-01-01

    Cerium compounds have been used as a fuel-borne catalyst to lower the generation of diesel exhaust particles (DEPs), but are emitted as cerium oxide nanoparticles (CeO2) along with DEP in the diesel exhaust. The present study investigates the effects of the combined exposure to DEP and CeO2 on the pulmonary system in a rat model. Specific pathogen-free male Sprague–Dawley rats were exposed to CeO2 and/or DEP via a single intratracheal instillation and were sacrificed at various time points post-exposure. This investigation demonstrated that CeO2 induces a sustained inflammatory response, whereas DEP elicits a switch of the pulmonary immune response from Th1 to Th2. Both CeO2 and DEP activated AM and lymphocyte secretion of the proinflammatory cytokines IL-12 and IFN-γ respectively. However, only DEP enhanced the anti-inflammatory cytokine IL-10 production in response to ex vivo LPS or Concanavalin A challenge that was not affected by the presence of CeO2, suggesting that DEP suppresses host defense capability by inducing the Th2 immunity. The micrographs of lymph nodes show that the particle clumps in DEP + CeO2 were significantly larger than CeO2 or DEP, exhibiting dense clumps continuous throughout the lymph nodes. Morphometric analysis demonstrates that the localization of collagen in the lung tissue after DEP + CeO2 reflects the combination of DEP-exposure plus CeO2-exposure. At 4 weeks post-exposure, the histological features demonstrated that CeO2 induced lung phospholipidosis and fibrosis. DEP induced lung granulomas that were not significantly affected by the presence of CeO2 in the combined exposure. Using CeO2 as diesel fuel catalyst may cause health concerns. PMID:24793434

  20. Interactive effects of cerium oxide and diesel exhaust nanoparticles on inducing pulmonary fibrosis.

    PubMed

    Ma, Jane Y C; Young, Shih-Houng; Mercer, Robert R; Barger, Mark; Schwegler-Berry, Diane; Ma, Joseph K; Castranova, Vincent

    2014-07-15

    Cerium compounds have been used as a fuel-borne catalyst to lower the generation of diesel exhaust particles (DEPs), but are emitted as cerium oxide nanoparticles (CeO2) along with DEP in the diesel exhaust. The present study investigates the effects of the combined exposure to DEP and CeO2 on the pulmonary system in a rat model. Specific pathogen-free male Sprague-Dawley rats were exposed to CeO2 and/or DEP via a single intratracheal instillation and were sacrificed at various time points post-exposure. This investigation demonstrated that CeO2 induces a sustained inflammatory response, whereas DEP elicits a switch of the pulmonary immune response from Th1 to Th2. Both CeO2 and DEP activated AM and lymphocyte secretion of the proinflammatory cytokines IL-12 and IFN-γ, respectively. However, only DEP enhanced the anti-inflammatory cytokine IL-10 production in response to ex vivo LPS or Concanavalin A challenge that was not affected by the presence of CeO2, suggesting that DEP suppresses host defense capability by inducing the Th2 immunity. The micrographs of lymph nodes show that the particle clumps in DEP+CeO2 were significantly larger than CeO2 or DEP, exhibiting dense clumps continuous throughout the lymph nodes. Morphometric analysis demonstrates that the localization of collagen in the lung tissue after DEP+CeO2 reflects the combination of DEP-exposure plus CeO2-exposure. At 4 weeks post-exposure, the histological features demonstrated that CeO2 induced lung phospholipidosis and fibrosis. DEP induced lung granulomas that were not significantly affected by the presence of CeO2 in the combined exposure. Using CeO2 as diesel fuel catalyst may cause health concerns.

  1. Potential of using cerium oxide nanoparticles for protecting healthy tissue during accelerated partial breast irradiation (APBI).

    PubMed

    Ouyang, Zi; Mainali, Madan Kumar; Sinha, Neeharika; Strack, Guinevere; Altundal, Yucel; Hao, Yao; Winningham, Thomas Andrew; Sajo, Erno; Celli, Jonathan; Ngwa, Wilfred

    2016-04-01

    The purpose of this study is to investigate the feasibility of using cerium oxide nanoparticles (CONPs) as radical scavengers during accelerated partial breast irradiation (APBI) to protect normal tissue. We hypothesize that CONPs can be slowly released from the routinely used APBI balloon applicators-via a degradable coating-and protect the normal tissue on the border of the lumpectomy cavity over the duration of APBI. To assess the feasibility of this approach, we analytically calculated the initial concentration of CONPs required to protect normal breast tissue from reactive oxygen species (ROS) and the time required for the particles to diffuse to various distances from the lumpectomy wall. Given that cerium has a high atomic number, we took into account the possible inadvertent dose enhancement that could occur due to the photoelectric interactions with radiotherapy photons. To protect against a typical MammoSite treatment fraction of 3.4Gy, 5ng·g(-1) of CONPs is required to scavenge hydroxyl radicals and hydrogen peroxide. Using 2nm sized NPs, with an initial concentration of 1mg·g(-1), we found that 2-10days of diffusion is required to obtain desired concentrations of CONPs in regions 1-2cm away from the lumpectomy wall. The resultant dose enhancement factor (DEF) is less than 1.01 under such conditions. Our results predict that CONPs can be employed for radioprotection during APBI using a new design in which balloon applicators are coated with the NPs for sustained/controlled in-situ release from within the lumpectomy cavity. PMID:27053452

  2. Untangling the biological effects of cerium oxide nanoparticles: the role of surface valence states

    NASA Astrophysics Data System (ADS)

    Pulido-Reyes, Gerardo; Rodea-Palomares, Ismael; Das, Soumen; Sakthivel, Tamil Selvan; Leganes, Francisco; Rosal, Roberto; Seal, Sudipta; Fernández-Piñas, Francisca

    2015-10-01

    Cerium oxide nanoparticles (nanoceria; CNPs) have been found to have both pro-oxidant and anti-oxidant effects on different cell systems or organisms. In order to untangle the mechanisms which underlie the biological activity of nanoceria, we have studied the effect of five different CNPs on a model relevant aquatic microorganism. Neither shape, concentration, synthesis method, surface charge (ζ-potential), nor nominal size had any influence in the observed biological activity. The main driver of toxicity was found to be the percentage of surface content of Ce3+ sites: CNP1 (58%) and CNP5 (40%) were found to be toxic whereas CNP2 (28%), CNP3 (36%) and CNP4 (26%) were found to be non-toxic. The colloidal stability and redox chemistry of the most and least toxic CNPs, CNP1 and CNP2, respectively, were modified by incubation with iron and phosphate buffers. Blocking surface Ce3+ sites of the most toxic CNP, CNP1, with phosphate treatment reverted toxicity and stimulated growth. Colloidal destabilization with Fe treatment only increased toxicity of CNP1. The results of this study are relevant in the understanding of the main drivers of biological activity of nanoceria and to define global descriptors of engineered nanoparticles (ENPs) bioactivity which may be useful in safer-by-design strategies of nanomaterials.

  3. Untangling the biological effects of cerium oxide nanoparticles: the role of surface valence states

    PubMed Central

    Pulido-Reyes, Gerardo; Rodea-Palomares, Ismael; Das, Soumen; Sakthivel, Tamil Selvan; Leganes, Francisco; Rosal, Roberto; Seal, Sudipta; Fernández-Piñas, Francisca

    2015-01-01

    Cerium oxide nanoparticles (nanoceria; CNPs) have been found to have both pro-oxidant and anti-oxidant effects on different cell systems or organisms. In order to untangle the mechanisms which underlie the biological activity of nanoceria, we have studied the effect of five different CNPs on a model relevant aquatic microorganism. Neither shape, concentration, synthesis method, surface charge (ζ-potential), nor nominal size had any influence in the observed biological activity. The main driver of toxicity was found to be the percentage of surface content of Ce3+ sites: CNP1 (58%) and CNP5 (40%) were found to be toxic whereas CNP2 (28%), CNP3 (36%) and CNP4 (26%) were found to be non-toxic. The colloidal stability and redox chemistry of the most and least toxic CNPs, CNP1 and CNP2, respectively, were modified by incubation with iron and phosphate buffers. Blocking surface Ce3+ sites of the most toxic CNP, CNP1, with phosphate treatment reverted toxicity and stimulated growth. Colloidal destabilization with Fe treatment only increased toxicity of CNP1. The results of this study are relevant in the understanding of the main drivers of biological activity of nanoceria and to define global descriptors of engineered nanoparticles (ENPs) bioactivity which may be useful in safer-by-design strategies of nanomaterials. PMID:26489858

  4. Untangling the biological effects of cerium oxide nanoparticles: the role of surface valence states.

    PubMed

    Pulido-Reyes, Gerardo; Rodea-Palomares, Ismael; Das, Soumen; Sakthivel, Tamil Selvan; Leganes, Francisco; Rosal, Roberto; Seal, Sudipta; Fernández-Piñas, Francisca

    2015-01-01

    Cerium oxide nanoparticles (nanoceria; CNPs) have been found to have both pro-oxidant and anti-oxidant effects on different cell systems or organisms. In order to untangle the mechanisms which underlie the biological activity of nanoceria, we have studied the effect of five different CNPs on a model relevant aquatic microorganism. Neither shape, concentration, synthesis method, surface charge (ζ-potential), nor nominal size had any influence in the observed biological activity. The main driver of toxicity was found to be the percentage of surface content of Ce(3+) sites: CNP1 (58%) and CNP5 (40%) were found to be toxic whereas CNP2 (28%), CNP3 (36%) and CNP4 (26%) were found to be non-toxic. The colloidal stability and redox chemistry of the most and least toxic CNPs, CNP1 and CNP2, respectively, were modified by incubation with iron and phosphate buffers. Blocking surface Ce(3+) sites of the most toxic CNP, CNP1, with phosphate treatment reverted toxicity and stimulated growth. Colloidal destabilization with Fe treatment only increased toxicity of CNP1. The results of this study are relevant in the understanding of the main drivers of biological activity of nanoceria and to define global descriptors of engineered nanoparticles (ENPs) bioactivity which may be useful in safer-by-design strategies of nanomaterials.

  5. Morphology of cerium oxide surfaces in an oxidzing enviroment:a first-principles investigation

    NASA Astrophysics Data System (ADS)

    Fronzi, Marco; Soon, Aloysius; Stampfl, Catherine; Delley, Bernard; Traversa, Enrico

    2007-03-01

    A good understanding of the stability and chemistry of CeO2 surfaces is crucial for a better designing of solid oxide fuel cells. As the first step, we use DFT [1] to study the structural and electronic ground state properties of bulk CeO2. various surface termination of the low-index surface of CeO2 are then investigated, namely the stoichiometric, metal- and oxygen- rich terminations, and defected surfaces. Using the concept of ab initio atomistic thermodynamics&[tilde;2], we calculate the surface free energy phase diagram. This allows us to identify and predict stable, and potentally catalytically important, structures. There is an evidence to suggest an interesting morphological change in the surface structures with varying oxygen concentration. Reaction pathways for methane oxidation on low energy cerium oxide surfaces are being investigated and will be reported.[1] Formulated in the DMol^3 code; B. Delley, J. Chem. Phys. 92, 508 (1990);ibid. 113, 7756 (2000).[2] K. Reuter, C. Stampfl and M. Scheffler, in Handbook of Materials Modeling, Volume 1, Fundamental Models and Methods, Sidney Yip (Ed)(2005).

  6. Cerium Oxide Nanoparticles Decorated Graphene Nanosheets for Selective Detection of Dopamine.

    PubMed

    Nayak, Pranati; Santhosh, P N; Ramaprabhu, S

    2015-07-01

    The fabrication of a novel amperometric biosensor based on selective determination of dopamine (DA) using nafion coated cerium oxide nanoparticles (NPs) decorated graphene nanosheets (CeO2-HEG-nafion) as a transducer candidate is reported. Graphene was synthesized by hydrogen exfoliation technique. Decoration of CeO2NPs over graphene nanosheets was done by chemical reduction method. The electrochemical impedance spectroscopy (EIS) study shows the enhanced electron transfer kinetics of the composite compared to HEG modified and bare glassy carbon electrode (GCE). The response of the composite towards dopamine displays a lower oxidation potential of 0.23 V and a high oxidation current. The sensor exhibits linearity from 10 µM to 780 µM with a detection limit of 1 µM. In the presence of nafion, it shows excellent selectivity for coexisting interference species like Ascorbic acid (AA) and Uric acid (UA). The excellent performance of the biosensor can be attributed to large active surface area, enhanced electron transfer kinetics and high catalytic activity of the composite.

  7. Real-time observation of dynamic process of oxygen vacancy migration in cerium oxides under electric field

    SciTech Connect

    Li, Xiaomin; Qi, Kuo; Sun, Muhua; Huang, Qianming; Xu, Zhi E-mail: xdbai@iphy.ac.cn; Wang, Wenlong; Bai, Xuedong E-mail: xdbai@iphy.ac.cn

    2015-11-23

    The dynamic process of oxygen vacancy migration driven by the external electric field is directly observed at atomic scale in the cerium oxides (CeO{sub 2}) thin film by in-situ transmission electron microscopy method. When a bias voltage of a proper value is applied across the CeO{sub 2} film, the oxygen vacancies are formed near the interface of CeO{sub 2}/anode, followed by their migration along the direction of the external electric field. The structural modulation occurs in the [110] zone axis due to the ordering of oxygen vacancies. The migration of oxygen vacancies results in the reversible structural transformation, i.e., releasing and storing oxygen processes in CeO{sub 2}, which is of great significance for the ionic and electronic applications of the cerium oxides materials, such as oxygen pump, gas sensor, resistive random access memory, etc.

  8. Enzyme-free Detection of Hydrogen Peroxide from Cerium Oxide Nanoparticles Immobilized on Poly(4-vinylpyridine) Self-Assembled Monolayers

    SciTech Connect

    Gaynor, James D.; Karakoti, Ajay S.; Inerbaev, Talgat; Sanghavi, Shail P.; Nachimuthu, Ponnusamy; Shutthanandan, V.; Seal, Sudipta; Thevuthasan, Suntharampillai

    2013-05-02

    A single layer of oxygen-deficient cerium oxide nanoparticles (CNPs) are immobilized on microscopic glass slide using poly(4-vinylpyridine) (PVP) self-assembled monolayers (SAMs). A specific colorimetric property of CNPs when reacted with hydrogen peroxide allows for the direct, single-step peroxide detection which can be used in medical diagnosis and explosives detection. Multiple PVP-CNP immobilized layers improve sensitivity of detection and the sensor can be regenerated for reuse.

  9. Evaluation of cerium oxide coated Cu cermets as inert anodes for aluminum electrowinning

    SciTech Connect

    Not Available

    1992-08-01

    Cu/NiFe{sub 2}O{sub 4} cermets were evaluated, with and without an in-situ deposited CEROX (TM; cerium oxide) coating, in 100 h laboratory A1 electrowinning tests. Bath ratio and current density were varied between tests and corrosion was determined by contamination of the aluminum and cryolite by cermet components (Cu, Fe, and Ni). Higher bath ratios of 1.5 to 1.6 led to less corrosion and thicker CEROX coatings. Lower current densities led to slightly less corrosion but much less oxidation of the Cu cermet substrate. At identical test conditions, the corrosion of the CEROX coated cermets was 1/7 that of an uncoated cermet. Corrosion was increased in CEROX coated cermets tested under unsaturated alumina conditions. The electrical conductivity of the CEROX coating was measured to be {approximately}0.2 ohm{sup {minus}1}cm{sup {minus}1}, resulting in a slight voltage penalty, depending on the thickness of the coating.

  10. Evidence for an oxygen evolving iron–oxo–cerium intermediate in iron-catalysed water oxidation

    PubMed Central

    Codolà, Zoel; Gómez, Laura; Kleespies, Scott T.; Que, Lawrence; Costas, Miquel; Lloret-Fillol, Julio

    2016-01-01

    The non-haem iron complex α-[FeII(CF3SO3)2(mcp)] (mcp = (N,N′-dimethyl-N,N′-bis(2-pyridylmethyl)-1,2-cis-diaminocyclohexane) reacts with CeIV to oxidize water to O2, representing an iron-based functional model for the oxygen evolving complex of photosystem II. Here we trap an intermediate, characterized by cryospray ionization high resolution mass spectrometry and resonance Raman spectroscopy, and formulated as [(mcp)FeIV(O) (μ-O)CeIV(NO3)3]+, the first example of a well-characterized inner-sphere complex to be formed in cerium(IV)-mediated water oxidation. The identification of this reactive FeIV–O–CeIV adduct may open new pathways to validate mechanistic notions of an analogous MnV–O–CaII unit in the oxygen evolving complex that is responsible for carrying out the key O–O bond forming step. PMID:25609387

  11. A nanostructured cerium oxide film-based immunosensor for mycotoxin detection

    NASA Astrophysics Data System (ADS)

    Kaushik, Ajeet; Rathee Solanki, Pratima; Ansari, Anees Ahmad; Ahmad, Sharif; Dhar Malhotra, Bansi

    2009-02-01

    Rabbit-immunoglobulin antibodies (r-IgGs) and bovine serum albumin (BSA) have been immobilized onto sol-gel-derived nanostructured cerium oxide (nanoCeO2) film fabricated onto an indium-tin-oxide (ITO) coated glass plate to detect ochratoxin-A (OTA). Broad reflection planes obtained in x-ray diffraction (XRD) patterns reveal the formation of CeO2 nanostructures. Electrochemical studies reveal that nanoCeO2 particles provide an increased electroactive surface area for loading of r-IgGs with desired orientation, resulting in enhanced electron communication between r-IgGs and electrode. BSA/r-IgGs/nano CeO2/ITO immunoelectrode exhibits improved characteristics such as linear range (0.5-6 ng dl-1), low detection limit (0.25 ng dl-1), fast response time (30 s) and high sensitivity (1.27 µA ng-1 dl-1 cm-2). The high value of the association constant (Ka, 0.9 × 1011 l mol-1) indicates the high affinity of the BSA/r-IgGs/nanoCeO2/ITO immunoelectrode to OTA.

  12. Gold-supported cerium-doped NiOx catalysts for water oxidation

    NASA Astrophysics Data System (ADS)

    Ng, Jia Wei Desmond; García-Melchor, Max; Bajdich, Michal; Chakthranont, Pongkarn; Kirk, Charlotte; Vojvodic, Aleksandra; Jaramillo, Thomas F.

    2016-05-01

    The development of high-performance catalysts for the oxygen-evolution reaction (OER) is paramount for cost-effective conversion of renewable electricity to fuels and chemicals. Here we report the significant enhancement of the OER activity of electrodeposited NiOx films resulting from the combined effects of using cerium as a dopant and gold as a metal support. This NiCeOx-Au catalyst delivers high OER activity in alkaline media, and is among the most active OER electrocatalysts yet reported. On the basis of experimental observations and theoretical modelling, we ascribe the activity to a combination of electronic, geometric and support effects, where highly active under-coordinated sites at the oxide support interface are modified by the local chemical binding environment and by doping the host Ni oxide with Ce. The NiCeOx-Au catalyst is further demonstrated in a device context by pairing it with a nickel-molybdenum hydrogen evolution catalyst in a water electrolyser, which delivers 50 mA consistently at 1.5 V over 24 h of continuous operation.

  13. Gold-supported cerium-doped NiOx catalysts for water oxidation

    NASA Astrophysics Data System (ADS)

    Ng, Jia Wei Desmond; García-Melchor, Max; Bajdich, Michal; Chakthranont, Pongkarn; Kirk, Charlotte; Vojvodic, Aleksandra; Jaramillo, Thomas F.

    2016-05-01

    The development of high-performance catalysts for the oxygen-evolution reaction (OER) is paramount for cost-effective conversion of renewable electricity to fuels and chemicals. Here we report the significant enhancement of the OER activity of electrodeposited NiOx films resulting from the combined effects of using cerium as a dopant and gold as a metal support. This NiCeOx–Au catalyst delivers high OER activity in alkaline media, and is among the most active OER electrocatalysts yet reported. On the basis of experimental observations and theoretical modelling, we ascribe the activity to a combination of electronic, geometric and support effects, where highly active under-coordinated sites at the oxide support interface are modified by the local chemical binding environment and by doping the host Ni oxide with Ce. The NiCeOx–Au catalyst is further demonstrated in a device context by pairing it with a nickel–molybdenum hydrogen evolution catalyst in a water electrolyser, which delivers 50 mA consistently at 1.5 V over 24 h of continuous operation.

  14. Plasma sprayed cerium oxide coating inhibits H2O2-induced oxidative stress and supports cell viability.

    PubMed

    Li, Kai; Xie, Youtao; You, Mingyu; Huang, Liping; Zheng, Xuebin

    2016-06-01

    Oxidative stress is a risk factor in the pathogenesis of osteoporosis, and plays a major role in bone regeneration of osteoporotic patients. Cerium oxide (CeO2) ceramics have the unique ability to protect various types of cells from oxidative damage, making them attractive for biomedical applications. In this study, we developed a plasma sprayed CeO2 coating with a hierarchical topography where ceria nanoparticles were superimposed in the micro-rough coating surface. The protective effects of the CeO2 coating on the response of osteoblasts to H2O2-induced oxidative stress have been demonstrated in terms of cell viability, apoptosis and differentiation. The CeO2 coating reversed the reduced superoxide dismutase activity, decreased reactive oxygen species production and suppressed malondialdehyde formation in H2O2-treated osteoblasts. It indicated that the CeO2 coating can preserve the intracellular antioxidant defense system. The cytocompatibility of the CeO2 coating was further assessed in vitro by cell viability assay and scanning electron microscopy analysis. Taken together, the CeO2 coating could provide an opportunity to be utilized as a potential candidate for bone regeneration under oxidative stress.

  15. Cerium Dioxide Nanoparticle Exposure Improves Microvascular Dysfunction and Reduces Oxidative Stress in Spontaneously Hypertensive Rats

    PubMed Central

    Minarchick, Valerie C.; Stapleton, Phoebe A.; Sabolsky, Edward M.; Nurkiewicz, Timothy R.

    2015-01-01

    The elevated production of reactive oxygen species (ROS) in the vascular wall is associated with cardiovascular diseases such as hypertension. This increase in oxidative stress contributes to various mechanisms of vascular dysfunction, such as decreased nitric oxide bioavailability. Therefore, anti-oxidants are being researched to decrease the high levels of ROS, which could improve the microvascular dysfunction associated with various cardiovascular diseases. From a therapeutic perspective, cerium dioxide nanoparticles (CeO2 NP) hold great anti-oxidant potential, but their in vivo activity is unclear. Due to this potential anti-oxidant action, we hypothesize that injected CeO2 NP would decrease microvascular dysfunction and oxidative stress associated with hypertension. In order to simulate a therapeutic application, spontaneously hypertensive (SH) and Wistar-Kyoto (WKY) rats were intravenously injected with either saline or CeO2 NP (100 μg suspended in saline). Twenty-four hours post-exposure mesenteric arteriolar reactivity was assessed via intravital microscopy. Endothelium-dependent and –independent function was assessed via acetylcholine and sodium nitroprusside. Microvascular oxidative stress was analyzed using fluorescent staining in isolated mesenteric arterioles. Finally, systemic inflammation was examined using a multiplex analysis and venular leukocyte flux was counted. Endothelium-dependent dilation was significantly decreased in the SH rats (29.68 ± 3.28%, maximal response) and this microvascular dysfunction was significantly improved following CeO2 NP exposure (43.76 ± 4.33%, maximal response). There was also an increase in oxidative stress in the SH rats, which was abolished following CeO2 NP treatment. These results provided evidence that CeO2 NP act as an anti-oxidant in vivo. There were also changes in the inflammatory profile in the WKY and SH rats. In WKY rats, IL-10 and TNF-α were increased following CeO2 NP treatment. Finally, leukocyte

  16. Influence of agglomeration of cerium oxide nanoparticles and speciation of cerium(III) on short term effects to the green algae Chlamydomonas reinhardtii.

    PubMed

    Röhder, Lena A; Brandt, Tanja; Sigg, Laura; Behra, Renata

    2014-07-01

    Cerium oxide nanoparticles (CeO2 NP) are increasingly used in industrial applications and may be released to the aquatic environment. The fate of CeO2 NP and effects on algae are largely unknown. In this study, the short term effects of CeO2 NP in two different agglomeration states on the green algae Chlamydomonas reinhardtii were examined. The role of dissolved cerium(III) on toxicity, its speciation and the dissolution of CeO2 NP were considered. The role of cell wall of C. reinhardtii as a barrier and its influence on the sensitivity to CeO2 NP and cerium(III) was evaluated by testing both, the wild type and the cell wall free mutant of C. reinhardtii. Characterization showed that CeO2 NP had a surface charge of ∼0mV at physiological pH and agglomerated in exposure media. Phosphate stabilized CeO2 NP at pH 7.5 over 24h. This effect was exploited to test CeO2 NP dispersed in phosphate with a mean size of 140nm and agglomerated in absence of phosphate with a mean size of 2000nm. The level of dissolved cerium(III) in CeO2 NP suspensions was very low and between 0.1 and 27nM in all tested media. Exposure of C. reinhardtii to Ce(NO3)3 decreased the photosynthetic yield in a concentration dependent manner with EC50 of 7.5±0.84μM for wild type and EC50 of 6.3±0.53μM for the cell wall free mutant. The intracellular level of reactive oxygen species (ROS) increased upon exposure to Ce(NO3)3 with effective concentrations similar to those inhibiting photosynthesis. The agglomerated CeO2 NP caused a slight decrease of photosynthetic yield at the highest concentrations (100μM), while no effect was observed for dispersed CeO2 NP. The low toxicity of agglomerated CeO2 NP was attributed quantitatively to Ce(3+) ions co-occurring in the nanoparticle suspension whereas for dispersed CeO2 NP, dissolved Ce(3+) was precipitated with phosphate and not bioavailable. Furthermore CeO2 NP did not affect the intracellular ROS level. The cell wall free mutant and wild type of C

  17. Influence of agglomeration of cerium oxide nanoparticles and speciation of cerium(III) on short term effects to the green algae Chlamydomonas reinhardtii.

    PubMed

    Röhder, Lena A; Brandt, Tanja; Sigg, Laura; Behra, Renata

    2014-07-01

    Cerium oxide nanoparticles (CeO2 NP) are increasingly used in industrial applications and may be released to the aquatic environment. The fate of CeO2 NP and effects on algae are largely unknown. In this study, the short term effects of CeO2 NP in two different agglomeration states on the green algae Chlamydomonas reinhardtii were examined. The role of dissolved cerium(III) on toxicity, its speciation and the dissolution of CeO2 NP were considered. The role of cell wall of C. reinhardtii as a barrier and its influence on the sensitivity to CeO2 NP and cerium(III) was evaluated by testing both, the wild type and the cell wall free mutant of C. reinhardtii. Characterization showed that CeO2 NP had a surface charge of ∼0mV at physiological pH and agglomerated in exposure media. Phosphate stabilized CeO2 NP at pH 7.5 over 24h. This effect was exploited to test CeO2 NP dispersed in phosphate with a mean size of 140nm and agglomerated in absence of phosphate with a mean size of 2000nm. The level of dissolved cerium(III) in CeO2 NP suspensions was very low and between 0.1 and 27nM in all tested media. Exposure of C. reinhardtii to Ce(NO3)3 decreased the photosynthetic yield in a concentration dependent manner with EC50 of 7.5±0.84μM for wild type and EC50 of 6.3±0.53μM for the cell wall free mutant. The intracellular level of reactive oxygen species (ROS) increased upon exposure to Ce(NO3)3 with effective concentrations similar to those inhibiting photosynthesis. The agglomerated CeO2 NP caused a slight decrease of photosynthetic yield at the highest concentrations (100μM), while no effect was observed for dispersed CeO2 NP. The low toxicity of agglomerated CeO2 NP was attributed quantitatively to Ce(3+) ions co-occurring in the nanoparticle suspension whereas for dispersed CeO2 NP, dissolved Ce(3+) was precipitated with phosphate and not bioavailable. Furthermore CeO2 NP did not affect the intracellular ROS level. The cell wall free mutant and wild type of C

  18. A phosphate-dependent shift in redox state of cerium oxide nanoparticles and its effects on catalytic properties

    SciTech Connect

    Singh, Sanjay; Dosani, Talib; Karakoti, Ajay S.; Kumar, Amit; Seal, Sudipta; Self, William

    2011-10-01

    Cerium oxide nanoparticles (CeNPs) have shown promise as catalytic antioxidants in cell culture and animal models as both superoxide dismutase and catalase mimetics. The reactivity of the cerium (Ce) atoms at the surface of its oxide particle is critical to such therapeutic properties, yet little is known about the potential for a protein or small molecule corona to form on these materials in vivo. Moreover Ce atoms in these active sites have the potential to interact with small molecule anions, peptides, or sugars when administered in culture or animal models. Several nanomaterials have been shown to alter or aggregate under these conditions, rendering them less useful for biomedical applications. In this work we have studied the change in catalytic properties of CeNPs when exposed to various biologically relevant conditions in vitro. We have found that CeNPs are resistant to broad changes in pH and also not altered by incubation in cell culture medium. However to our surprise phosphate anions significantly altered the characteristics of these nanomaterials and shifted the catalytic behavior due to the binding of phosphate anions to cerium. Given the abundance of phosphate in biological systems in an inorganic form, it is likely that the action of CeNPs as a catalyst may be strongly influenced by the local concentration of phosphate in the cells and/or tissues in which it has been introduced.

  19. A phosphate-dependent shift in redox state of cerium oxide nanoparticles and its effects on catalytic properties

    PubMed Central

    Singh, Sanjay; Dosani, Talib; Karakoti, Ajay; Kumar, Amit; Seal, Sudipta; Self, William T.

    2011-01-01

    Cerium oxide nanoparticles (CeNPs) have shown promise as catalytic antioxidants in cell culture and animal models as both superoxide dismutase and catalase mimetics. The reactivity of the cerium (Ce) atoms at the surface of its oxide particle is critical to such therapeutic properties, yet little is known about the potential for a protein or small molecule corona to form on these materials in vivo. Moreover Ce atoms in these active sites have the potential to interact with small molecule anions, peptides, or sugars when administered in culture or animal models. Several nanomaterials have been shown to alter or aggregate under these conditions, rendering them less useful for biomedical applications. In this work we have studied the change in catalytic properties of CeNPs when exposed to various biologically relevant conditions in vitro. We have found that CeNPs are resistant to broad changes in pH and also not altered by incubation in cell culture medium. However to our surprise phosphate anions significantly altered the characteristics of these nanomaterials and shifted the catalytic behavior due to the binding of phosphate anions to cerium. Given the abundance of phosphate in biological systems in an inorganic form, it is likely that the action of CeNPs as a catalyst may be strongly influenced by the local concentration of phosphate in the cells and/or tissues in which it has been introduced. PMID:21704369

  20. Predicting contamination by the fuel additive cerium oxide engineered nanoparticles within the United Kingdom and the associated risks.

    PubMed

    Johnson, Andrew C; Park, Barry

    2012-11-01

    As a fuel additive, cerium oxide nanoparticles may become widely dispersed throughout the environment. Commercial information from the United Kingdom (UK) on the use of cerium oxide nanoparticles was used to perform a modeling and risk assessment exercise. Discharge from exhausts took into account the likely removal by filters fitted to these vehicles. For predicting current soil exposure, scenarios were examined, ranging from dispersion occurring across the entire UK landmass to only within the urban area to only 20 m on either side of road networks. For soils, the highest predicted contamination level was 0.016 mg/kg within 20 m of a road following seven years of continuous deposition. This value would represent 0.027% of reported natural background cerium. If usage were to double for five more years, levels would not be expected to exceed 0.04 mg/kg. River water contamination considered direct aerial deposition and indirect contamination via runoff in the water and entrained soil sediment, with the highest level of 0.02 ng/L predicted. The highest predicted water concentration of 300 ng/L was associated with water draining from a road surface, assuming a restricted deposition spread. These predictions are well below most toxicological levels of concern.

  1. Correlation of the oxidation state of cerium in sol?gel glasses as a function of thermal treatment via optical spectroscopy and XANES studies

    NASA Astrophysics Data System (ADS)

    Assefa, Zerihun; Haire, R. G.; Caulder, D. L.; Shuh, D. K.

    2004-07-01

    Sol-gel glass matrices containing lanthanides have numerous technological applications and their formation involves several chemical facets. In the case of cerium, its ability to exist in two different oxidation states or in mixed valence state provides additional complexities for the sol-gel process. The oxidation state of cerium present during different facets of preparation of sol-gel glasses, and also as a function of the starting oxidation state of cerium added, were studied both by optical spectroscopy and X-ray absorption near-edge structures (XANES). The findings acquired by each approach were compared. The primary focus was on the redox chemistries associated with sample preparation, gelation, and thermal treatment. When Ce 3+ is introduced into the starting sols, the trivalent state normally prevails in the wet and room temperature-dried gels. Heating in air at >100 °C can generate a light yellow coloration with partial oxidation to the tetravalent state. Above 200 °C and up to ˜1000 °C, cerium is oxidized to its tetravalent state. In contrast, when tetravalent cerium is introduced into the sol, both the wet and room temperature-dried gels lose the yellow-brown color of the initial ceric ammonium nitrate solution. When the sol-gel is heated to 110 °C it turns yellowish as the cerium tends to be re-oxidized. The yellow color is believed to represent the effect of oxidation and oligomerization of the cerium-silanol units in the matrix. The luminescence properties are also affected by these changes, the details of which are reported herein.

  2. Cellular uptake and activity of heparin functionalised cerium oxide nanoparticles in monocytes.

    PubMed

    Ting, S R Simon; Whitelock, John M; Tomic, Romana; Gunawan, Cindy; Teoh, Wey Yang; Amal, Rose; Lord, Megan S

    2013-06-01

    Cerium oxide nanoparticles (nanoceria) are effective in scavenging intracellular reactive oxygen species (ROS). In this study nanoceria synthesized by flame spray pyrolysis (dXRD = 12 nm) were functionalised with heparin via an organosilane linker, 3-aminopropyltriethoxysilane. Nanoceria were functionalised with approximately 130 heparin molecules per nanoparticle as determined by thermo gravimetric analysis. Heparin functionalised nanoceria were more effectively internalised by the human monocyte cell line, U937, and U937 cells that had been activated with phorbol 12 myristate 13-acetate (PMA) than bare nanoceria. The heparin functionalised nanoceria were also more effective in scavenging ROS than nanoceria in both activated and unactivated U937 cells. Heparin coupled nanoceria were found to be biologically active due to their ability to bind fibroblast growth factor 2 and signal through FGF receptor 1. Additionally, the heparin-coupled nanoceria, once internalised by the cells, were found to be degraded by 48 h. Together these data demonstrated that heparin enhanced the biological properties of nanoceria in terms of cellular uptake and ROS scavenging, while the nanoceria themselves were more effective at delivering heparin intracellularly than exposing cells to heparin in solution. PMID:23478040

  3. Role of phosphate on stability and catalase mimetic activity of cerium oxide nanoparticles.

    PubMed

    Singh, Ragini; Singh, Sanjay

    2015-08-01

    Cerium oxide nanoparticles (CeNPs) have been recently shown to scavenge reactive oxygen and nitrogen species (ROS and RNS) in different experimental model systems. CeNPs (3+) and CeNPs (4+) have been shown to exhibit superoxide dismutase (SOD) and catalase mimetic activity, respectively. Due to their nanoscale dimension, CeNPs are expected to interact with the components of biologically relevant buffers and medium, which could alter their catalytic properties. We have demonstrated earlier that CeNPs (3+) interact with phosphate and lose the SOD activity. However, very little is known about the interaction of CeNPs (4+) with the phosphate and other anions, predominantly present in biological buffers and their effects on the catalase mimetic-activity of these nanoparticles. In this study, we report that catalase mimetic-activity of CeNPs (4+) is resistant to the phosphate anions, pH changes and composition of cell culture media. Given the abundance of phosphate anions in the biological system, it is likely that internalized CeNPs would be influenced by cytoplasmic and nucleoplasmic concentration of phosphate.

  4. Antioxidant Potential and Toxicity Study of the Cerium Oxide Nanoparticles Synthesized by Microwave-Mediated Synthesis.

    PubMed

    Soren, Siba; Jena, Soumya Ranjan; Samanta, Luna; Parhi, Purnendu

    2015-09-01

    Monodispersed cerium oxide nanoparticle has been synthesized by microwave-mediated hydrothermal as well as microwave-mediated solvothermal synthesis. X-ray diffraction (XRD) data shows that the synthesized particles are single phase. SEM and TEM analysis suggest that particle synthesized by microwave-mediated solvothermal method are less agglomerated. In vitro toxicology study of the synthesized nanoceria particles has shown good free radical scavenging activity for NO and 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical assayed except superoxide radical within a concentration range of 25 to 75 ng ml(-1). Nanoceria particle also showed inhibition of Fe-ascorbate-induced lipid peroxidation (LPx) in chick liver mitochondrial fractions. Solvothermally synthesized nanoceria showed better protection against Fe-ascorbate-induced LPx than the hydrothermal one while the hydrothermally synthesized nanoceria showed better DPPH and NO scavenging activity. The ceria nanoparticles also prevented Fe-ascorbate-H2O2-induced carbonylation of bovine serum albumin in a dose-dependent manner. At higher concentration, i.e., 100 ng ml(-1), the synthesized nanoparticles showed a reverse trend in all the parameters measured indicating its toxicity at higher doses.

  5. Preparation and evaluation of cerium oxide-bovine hydroxyapatite composites for biomedical engineering applications.

    PubMed

    Gunduz, O; Gode, C; Ahmad, Z; Gökçe, H; Yetmez, M; Kalkandelen, C; Sahin, Y M; Oktar, F N

    2014-07-01

    The fabrication and characterization of bovine hydroxyapatite (BHA) and cerium oxide (CeO2) composites are presented. CeO2 (at varying concentrations 1, 5 and 10wt%) were added to calcinated BHA powder. The resulting mixtures were shaped into green cylindrical samples by powder pressing (350MPa) followed by sintering in air (1000-1300°C for 4h). Density, Vickers microhardness (HV), compression strength, scanning electron microscopy (SEM) and X-ray diffraction (XRD) studies were performed on the products. The sintering behavior, microstructural characteristics and mechanical properties were evaluated. Differences in the sintering temperature (for 1wt% CeO2 composites) between 1200 and 1300°C, show a 3.3% increase in the microhardness (564 and 582.75HV, respectively). Composites prepared at 1300°C demonstrate the greatest compression strength with comparable results for 5 and 10wt% CeO2 content (106 and 107MPa) which are significantly better than those for 1wt% and those that do not include any CeO2 (90 and below 60MPa, respectively). The results obtained suggest optimal parameters to be used in preparation of BHA and CeO2 composites, while also highlighting the potential of such materials in several biomedical engineering applications.

  6. CO responses of sensors based on cerium oxide thick films prepared from clustered spherical nanoparticles.

    PubMed

    Izu, Noriya; Matsubara, Ichiro; Itoh, Toshio; Akamatsu, Takafumi; Shin, Woosuck

    2013-01-01

    Various types of CO sensors based on cerium oxide (ceria) have been reported recently. It has also been reported that the response speed of CO sensors fabricated from porous ceria thick films comprising nanoparticles is extremely high. However, the response value of such sensors is not suitably high. In this study, we investigated methods of improving the response values of CO sensors based on ceria and prepared gas sensors from core-shell ceria polymer hybrid nanoparticles. These hybrid nanoparticles have been reported to have a unique structure: The core consists of a cluster of ceria crystallites several nanometers in size. We compared the characteristics of the sensors based on thick films prepared from core-shell nanoparticles with those of sensors based on thick films prepared from conventionally used precipitated nanoparticles. The sensors prepared from the core-shell nanoparticles exhibited a resistance that was ten times greater than that of the sensors prepared from the precipitated nanoparticles. The response values of the gas sensors based on the core-shell nanoparticles also was higher than that of the sensors based on the precipitated nanoparticles. Finally, improvements in sensor response were also noticed after the addition of Au nanoparticles to the thick films used to fabricate the two types of sensors. PMID:23529123

  7. Cerium oxide nanoparticles inhibit the migration and proliferation of gastric cancer by increasing DHX15 expression

    PubMed Central

    Xiao, Yu-Feng; Li, Jian-Mei; Wang, Su-Min; Yong, Xin; Tang, Bo; Jie, Meng-Meng; Dong, Hui; Yang, Xiao-Chao; Yang, Shi-Ming

    2016-01-01

    Gastric cancer is one of the leading causes of tumor-related deaths in the world. Current treatment options do not satisfy doctors and patients, and new therapies are therefore needed. Cerium oxide nanoparticles (CNPs) have been studied as a potential therapeutic approach for treating many diseases. However, their effects on human gastric cancer are currently unknown. Therefore, in this study, we aimed to characterize the effects of CNPs on human gastric cancer cell lines (MKN28 and BGC823). Gastric cancer cells were cocultured with different concentrations of CNPs, and proliferation and migration were measured both in vitro and in vivo. We found that CNPs inhibited the migration of gastric cancer cells when applied at different concentrations, but only a relatively high concentration (10 µg/mL) of CNPs suppressed proliferation. Furthermore, we found that CNPs increased the expression of DHX15 and its downstream signaling pathways. We therefore provide evidence showing that CNPs may be a promising approach to suppress malignant activity of gastric cancer by increasing the expression of DHX15. PMID:27486320

  8. Physiological and biochemical response of soil-grown barley (Hordeum vulgare L.) to cerium oxide nanoparticles.

    PubMed

    Rico, Cyren M; Barrios, Ana C; Tan, Wenjuan; Rubenecia, Rosnah; Lee, Sang Chul; Varela-Ramirez, Armando; Peralta-Videa, Jose R; Gardea-Torresdey, Jorge L

    2015-07-01

    A soil microcosm study was performed to examine the impacts of cerium oxide nanoparticles (nCeO2) on the physiology, productivity, and macromolecular composition of barley (Hordeum vulgare L.). The plants were cultivated in soil treated with nCeO2 at 0, 125, 250, and 500 mg kg(-1) (control, nCeO2-L, nCeO2-M, and nCeO2-H, respectively). Accumulation of Ce in leaves/grains and its effects on plant stress and nutrient loading were analyzed. The data revealed that nCeO2-H promoted plant development resulting in 331 % increase in shoot biomass compared with the control. nCeO2 treatment modified the stress levels in leaves without apparent signs of toxicity. However, plants exposed to nCeO2-H treatment did not form grains. Compared with control, nCeO2-M enhanced grain Ce accumulation by as much as 294 % which was accompanied by remarkable increases in P, K, Ca, Mg, S, Fe, Zn, Cu, and Al. Likewise, nCeO2-M enhanced the methionine, aspartic acid, threonine, tyrosine, arginine, and linolenic acid contents in the grains by up to 617, 31, 58, 141, 378, and 2.47 % respectively, compared with the rest of the treatments. The findings illustrate the beneficial and harmful effects of nanoceria in barley.

  9. Effects of cerium oxide nanoparticles on soil enzymatic activities and wheat grass nutrients uptake

    NASA Astrophysics Data System (ADS)

    Li, Biting; Chen, Yirui; Bai, Lingyun; Jacobson, Astrid; Darnault, Christophe

    2015-04-01

    The US National Science Foundation estimated that the use of nanomaterials and nanotechnology would reach a global market value of 1 million this year. Concomitant with the wide applications of nanoparticles is an increasing risk of adverse effects to the environment and human health. As a common nanomaterial used as a fuel catalyst and polish material, cerium (IV) oxide nanoparticles (CeO2 NP) were tested for their potential impact on soil health and plant growth. Through exposure by air, water, and solid deposition, nanoparticles may accumulate in soils and impact agricultural systems. The objectives of this research were to determine whether CeO2 NPs affect the growth of wheat grass and selected soil enzyme activities chose as indicators of soil health. Wheat grass was grown in plant boxes containing CeO2 NPs mixed with agricultural soil at different concentrations. Two control groups were included: one consisting of soil with plants but no CeO2 NPs, and one containing only soil, i.e., no NP or wheat plants added. The plants were grown for 10 weeks and harvested every two weeks in a laboratory under sodium growth lights. At the end of the each growing period, two weeks, soils were assayed for phosphatase, β-glucosidase, and urease activities, and NPK values. Spectrophotometer analyses were used to assess enzyme activities, and NPK values were tested by Clemson Agricultural Center. Wheat yields were estimated by shoot and root lengths and weights.

  10. Electroanalytical evaluation of antioxidant activity of cerium oxide nanoparticles by nanoparticle collisions at microelectrodes.

    PubMed

    Sardesai, Naimish P; Andreescu, Daniel; Andreescu, Silvana

    2013-11-13

    We describe a simple, cost-effective and rapid electrochemical screening approach to evaluate antioxidant activity of cerium oxide nanoparticles (CeO2 NPs) by single nanoparticle collision at microelectrodes. The method is based on direct monitoring of the interaction between a Pt microelectrode and surface bound superoxo and peroxo anions of CeO2 NPs (Ce-O2(-)/O2(2-)) formed upon exposure to H2O2, selected here as a model reactive oxygen species. We observe an increase in spike current frequency for CeO2 NPs exposed to H2O2, which we attribute to the reduction of surface bound oxygen species when the particles collide with the microelectrode. The results were confirmed with spectroscopic techniques that demonstrate changes in surface reactivity and composition. The spike frequency was found to correlate well with the superoxide dismutase activity of these particles. This approach could enable routine screening of antioxidant NPs using a rapid and inexpensive assay.

  11. Intratracheal instillation of cerium oxide nanoparticles induces hepatic toxicity in male Sprague-Dawley rats

    PubMed Central

    Nalabotu, Siva K; Kolli, Madhukar B; Triest, William E; Ma, Jane Y; Manne, Nandini DPK; Katta, Anjaiah; Addagarla, Hari S; Rice, Kevin M; Blough, Eric R

    2011-01-01

    Background Cerium oxide (CeO2) nanoparticles have been posited to have both beneficial and toxic effects on biological systems. Herein, we examine if a single intratracheal instillation of CeO2 nanoparticles is associated with systemic toxicity in male Sprague-Dawley rats. Methods and results Compared with control animals, CeO2 nanoparticle exposure was associated with increased liver ceria levels, elevations in serum alanine transaminase levels, reduced albumin levels, a diminished sodium-potassium ratio, and decreased serum triglyceride levels (P < 0.05). Consistent with these data, rats exposed to CeO2 nanoparticles also exhibited reductions in liver weight (P < 0.05) and dose-dependent hydropic degeneration, hepatocyte enlargement, sinusoidal dilatation, and accumulation of granular material. No histopathological alterations were observed in the kidney, spleen, and heart. Analysis of serum biomarkers suggested an elevation of acute phase reactants and markers of hepatocyte injury in the rats exposed to CeO2 nanoparticles. Conclusion Taken together, these data suggest that intratracheal instillation of CeO2 nanoparticles can result in liver damage. PMID:22072870

  12. CO responses of sensors based on cerium oxide thick films prepared from clustered spherical nanoparticles.

    PubMed

    Izu, Noriya; Matsubara, Ichiro; Itoh, Toshio; Akamatsu, Takafumi; Shin, Woosuck

    2013-03-08

    Various types of CO sensors based on cerium oxide (ceria) have been reported recently. It has also been reported that the response speed of CO sensors fabricated from porous ceria thick films comprising nanoparticles is extremely high. However, the response value of such sensors is not suitably high. In this study, we investigated methods of improving the response values of CO sensors based on ceria and prepared gas sensors from core-shell ceria polymer hybrid nanoparticles. These hybrid nanoparticles have been reported to have a unique structure: The core consists of a cluster of ceria crystallites several nanometers in size. We compared the characteristics of the sensors based on thick films prepared from core-shell nanoparticles with those of sensors based on thick films prepared from conventionally used precipitated nanoparticles. The sensors prepared from the core-shell nanoparticles exhibited a resistance that was ten times greater than that of the sensors prepared from the precipitated nanoparticles. The response values of the gas sensors based on the core-shell nanoparticles also was higher than that of the sensors based on the precipitated nanoparticles. Finally, improvements in sensor response were also noticed after the addition of Au nanoparticles to the thick films used to fabricate the two types of sensors.

  13. Electroanalytical evaluation of antioxidant activity of cerium oxide nanoparticles by nanoparticle collisions at microelectrodes.

    PubMed

    Sardesai, Naimish P; Andreescu, Daniel; Andreescu, Silvana

    2013-11-13

    We describe a simple, cost-effective and rapid electrochemical screening approach to evaluate antioxidant activity of cerium oxide nanoparticles (CeO2 NPs) by single nanoparticle collision at microelectrodes. The method is based on direct monitoring of the interaction between a Pt microelectrode and surface bound superoxo and peroxo anions of CeO2 NPs (Ce-O2(-)/O2(2-)) formed upon exposure to H2O2, selected here as a model reactive oxygen species. We observe an increase in spike current frequency for CeO2 NPs exposed to H2O2, which we attribute to the reduction of surface bound oxygen species when the particles collide with the microelectrode. The results were confirmed with spectroscopic techniques that demonstrate changes in surface reactivity and composition. The spike frequency was found to correlate well with the superoxide dismutase activity of these particles. This approach could enable routine screening of antioxidant NPs using a rapid and inexpensive assay. PMID:24079646

  14. Cerium oxide nanoparticle aggregates affect stress response and function in Caenorhabditis elegans

    PubMed Central

    Rogers, Steven; Rice, Kevin M; Manne, Nandini DPK; Shokuhfar, Tolou; He, Kun; Selvaraj, Vellaisamy

    2015-01-01

    Objective: The continual increase in production and disposal of nanomaterials raises concerns regarding the safety of nanoparticles on the environmental and human health. Recent studies suggest that cerium oxide (CeO2) nanoparticles may possess both harmful and beneficial effects on biological processes. The primary objective of this study is to evaluate how exposure to different concentrations (0.17–17.21 µg/mL) of aggregated CeO2 nanoparticles affects indices of whole animal stress and survivability in Caenorhabditis elegans. Methods: Caenorhabditis elegans were exposed to different concentrations of CeO2 nanoparticles and evaluated. Results: Our findings demonstrate that chronic exposure of CeO2 nanoparticle aggregates is associated with increased levels of reactive oxygen species and heat shock stress response (HSP-4) in Caenorhabditis elegans, but not mortality. Conversely, CeO2 aggregates promoted strain-dependent decreases in animal fertility, a decline in stress resistance as measured by thermotolerance, and shortened worm length. Conclusion: The data obtained from this study reveal the sublethal toxic effects of CeO2 nanoparticle aggregates in Caenorhabditis elegans and contribute to our understanding of how exposure to CeO2 may affect the environment. PMID:26770770

  15. Grain size dependence of dielectric relaxation in cerium oxide as high-k layer

    PubMed Central

    2013-01-01

    Cerium oxide (CeO2) thin films used liquid injection atomic layer deposition (ALD) for deposition and ALD procedures were run at substrate temperatures of 150°C, 200°C, 250°C, 300°C, and 350°C, respectively. CeO2 were grown on n-Si(100) wafers. Variations in the grain sizes of the samples are governed by the deposition temperature and have been estimated using Scherrer analysis of the X-ray diffraction patterns. The changing grain size correlates with the changes seen in the Raman spectrum. Strong frequency dispersion is found in the capacitance-voltage measurement. Normalized dielectric constant measurement is quantitatively utilized to characterize the dielectric constant variation. The relationship extracted between grain size and dielectric relaxation for CeO2 suggests that tuning properties for improved frequency dispersion can be achieved by controlling the grain size, hence the strain at the nanoscale dimensions. PMID:23587419

  16. Effects of amorphous silica coating on cerium oxide nanoparticles induced pulmonary responses

    PubMed Central

    Ma, Jane; Mercer, Robert R.; Barger, Mark; Schwegler-Berry, Diane; Cohen, Joel M.; Demokritou, Philip; Castranova, Vincent

    2015-01-01

    Recently cerium compounds have been used in a variety of consumer products, including diesel fuel additives, to increase fuel combustion efficiency and decrease diesel soot emissions. However, cerium oxide (CeO2) nanoparticles have been detected in the exhaust, which raises a health concern. Previous studies have shown that exposure of rats to nanoscale CeO2 by intratracheal instillation (IT) induces sustained pulmonary inflammation and fibrosis. In the present study, male Sprague–Dawley rats were exposed to CeO2 or CeO2 coated with a nano layer of amorphous SiO2 (aSiO2/CeO2) by a single IT and sacrificed at various times post-exposure to assess potential protective effects of the aSiO2 coating. The first acellular bronchoalveolar lavage (BAL) fluid and BAL cells were collected and analyzed from all exposed animals. At the low dose (0.15 mg/kg), CeO2 but not aSiO2/CeO2 exposure induced inflammation. However, at the higher doses, both particles induced a dose-related inflammation, cytotoxicity, inflammatory cytokines, matrix metalloproteinase (MMP)-9, and tissue inhibitor of MMP at 1 day post-exposure. Morphological analysis of lung showed an increased inflammation, surfactant and collagen fibers after CeO2 (high dose at 3.5 mg/kg) treatment at 28 days post-exposure. aSiO2 coating significantly reduced CeO2-induced inflammatory responses in the airspace and appeared to attenuate phospholipidosis and fibrosis. Energy dispersive X-ray spectroscopy analysis showed Ce and phosphorous (P) in all particle-exposed lungs, whereas Si was only detected in aSiO2/CeO2-exposed lungs up to 3 days after exposure, suggesting that aSiO2 dissolved off the CeO2 core, and some of the CeO2 was transformed to CePO4 with time. These results demonstrate that aSiO2 coating reduce CeO2-induced inflammation, phospholipidosis and fibrosis. PMID:26210349

  17. Interactive effects of cerium oxide and diesel exhaust nanoparticles on inducing pulmonary fibrosis

    SciTech Connect

    Ma, Jane Y.C.; Young, Shih-Houng; Mercer, Robert R.; Barger, Mark; Schwegler-Berry, Diane; Ma, Joseph K.; Castranova, Vincent

    2014-07-15

    Cerium compounds have been used as a fuel-borne catalyst to lower the generation of diesel exhaust particles (DEPs), but are emitted as cerium oxide nanoparticles (CeO{sub 2}) along with DEP in the diesel exhaust. The present study investigates the effects of the combined exposure to DEP and CeO{sub 2} on the pulmonary system in a rat model. Specific pathogen-free male Sprague–Dawley rats were exposed to CeO{sub 2} and/or DEP via a single intratracheal instillation and were sacrificed at various time points post-exposure. This investigation demonstrated that CeO{sub 2} induces a sustained inflammatory response, whereas DEP elicits a switch of the pulmonary immune response from Th1 to Th2. Both CeO{sub 2} and DEP activated AM and lymphocyte secretion of the proinflammatory cytokines IL-12 and IFN-γ, respectively. However, only DEP enhanced the anti-inflammatory cytokine IL-10 production in response to ex vivo LPS or Concanavalin A challenge that was not affected by the presence of CeO{sub 2}, suggesting that DEP suppresses host defense capability by inducing the Th2 immunity. The micrographs of lymph nodes show that the particle clumps in DEP + CeO{sub 2} were significantly larger than CeO{sub 2} or DEP, exhibiting dense clumps continuous throughout the lymph nodes. Morphometric analysis demonstrates that the localization of collagen in the lung tissue after DEP + CeO{sub 2} reflects the combination of DEP-exposure plus CeO{sub 2}-exposure. At 4 weeks post-exposure, the histological features demonstrated that CeO{sub 2} induced lung phospholipidosis and fibrosis. DEP induced lung granulomas that were not significantly affected by the presence of CeO{sub 2} in the combined exposure. Using CeO{sub 2} as diesel fuel catalyst may cause health concerns. - Highlights: • DEP induced acute lung inflammation and switched immune response from Th1 to Th2. • DEP induced lung granulomas were not affected by the presence of CeO{sub 2}. • CeO{sub 2} induced sustained lung

  18. The biological effects of subacute inhalation of diesel exhaust following addition of cerium oxide nanoparticles in atherosclerosis-prone mice☆

    PubMed Central

    Cassee, Flemming R.; Campbell, Arezoo; Boere, A. John F.; McLean, Steven G.; Duffin, Rodger; Krystek, Petra; Gosens, Ilse; Miller, Mark R.

    2012-01-01

    Background Cerium oxide (CeO2) nanoparticles improve the burning efficiency of fuel, however, little is known about health impacts of altered emissions from the vehicles. Methods Atherosclerosis-prone apolipoprotein E knockout (ApoE−/−) mice were exposed by inhalation to diluted exhaust (1.7 mg/m3, 20, 60 or 180 min, 5 day/week, for 4 weeks), from an engine using standard diesel fuel (DE) or the same diesel fuel containing 9 ppm cerium oxide nanoparticles (DCeE). Changes in hematological indices, clinical chemistry, atherosclerotic burden, tissue levels of inflammatory cytokines and pathology of the major organs were assessed. Results Addition of CeO2 to fuel resulted in a reduction of the number (30%) and surface area (10%) of the particles in the exhaust, whereas the gaseous co-pollutants were increased (6–8%). There was, however, a trend towards an increased size and complexity of the atherosclerotic plaques following DE exposure, which was not evident in the DCeE group. There were no clear signs of altered hematological or pathological changes induced by either treatment. However, levels of proinflammatory cytokines were modulated in a brain region and liver following DCeE exposure. Conclusions These results imply that addition of CeO2 nanoparticles to fuel decreases the number of particles in exhaust and may reduce atherosclerotic burden associated with exposure to standard diesel fuel. From the extensive assessment of biological parameters performed, the only concerning effect of cerium addition was a slightly raised level of cytokines in a region of the central nervous system. Overall, the use of cerium as a fuel additive may be a potentially useful way to limit the health effects of vehicle exhaust. However, further testing is required to ensure that such an approach is not associated with a chronic inflammatory response which may eventually cause long-term health effects. PMID:22507957

  19. The biological effects of subacute inhalation of diesel exhaust following addition of cerium oxide nanoparticles in atherosclerosis-prone mice

    SciTech Connect

    Cassee, Flemming R.; Campbell, Arezoo; Boere, A. John F.; McLean, Steven G.; Krystek, Petra; Gosens, Ilse; Miller, Mark R.

    2012-05-15

    Background: Cerium oxide (CeO{sub 2}) nanoparticles improve the burning efficiency of fuel, however, little is known about health impacts of altered emissions from the vehicles. Methods: Atherosclerosis-prone apolipoprotein E knockout (ApoE{sup -/-}) mice were exposed by inhalation to diluted exhaust (1.7 mg/m{sup 3}, 20, 60 or 180 min, 5 day/week, for 4 weeks), from an engine using standard diesel fuel (DE) or the same diesel fuel containing 9 ppm cerium oxide nanoparticles (DCeE). Changes in hematological indices, clinical chemistry, atherosclerotic burden, tissue levels of inflammatory cytokines and pathology of the major organs were assessed. Results: Addition of CeO{sub 2} to fuel resulted in a reduction of the number (30%) and surface area (10%) of the particles in the exhaust, whereas the gaseous co-pollutants were increased (6-8%). There was, however, a trend towards an increased size and complexity of the atherosclerotic plaques following DE exposure, which was not evident in the DCeE group. There were no clear signs of altered hematological or pathological changes induced by either treatment. However, levels of proinflammatory cytokines were modulated in a brain region and liver following DCeE exposure. Conclusions: These results imply that addition of CeO{sub 2} nanoparticles to fuel decreases the number of particles in exhaust and may reduce atherosclerotic burden associated with exposure to standard diesel fuel. From the extensive assessment of biological parameters performed, the only concerning effect of cerium addition was a slightly raised level of cytokines in a region of the central nervous system. Overall, the use of cerium as a fuel additive may be a potentially useful way to limit the health effects of vehicle exhaust. However, further testing is required to ensure that such an approach is not associated with a chronic inflammatory response which may eventually cause long-term health effects.

  20. Effects of cerium oxide nanoparticles on the growth of keratinocytes, fibroblasts and vascular endothelial cells in cutaneous wound healing.

    PubMed

    Chigurupati, Srinivasulu; Mughal, Mohamed R; Okun, Eitan; Das, Soumen; Kumar, Amit; McCaffery, Michael; Seal, Sudipta; Mattson, Mark P

    2013-03-01

    Rapid and effective wound healing requires a coordinated cellular response involving fibroblasts, keratinocytes and vascular endothelial cells (VECs). Impaired wound healing can result in multiple adverse health outcomes and, although antibiotics can forestall infection, treatments that accelerate wound healing are lacking. We now report that topical application of water soluble cerium oxide nanoparticles (Nanoceria) accelerates the healing of full-thickness dermal wounds in mice by a mechanism that involves enhancement of the proliferation and migration of fibroblasts, keratinocytes and VECs. The Nanoceria penetrated into the wound tissue and reduced oxidative damage to cellular membranes and proteins, suggesting a therapeutic potential for topical treatment of wounds with antioxidant nanoparticles.

  1. Influence of the surface pre-treatment of aluminum on the processes of formation of cerium oxides protective films

    NASA Astrophysics Data System (ADS)

    Andreeva, R.; Stoyanova, E.; Tsanev, A.; Stoychev, D.

    2016-03-01

    It is known that there is special interest in the contemporary investigations on conversion treatment of aluminum aimed at promoting its corrosion stability, which is focused on electrolytes on the basis of salts of metals belonging to the group of rare-earth elements. Their application is especially attractive, as it enables a successful substitution of the presently applied highly efficient, but at the same time toxic Cr6+-containing electrolytes. The present paper presents a study on the influence of the preliminary alkaline activation and acidic de-oxidation of the aluminum surface on the processes of immersion formation of protective cerium oxides films on Al 1050. The results obtained show that their deposition from simple electrolytes (containing only salts of Ce3+ ions) on the Al surface, treated only in alkaline solution, occurs at a higher rate, which leads to preparing thicker oxide films having a better protective ability. In the cases when the formation of oxide films is realized in a complex electrolyte (containing salts of Ce3+ and Cu2+ ions), better results are obtained with respect to the morphology and protective action of cerium oxides film on samples that have been consecutively activated in alkaline solution and deoxidized in acidic solution. Electrochemical investigations were carried out in a model corrosion medium (0.1 M NaCl); it was shown that the cerium protective films, deposited by immersion, have a cathodic character with regard to the aluminum support and inhibit the occurrence of the depolarizing corrosion process -- the reaction of oxygen reduction.

  2. Hazard and risk assessment of a nanoparticulate cerium oxide-based diesel fuel additive - a case study.

    PubMed

    Park, Barry; Donaldson, Kenneth; Duffin, Rodger; Tran, Lang; Kelly, Frank; Mudway, Ian; Morin, Jean-Paul; Guest, Robert; Jenkinson, Peter; Samaras, Zissis; Giannouli, Myrsini; Kouridis, Haris; Martin, Patricia

    2008-04-01

    Envirox is a scientifically and commercially proven diesel fuel combustion catalyst based on nanoparticulate cerium oxide and has been demonstrated to reduce fuel consumption, greenhouse gas emissions (CO(2)), and particulate emissions when added to diesel at levels of 5 mg/L. Studies have confirmed the adverse effects of particulates on respiratory and cardiac health, and while the use of Envirox contributes to a reduction in the particulate content in the air, it is necessary to demonstrate that the addition of Envirox does not alter the intrinsic toxicity of particles emitted in the exhaust. The purpose of this study was to evaluate the safety in use of Envirox by addressing the classical risk paradigm. Hazard assessment has been addressed by examining a range of in vitro cell and cell-free endpoints to assess the toxicity of cerium oxide nanoparticles as well as particulates emitted from engines using Envirox. Exposure assessment has taken data from modeling studies and from airborne monitoring sites in London and Newcastle adjacent to routes where vehicles using Envirox passed. Data have demonstrated that for the exposure levels measured, the estimated internal dose for a referential human in a chronic exposure situation is much lower than the no-observed-effect level (NOEL) in the in vitro toxicity studies. Exposure to nano-size cerium oxide as a result of the addition of Envirox to diesel fuel at the current levels of exposure in ambient air is therefore unlikely to lead to pulmonary oxidative stress and inflammation, which are the precursors for respiratory and cardiac health problems. PMID:18444008

  3. The Effect of Cerium Oxide Nanoparticle Valence State on Reactive Oxygen Species and Toxicity.

    PubMed

    Dunnick, Katherine M; Pillai, Rajalekshmi; Pisane, Kelly L; Stefaniak, Aleksandr B; Sabolsky, Edward M; Leonard, Stephen S

    2015-07-01

    Cerium oxide (CeO2) nanoparticles, which are used in a variety of products including solar cells, gas sensors, and catalysts, are expected to increase in industrial use. This will subsequently lead to additional occupational exposures, making toxicology screenings crucial. Previous toxicology studies have presented conflicting results as to the extent of CeO2 toxicity, which is hypothesized to be due to the ability of Ce to exist in both a +3 and +4 valence state. Thus, to study whether valence state and oxygen vacancy concentration are important in CeO2 toxicity, CeO2 nanoparticles were doped with gadolinium to adjust the cation (Ce, Gd) and anion (O) defect states. The hypothesis that doping would increase toxicity and decrease antioxidant abilities as a result of increased oxygen vacancies and inhibition of +3 to +4 transition was tested. Differences in toxicity and reactivity based on valence state were determined in RLE-6TN rat alveolar epithelial and NR8383 rat alveolar macrophage cells using enhanced dark field microscopy, electron paramagnetic resonance (EPR), and annexin V/propidium iodide cell viability stain. Results from EPR indicated that as doping increased, antioxidant potential decreased. Alternatively, doping had no effect on toxicity at 24 h. The present results imply that as doping increases, thus subsequently increasing the Ce(3+)/Ce(4+) ratio, antioxidant potential decreases, suggesting that differences in reactivity of CeO2 are due to the ability of Ce to transition between the two valence states and the presence of increased oxygen vacancies, rather than dependent on a specific valence state.

  4. Cytotoxicity and antibacterial activity of gold-supported cerium oxide nanoparticles

    PubMed Central

    Suresh Babu, K; Anandkumar, M; Tsai, TY; Kao, TH; Stephen Inbaraj, B; Chen, BH

    2014-01-01

    Background Cerium oxide nanoparticles (CeO2) have been shown to be a novel therapeutic in many biomedical applications. Gold (Au) nanoparticles have also attracted widespread interest due to their chemical stability and unique optical properties. Thus, decorating Au on CeO2 nanoparticles would have potential for exploitation in the biomedical field. Methods In the present work, CeO2 nanoparticles synthesized by a chemical combustion method were supported with 3.5% Au (Au/CeO2) by a deposition-precipitation method. The as-synthesized Au, CeO2, and Au/CeO2 nanoparticles were evaluated for antibacterial activity and cytotoxicity in RAW 264.7 normal cells and A549 lung cancer cells. Results The as-synthesized nanoparticles were characterized by X-ray diffraction, scanning and transmission electron microscopy, and ultraviolet-visible measurements. The X-ray diffraction study confirmed the formation of cubic fluorite-structured CeO2 nanoparticles with a size of 10 nm. All synthesized nanoparticles were nontoxic towards RAW 264.7 cells at doses of 0–1,000 μM except for Au at >100 μM. For A549 cancer cells, Au/CeO2 had the highest inhibitory effect, followed by both Au and CeO2 which showed a similar effect at 500 and 1,000 μM. Initial binding of nanoparticles occurred through localized positively charged sites in A549 cells as shown by a shift in zeta potential from positive to negative after 24 hours of incubation. A dose-dependent elevation in reactive oxygen species indicated that the pro-oxidant activity of the nanoparticles was responsible for their cytotoxicity towards A549 cells. In addition, cellular uptake seen on transmission electron microscopic images indicated predominant localization of nanoparticles in the cytoplasmic matrix and mitochondrial damage due to oxidative stress. With regard to antibacterial activity, both types of nanoparticles had the strongest inhibitory effect on Bacillus subtilis in monoculture systems, followed by Salmonella

  5. Cerium oxides and cerium-platinum surface alloys on Pt(111) single-crystal surfaces studied by scanning tunneling microscopy

    NASA Astrophysics Data System (ADS)

    Berner, Ulrich; Schierbaum, Klaus-Dieter

    2002-06-01

    Three-dimensional clusters of metallic Ce are deposited on Pt(111) surfaces by thermal evaporation in ultrahigh vacuum. Different reactions occur upon heating of the sample in ultrahigh vacuum and during the exposure of oxygen that lead to distinct well-ordered surface phases. Their geometric structures are determined by scanning tunneling microscopy (STM). A two-dimensional ordered surface alloy of Pt5Ce is obtained by annealing at 1000 K. It forms two different incommensurate overlayers on Pt(111) with long-distance spacings in the moiré patterns (13.7 and 14.8 Å). Hexagonally shaped two-dimensional islands are formed upon heating the Pt(111) single crystal with a submonolayer coverage of Ce at 900 K. They are localized at step edges. STM reveals a local 2×2 structure with respect to Pt(111). It is assigned to a precursor state of alloy formation. Ordered CeO2 phases result from annealing the alloy at 1000 K in oxygen. The surface structure is consistent with oxygen-terminated fluorite-type CeO2(111). During decomposition of CeO2 at 900 K, an oxide structure is identified which is attributed to an ultrathin ordered phase of surface-Ce2O3.

  6. Radioprotective cerium oxide nanoparticles: Molecular imaging investigations of conps' pharmacokinetics, efficacy, and mechanisms of action

    NASA Astrophysics Data System (ADS)

    McDonagh, Philip Reed Wills, III

    Cerium oxide nanoparticles (CONPs) are being investigated for several anti-oxidant applications in medicine. One of their most promising applications is as a radioprotective drug, an area of research in need due to the severe side effects from radiation therapy. In this work, the potential of CONPs as a radioprotective drug is examined using four criteria: favorable biodistribution/pharmacokinetics, low toxicity, ability to protect normal tissue from radiation damage, and lack of protection of tumor. The mechanisms of action of CONPs are also studied. Biodistribution was determined in radiolabeled CONPs with surface coatings including citrate, dextran T10-amine (DT10-NH2), dextran T10-polyethylene glycol (DT10-PEG), dextran T10-sulfobetaine (DT10-SB) and poly(acrylic acid) (PAA), and compared to uncoated. 89Zr was incorporated into CONPs for positron emission tomography (PET) imaging and ex vivo tissue analysis in tumor bearing mice. Compared to uncoated [ 89Zr]CONPs, coated [89Zr]CONPs showed improved biodistribution, including significantly enhanced renal clearance of PAA- [89Zr]CONPs. The toxicity of CONPs was evaluated in vitro and in vivo, with low toxicity at therapeutic doses. After clinically mimetic radiation therapy, pre-treatment of mice with coated and uncoated CONPs showed greater than 50% reduction of cell death in normal colon tissue, comparable to the clinically available radioprotective drug amifostine. Tumor control after irradiation of spontaneous colon tumors was unchanged with PAA-CONP pre-treatment, while citrate, DT10-PEG, and uncoated CONP pre-treatment had slightly less tumor control. Xenograft tumors were irradiated after pH normalizing treatment with sodium bicarbonate and PAA-CONP pre-treatment. Treatment of these tumors showed slightly less tumor control than irradiation alone or PAA-CONP plus irradiation, demonstrating that the acidic pH of the tumor microenvironment may be the basis of preventing CONPs' radioprotective properties in

  7. Oxidative Stress, Inflammation, and DNA Damage Responses Elicited by Silver, Titanium Dioxide, and Cerium Oxide Nanomaterials

    EPA Science Inventory

    Previous literature on the biological effects of engineered nanomaterials has focused largely on oxidative stress and inflammation endpoints without further investigating potential pathways. Here we examine time-sensitive biological response pathways affected by engineered nanoma...

  8. Cerium (IV) oxide nanotubes prepared by low temperature deposition at normal pressure.

    PubMed

    Boehme, M; Fu, G; Ionescu, E; Ensinger, W

    2011-02-11

    This paper reports the synthesis of cerium dioxide nanotubes (CeNTs) by electroless deposition using ion-track-etched polycarbonate templates. To achieve nanotubes with thin walls and small surface roughness the tubes were generated by a several-step-containing procedure under aqueous conditions. The approach reported below will process open end nanotubes with well-defined outer diameter and wall thickness.

  9. Cerium oxide coated anodes for aluminum electrowinning: Topical report, October 1, 1986-June 30, 1987

    SciTech Connect

    Walker, J. K.

    1987-12-01

    Because of the cost of building and maintaining a carbon anode plant and the energy penalties associated with the use of carbon anodes in the production of aluminum, the use of inert anodes has long been proposed. Various cermet anodes have been investigated. In this paper, tests on a material, cerium oxyfluoride (CEROX), deposited in situ as an anode, are reported. (JDH)

  10. Imaging nanostructural modifications induced by electronic metal-support interaction effects at Au||cerium-based oxide nanointerfaces.

    PubMed

    López-Haro, Miguel; Cíes, José M; Trasobares, Susana; Pérez-Omil, José A; Delgado, Juan J; Bernal, Serafín; Bayle-Guillemaud, Pascale; Stéphan, Odile; Yoshida, Kenta; Boyes, Edward D; Gai, Pratibha L; Calvino, José J

    2012-08-28

    A variety of advanced (scanning) transmission electron microscopy experiments, carried out in aberration-corrected equipment, provide direct evidence about subtle structural changes taking place at nanometer-sized Au||ceria oxide interfaces, which agrees with the occurrence of charge transfer effects between the reduced support and supported gold nanoparticles suggested by macroscopic techniques. Tighter binding of the gold nanoparticles onto the ceria oxide support when this is reduced is revealed by the structural analysis. This structural modification is accompanied by parallel deactivation of the CO chemisorption capacity of the gold nanoparticles, which is interpreted in exact quantitative terms as due to deactivation of the gold atoms at the perimeter of the Au||cerium oxide interface.

  11. Sulfonated macro-RAFT agents for the surfactant-free synthesis of cerium oxide-based hybrid latexes.

    PubMed

    Garnier, Jérôme; Warnant, Jérôme; Lacroix-Desmazes, Patrick; Dufils, Pierre-Emmanuel; Vinas, Jérôme; van Herk, Alex

    2013-10-01

    Three types of amphiphatic macro-RAFT agents were employed as compatibilizers to promote the polymerization reaction at the surface of nanoceria for the synthesis of CeO2-based hybrid latexes. Macro-RAFT copolymers and terpolymers were first synthesized employing various combinations of butyl acrylate as a hydrophobic monomer and acrylic acid (AA) and/or 2-acrylamido-2-methylpropane sulfonic acid (AMPS) as hydrophilic monomers. After characterizing the adsorption of these macro-RAFT agents at the cerium oxide surface by UV-visible spectrometry, emulsion copolymerization reactions of styrene and methyl acrylate were then carried out in the presence of the surface-modified nanoceria. Dynamic Light Scattering and cryo-Transmission Electron Microscopy were employed to confirm the hybrid structure of the final CeO2/polymer latexes, and proved that the presence of acrylic acid units in amphiphatic macro-RAFT agents enabled an efficient formation of hybrid structures, while the presence of AMPS units, when combined with AA units, resulted in a better distribution of cerium oxide nanoclusters between latex particles.

  12. Nafion-porous cerium oxide nanotubes composite membrane for polymer electrolyte fuel cells operated under dry conditions

    NASA Astrophysics Data System (ADS)

    Ketpang, Kriangsak; Oh, Kwangjin; Lim, Sung-Chul; Shanmugam, Sangaraju

    2016-10-01

    A composite membrane operated in polymer electrolyte fuel cells (PEFCs) under low relative humidity (RH) is developed by incorporating cerium oxide nanotubes (CeNT) into a perfluorosulfonic acid (Nafion®) membrane. Porous CeNT is synthesized by direct heating a precursor impregnated polymer fibers at 500 °C under an air atmosphere. Compared to recast Nafion and commercial Nafion (NRE-212) membranes, the Nafion-CeNT composite membrane generates 1.1 times higher power density at 0.6 V, operated at 80 °C under 100% RH. Compared to Nafion-cerium oxide nanoparticles (Nafion-CeNP) membrane, the Nafion-CeNT provides 1.2 and 1.7 times higher PEFC performance at 0.6 V when operated at 80 °C under 100% and 18% RH, respectively. Additionally, the Nafion-CeNT composite membrane exhibits a good fuel cell operation under 18% RH at 80 °C. Specifically, the fluoride emission rate of Nafion-CeNT composite membrane is 20 times lower than that of the commercial NRE-212 membrane when operated under 18% RH at 80 °C for 96 h. The outstanding PEFC performance and durability operated under dry conditions is mainly attributed to the facile water diffusion capability as well as the effective hydroxyl radical scavenging property of the CeNT filler, resulting in significantly mitigating both the ohmic resistance and Nafion membrane degradation.

  13. Cerium oxide nanoparticle uptake kinetics from the gas-phase into lung cells in vitro is transport limited.

    PubMed

    Raemy, David O; Limbach, Ludwig K; Rothen-Rutishauser, Barbara; Grass, Robert N; Gehr, Peter; Birbaum, Karin; Brandenberger, Christina; Günther, Detlef; Stark, Wendelin J

    2011-04-01

    Nowadays, aerosol processes are widely used for the manufacture of nanoparticles (NPs), creating an increased occupational exposure risk of workers, laboratory personnel and scientists to airborne particles. There is evidence that possible adverse effects are linked with the accumulation of NPs in target cells, pointing out the importance of understanding the kinetics of particle internalization. In this context, the uptake kinetics of representative airborne NPs over 30 min and their internalization after 24 h post-exposure were investigated by the use of a recently established exposure system. This system combines the production of aerosolized cerium oxide (CeO(2)) NPs by flame spray synthesis with its simultaneous particle deposition from the gas-phase onto A549 lung cells, cultivated at the air-liquid interface. Particle uptake was quantified by mass spectrometry after several exposure times (0, 5, 10, 20 and 30 min). Over 35% of the deposited mass was found internalized after 10 min exposure, a value that increased to 60% after 30 min exposure. Following an additional 24 h post-incubation, a time span, after which adverse biological effects were observed in previous experiments, over 80% of total CeO(2) could be detected intracellularly. On the ultrastructural level, focal cerium aggregates were present on the apical surface of A549 cells and could also be localized intracellularly in vesicular structures. The uptake behaviour of aerosolized CeO(2) is in line with observations on cerium suspensions, where particle mass transport was identified as the rate-limiting factor for NP internalization. PMID:21118721

  14. Gadolinium doped cerium oxide for soot oxidation: Influence of interfacial metal-support interactions

    NASA Astrophysics Data System (ADS)

    Durgasri, D. Naga; Vinodkumar, T.; Lin, Fangjian; Alxneit, Ivo; Reddy, Benjaram M.

    2014-09-01

    The aim of the present investigation was to ascertain the role of Al2O3, SiO2, and TiO2 supports in modulating the catalytic performance of ceria-based solid solutions. In this study, we prepared nanosized Ce-Gd/Al2O3, Ce-Gd/SiO2, and Ce-Gd/TiO2 catalysts by a deposition coprecipitation method and evaluated for soot oxidation. The synthesized catalysts were calcined at two different temperatures to assess their thermal stability and extensively characterized by various techniques, namely, XRD, Raman, BET surface area, TEM, H2-TPR, and UV-vis DRS. XRD and TEM results indicate that Ce-Gd-oxide nanoparticles are in highly dispersed form on the surface of the supports. Raman results show a prominent sharp peak and a broad peak corresponding to the F2g mode of ceria and the presence of oxygen vacancies, respectively. The presence of a significant number of oxygen vacancies in all samples is also confirmed from UV-vis DRS measurements. The H2-TPR results suggest that Gd-doping facilitates the reduction of the materials and decreases the onset temperature of reduction. Among the prepared samples, Ce-Gd/TiO2 catalyst exhibited the highest activity, suggesting the existence of strong interfacial metal support interaction between the active metal oxide and the support.

  15. Metal-organic chemical vapor deposition of cerium oxide, gallium-indium-oxide, and magnesium oxide thin films: Precursor design, film growth, and film characterization

    NASA Astrophysics Data System (ADS)

    Edleman, Nikki Lynn

    A new class of volatile, low-melting, fluorine-free lanthanide metal-organic chemical vapor deposition (MOCVD) precursors has been developed. The neutral, monomeric cerium, neodymium, gadolinium, and erbium complexes are coordinatively saturated by a versatile, multidentate, ether-functionalized beta-ketoiminate ligand, and complex melting point and volatility characteristics can be tuned by altering the alkyl substituents on the ligand periphery. Direct comparison with lanthanide beta-diketonate complexes reveals that the present precursor class is a superior choice for lanthanide oxide MOCVD. Epitaxial CeO 2 buffer layer films have been grown on (001) YSZ substrates by MOCVD at significantly lower temperatures than previously reported using one of the newly developed cerium precursors. High-quality YBCO films grown on these CeO2 buffer layers by POMBE exhibit very good electrical transport properties. The cerium complex has therefore been explicitly demonstrated to be a stable and volatile precursor and is attractive for low-temperature growth of coated conductor multilayer structures by MOCVD. Gallium-indium-oxide thin films (GaxIn2-xO 3), x = 0.0˜1.1, have been grown by MOCVD using the volatile metal-organic precursors In(dpm)3 and Ga(dpm)3. The films have a homogeneously Ga-substituted, cubic In2O3 microstructure randomly oriented on quartz or heteroepitaxial on (100) YSZ single-crystal substrates. The highest conductivity of the as-grown films is found at x = 0.12. The optical transmission window and absolute transparency of the films rivals or exceeds that of the most transparent conductive oxides known. Reductive annealing results in improved charge transport characteristics with little loss of optical transparency. No significant difference in electrical properties is observed between randomly oriented and heteroepitaxial films, thus arguing that carrier scattering effects at high-angle grain boundaries play a minor role in the film conductivity mechanism

  16. Oxidation of SO2 to SO3 by Cerium Oxide Cluster Cations Ce2O4(+) and Ce3O6(.).

    PubMed

    Zhou, Zhen-Xun; Wang, Li Na; Li, Zi-Yu; He, Sheng-Gui; Ma, Tong-Mei

    2016-06-01

    Cerium oxide cationic clusters (CeO2)1-3(+) were generated through laser ablation and then reacted with sulfur dioxide (SO2) at ambient conditions in an ion trap reactor and those reactions were studied and characterized by combining the art of time-of-flight mass spectrometry (TOF-MS) with density functional theory (DFT) calculations. Molecule association and oxygen atom transfer (OAT) were observed for the CeO2(+) and (CeO2)2,3(+) reaction systems, respectively. The mechanistic analysis indicates that the weak Ce-O bond strength associated with the oxygen release capacity of cerium oxide clusters is considered as the key factor to achieve the oxidation of SO2. To our best knowledge, this research should be the first example to identify the OAT reactivity of metal oxide cluster ions toward sulfur dioxide under thermal collision conditions, and a fundamental understanding of the elementary oxidation of SO2 to SO3 is provided.

  17. Oxidation of SO2 to SO3 by Cerium Oxide Cluster Cations Ce2O4(+) and Ce3O6(.).

    PubMed

    Zhou, Zhen-Xun; Wang, Li Na; Li, Zi-Yu; He, Sheng-Gui; Ma, Tong-Mei

    2016-06-01

    Cerium oxide cationic clusters (CeO2)1-3(+) were generated through laser ablation and then reacted with sulfur dioxide (SO2) at ambient conditions in an ion trap reactor and those reactions were studied and characterized by combining the art of time-of-flight mass spectrometry (TOF-MS) with density functional theory (DFT) calculations. Molecule association and oxygen atom transfer (OAT) were observed for the CeO2(+) and (CeO2)2,3(+) reaction systems, respectively. The mechanistic analysis indicates that the weak Ce-O bond strength associated with the oxygen release capacity of cerium oxide clusters is considered as the key factor to achieve the oxidation of SO2. To our best knowledge, this research should be the first example to identify the OAT reactivity of metal oxide cluster ions toward sulfur dioxide under thermal collision conditions, and a fundamental understanding of the elementary oxidation of SO2 to SO3 is provided. PMID:27184540

  18. The Chemical Behavior and Degradation Mitigation Effect of Cerium Oxide Nanoparticles in Perfluorosulfonic Acid Polymer Electrolyte Membranes

    SciTech Connect

    Pearman, Benjamin P; Mohajeri, Nahid; Slattery, Darlene; Hampton, Michael; Seal, Sudipta; Cullen, David A

    2013-01-01

    Perfluorosulfonic acid membranes, the polymer of choice for polymer electrolyte hydrogen fuel cells, are susceptible to degradation due to attacks on polymer chains from radicals. Mitigation of this attack by cerium-based radical scavengers is an approach that has shown promise. In this work, two formulations of single-crystal cerium oxide nanoparticles, with an order of magnitude difference in particle size, are incorporated into said membranes and subjected to proton conductivity measurements and ex-situ durability tests. We found that ceria is reduced to Ce(III) ions in the acidic environment of a heated, humidified membrane which negatively impacts proton conductivity. In liquid and gas Fenton testing, fluoride emission is reduced by an order of magnitude, drastically increasing membrane longevity. Side-product analysis demonstrated that in the liquid Fenton test, the main point of attack are weak polymer end groups, while in the gas Fenton test, there is additional side-chain attack. Both mechanisms are mitigated by the addition of the ceria nanoparticles, whereby the extent of the durability improvement is found to be independent of particle size.

  19. Laser induced densification of cerium gadolinium oxide: Application to single-chamber solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Mariño, Mariana; Rieu, Mathilde; Viricelle, Jean-Paul; Garrelie, Florence

    2016-06-01

    In single-chamber solid oxide fuel cells (SC-SOFC), anode and cathode are placed in a gas chamber where they are exposed to a fuel/air mixture. Similarly to conventional dual-chamber SOFC, the anode and the cathode are separated by an electrolyte. However, as in the SC-SOFC configuration the electrolyte does not play tightness role between compartments, this one can be a porous layer. Nevertheless, it is necessary to have a diffusion barrier to prevent the transportation of hydrogen produced locally at the anode to the cathode that reduces fuel cell performances. This study aims to obtain directly a diffusion barrier through the surface densification of the electrolyte Ce0.9Gd0.1O1.95 (CGO) by a laser treatment. KrF excimer laser and Yb fiber laser irradiations were used at different fluences and number of pulses to modify the density of the electrolyte coating. Microstructural characterizations confirmed the modifications on the surface of the electrolyte for appropriate experimental conditions showing either grain growth or densified but cracked surfaces. Gas permeation and electrical conductivities of the modified electrolyte were evaluated. Finally SC-SOFC performances were improved for the cells presenting grain growth at the electrolyte surface.

  20. Uptake and release of cerium during Fe-oxide formation and transformation in Fe(II) solutions.

    PubMed

    Nedel, S; Dideriksen, K; Christiansen, B C; Bovet, N; Stipp, S L S

    2010-06-15

    Fe-oxides are ubiquitous in soils and sediments and form during Fe(0) corrosion. Depending on redox conditions and solution composition, Fe-oxides such as ferrihydrite, goethite, magnetite, and green rust (GR) may form. These phases typically have high surface area and large affinity for adsorption of trace components. Further, Fe(II)-Fe(III) (hydr)oxides are redox active. Cerium, a member of the lanthanide family, can be used as an analogue for the tri- and tetra-valent actinides found in radioactive waste, expected to be stored in subsurface repositories. In experiments with ferrihydrite, Ce(III) was effectively scavenged from Fe(II)-bearing solutions within 5 min at pH 7. During transformation of ferrihydrite to green rust, however, all Ce(III) was released to solution. By varying initial solution Fe(II):Fe(III) ratio, magnetite and goethite formed together with GR(Na,SO(4)), resulting in decreased Ce(III) release. X-ray photoelectron spectroscopy revealed Ce(III) adsorbed on magnetite. When Fe-oxides were synthesized by air oxidation of Fe(II) solutions at pH 7, GR(Na,SO(4)) played a catalytic role in the oxidation of Ce(III) to Ce(IV) by O(2), removing more than 90% of the dissolved Ce. Transmission electron microscopy revealed that it formed discrete nanocrystals of CeO(2(s)). These results demonstrate that Fe-oxide interaction with radionuclides is likely to depend strongly on the local redox conditions. By analogy with Ce, the trivalent actinides are not expected to be sequestered by preformed GR in anoxic environments. Our results also suggest that trivalent actinides and lanthanides are released when dissimilatory iron reduction of Fe(III)-oxides leads to GR formation However, under oxidizing conditions, GR may influence radionuclide mobility by catalyzing their transformation to a higher oxidation state. PMID:20496931

  1. Preliminary study of phosphate adsorption onto cerium oxide nanoparticles for use in water purification; nanoparticles synthesis and characterization.

    PubMed

    Recillas, Sonia; García, Ana; González, Edgar; Casals, Eudald; Puntes, Victor; Sánchez, Antoni; Font, Xavier

    2012-01-01

    In this study, the synthesis and characterization of cerium oxide nanoparticles (CeO(2)-NPs) and their adsorption potential for removing phosphate from water was evaluated using a multi-factor experimental design to explore the effect of various factors on adsorption. The objective function selected was the percentage of phosphate removed from water, in which the phosphate concentration and the CeO(2)-NP concentration are quantitative variables (factors in the experimental design). A lineal polynomial fitted the experimental results well (R(2) = 0.9803). The nanostructure was studied by transmission electron microscopy (TEM) and high-resolution TEM techniques before and after the adsorption process. During the adsorption and desorption processes several changes in the morphology and surface chemistry of the CeO(2)-NPs were observed.

  2. Stability and mobility of cerium oxide nanoparticles in soils: effects of humic substances, pH and ionic strength

    NASA Astrophysics Data System (ADS)

    Chen, Yirui; Mu, Linlin; Li, Chunyan; Bai, Lingyun; Jacobson, Astrid; Darnault, Christophe

    2015-04-01

    Among the large number of types of nanomaterials used in the field of nanotechnology, cerium oxide nanoparticles (CeO2 NPs) are among the top five most commonly utilized by industry, agriculture and nanomedicine for their unique physico-chemical properties. They are used, for example, in the production of catalysts, as fuel additives, and as polishing agents. Therefore, the release and encounter of CeO2 NPs in the environment following their application, waste disposal, life-cycle and accidents is inevitable. It is critical to examine the behavior of CeO2 NPs released in the environment to assess the risk they pose to the environmental and public health. In particular, little is known about the fate and transport of CeO2 NPs in soils and groundwater. To assess the behavior of CeO2 NPs, it is important to investigate the factors that affect their stability and mobility. Humic substances are a major component of soils and have been shown to have the potential to impact the transport and retention of nanoparticles in soils. Consequently, our study characterizes the impacts of humic and fulvic acids on the stability and mobility of cerium oxides in model porous media under various pH and ionic strength conditions. Batch experiments conducted at various concentrations of humic and fulvic acids coupled with a wide range of pHs and ionic strengths were investigated. Selected parameters from these batch studies were then used as experimental conditions representative of environmental systems to perform column transport experiments to assess of the mobility of CeO2 NPs in saturated porous media, which is the first step in simulating their behavior in soil and groundwater systems.

  3. Sorption of trivalent cerium by a mixture of microbial cells and manganese oxides: Effect of microbial cells on the oxidation of trivalent cerium

    NASA Astrophysics Data System (ADS)

    Ohnuki, Toshihiko; Jiang, Mingyu; Sakamoto, Fuminori; Kozai, Naofumi; Yamasaki, Shinya; Yu, Qianqian; Tanaka, Kazuya; Utsunomiya, Satoshi; Xia, Xiaobin; Yang, Ke; He, Jianhua

    2015-08-01

    Sorption of Ce by mixtures of synthetic Mn oxides and microbial cells of Pseudomonas fluorescens was investigated to elucidate the role of microorganisms on Ce(III) oxidative migration in the environment. The mixtures, upon which Ce was sorbed following exposure to solutions containing 1.0 × 10-4 or 1.0 × 10-5 mol L-1 Ce(III), were analyzed by scanning electron microscopy energy dispersive X-ray spectroscopy (SEM-EDS) and micro-X-ray fluorescence (micro-XRF) at synchrotron facilities. A Ce LIII-edge micro XANES spectra analysis was also performed to determine the oxidation states of Ce adsorbed to the Mn oxides and microbial cells in the mixtures. The distribution ratios (Kd) of Ce between the individual solids and solution increased with increasing pH of the solution, and was nearly the same in mixtures containing varying amounts of microbial cells. SEM-EDS and micro-XRF analyses showed that Ce was sorbed by both MnO2 and microbial cells (1.7 × 10-1 or 3.3 × 10-1 g L-1). In addition, nano-particles containing Ce and P developed on the surface of the microbial cells. XANES analysis showed that lower fractions of Ce(III) were oxidized to Ce(IV) in the mixtures containing greater amounts of microbial cells. Micro-XANES analysis revealed that Ce was present as Ce(III) on the microbial cells and as Ce(IV) on Mn oxides. These results strongly suggest that the association of Ce(III) with the microbial cell surface and the formation of Ce phosphate nano-particles are responsible for suppressing the oxidation of Ce(III) to Ce(IV) in the mixtures.

  4. Influence of alloy content and a cerium surface treatment on the oxidation behavior of Fe-Cr ferritic stainless steels

    SciTech Connect

    Alman, D.E.; Jablonski, P.D.

    2006-01-01

    The cost of solid oxide fuel cells (SOFC) can be significantly reduced by using interconnects made from ferritic stainless steels. In fact, several alloys have been developed specifically for this application (Crofer 22APU and Hitachi ZMG323). However, these steels lack environmental stability in SOFC environments, and as a result, degrade the performance of the SOFC. A steel interconnect can contribute to performance degradation through: (i) Cr poisoning of electrochemically active sites within the cathode; (ii) formation of non-conductive oxides, such as SiO2 or Al2O3 from residual or minor alloying elements, at the base metal-oxide scale interface; and/or (iii) excessive oxide scale growth, which may also retard electrical conductivity. Consequently, there has been considerable attention on developing coatings to protect steel interconnects in SOFC environments and controlling trace elements during alloy production. Recently, we have reported on the development of a Cerium surface treatment that improves the oxidation behavior of a variety alloys, including Crofer 22APU [1-5]. Initial results indicated that the treatment may improve the performance of Crofer 22APU for SOFC application by: (i) retarding scale growth resulting in a thinner oxide scale; and (ii) suppressing the formation of a deleterious continuous SiO2 layer that can form at the metal-oxide scale interface in materials with high residual Si content [5]. Crofer 22 APU contains Fe-22Cr-0.5Mn-0.1Ti (weight percent). Depending on current market prices and the purity of raw materials utilized for ingot production, Cr can contribute upwards of 90 percent of the raw materials cost. The present research was undertaken to determine the influence of Cr content and minor element additions, especially Ti, on the effectiveness of the Ce surface treatment. Particular emphasis is placed on the behavior of low Cr alloys.

  5. Cerium oxide nanoparticles promote neurogenesis and abrogate hypoxia-induced memory impairment through AMPK–PKC–CBP signaling cascade

    PubMed Central

    Arya, Aditya; Gangwar, Anamika; Singh, Sushil Kumar; Roy, Manas; Das, Mainak; Sethy, Niroj Kumar; Bhargava, Kalpana

    2016-01-01

    Structural and functional integrity of the brain is adversely affected by reduced oxygen saturation, especially during chronic hypoxia exposure and often encountered by altitude travelers or dwellers. Hypoxia-induced generation of reactive nitrogen and oxygen species reportedly affects the cortex and hippocampus regions of the brain, promoting memory impairment and cognitive dysfunction. Cerium oxide nanoparticles (CNPs), also known as nanoceria, switch between +3 and +4 oxidation states and reportedly scavenge superoxide anions, hydrogen peroxide, and peroxynitrite in vivo. In the present study, we evaluated the neuroprotective as well as the cognition-enhancing activities of nanoceria during hypobaric hypoxia. Using polyethylene glycol-coated 3 nm nanoceria (PEG-CNPs), we have demonstrated efficient localization of PEG-CNPs in rodent brain. This resulted in significant reduction of oxidative stress and associated damage during hypoxia exposure. Morris water maze-based memory function tests revealed that PEG-CNPs ameliorated hypoxia-induced memory impairment. Using microscopic, flow cytometric, and histological studies, we also provide evidences that PEG-CNPs augmented hippocampus neuronal survival and promoted neurogenesis. Molecular studies revealed that PEG-CNPs promoted neurogenesis through the 5′-adenine monophosphate-activated protein kinase–protein kinase C–cyclic adenosine monophosphate response element-binding protein binding (AMPK-PKC-CBP) protein pathway. Our present study results suggest that nanoceria can be translated as promising therapeutic molecules for neurodegenerative diseases. PMID:27069362

  6. Evaluation of cerium oxide coated Cu cermets as inert anodes for aluminum electrowinning. Final report, August 1990--March 1992

    SciTech Connect

    Not Available

    1992-08-01

    Cu/NiFe{sub 2}O{sub 4} cermets were evaluated, with and without an in-situ deposited CEROX (TM; cerium oxide) coating, in 100 h laboratory A1 electrowinning tests. Bath ratio and current density were varied between tests and corrosion was determined by contamination of the aluminum and cryolite by cermet components (Cu, Fe, and Ni). Higher bath ratios of 1.5 to 1.6 led to less corrosion and thicker CEROX coatings. Lower current densities led to slightly less corrosion but much less oxidation of the Cu cermet substrate. At identical test conditions, the corrosion of the CEROX coated cermets was 1/7 that of an uncoated cermet. Corrosion was increased in CEROX coated cermets tested under unsaturated alumina conditions. The electrical conductivity of the CEROX coating was measured to be {approximately}0.2 ohm{sup {minus}1}cm{sup {minus}1}, resulting in a slight voltage penalty, depending on the thickness of the coating.

  7. Elimination of Flammable Gas Effects in Cerium Oxide Semiconductor-Type Resistive Oxygen Sensors for Monitoring Low Oxygen Concentrations

    PubMed Central

    Itoh, Toshio; Izu, Noriya; Akamatsu, Takafumi; Shin, Woosuck; Miki, Yusuke; Hirose, Yasuo

    2015-01-01

    We have investigated the catalytic layer in zirconium-doped cerium oxide, Ce0.9Zr0.1O2 (CeZr10) resistive oxygen sensors for reducing the effects of flammable gases, namely hydrogen and carbon monoxide. When the concentration of flammable gases is comparable to that of oxygen, the resistance of CeZr10 is affected by the presence of these gases. We have developed layered thick films, which consist of an oxygen sensor layer (CeZr10), an insulation layer (Al2O3), and a catalytic layer consisting of CeZr10 with 3 wt% added platinum, which was prepared via the screen printing method. The Pt-CeZr10 catalytic layer was found to prevent the detrimental effects of the flammable gases on the resistance of the sensor layer. This effect is due to the catalytic layer promoting the oxidation of hydrogen and carbon monoxide through the consumption of ambient O2 and/or the lattice oxygen atoms of the Pt-CeZr10 catalytic layer. PMID:25905705

  8. Cerium Oxide Nanoparticles Induced Toxicity in Human Lung Cells: Role of ROS Mediated DNA Damage and Apoptosis

    PubMed Central

    Pandey, Alok K.

    2014-01-01

    Cerium oxide nanoparticles (CeO2 NPs) have promising industrial and biomedical applications. In spite of their applications, the toxicity of these NPs in biological/physiological environment is a major concern. Present study aimed to understand the molecular mechanism underlying the toxicity of CeO2 NPs on lung adenocarcinoma (A549) cells. After internalization, CeO2 NPs caused significant cytotoxicity and morphological changes in A549 cells. Further, the cell death was found to be apoptotic as shown by loss in mitochondrial membrane potential and increase in annexin-V positive cells and confirmed by immunoblot analysis of BAX, BCl-2, Cyt C, AIF, caspase-3, and caspase-9. A significant increase in oxidative DNA damage was found which was confirmed by phosphorylation of p53 gene and presence of cleaved poly ADP ribose polymerase (PARP). This damage could be attributed to increased production of reactive oxygen species (ROS) with concomitant decrease in antioxidant “glutathione (GSH)” level. DNA damage and cell death were attenuated by the application of ROS and apoptosis inhibitors N-acetyl-L- cysteine (NAC) and Z-DEVD-fmk, respectively. Our study concludes that ROS mediated DNA damage and cell cycle arrest play a major role in CeO2 NPs induced apoptotic cell death in A549 cells. Apart from beneficial applications, these NPs also impart potential harmful effects which should be properly evaluated prior to their use. PMID:24987704

  9. Carbon nanotubes supported cerium dioxide and platinum nanohybrids: Layer-by-layer synthesis and enhanced electrocatalytic activity for methanol oxidation

    NASA Astrophysics Data System (ADS)

    Lou, Xinyuan; Chen, Jiayi; Wang, Mengdi; Gu, Jialei; Wu, Ping; Sun, Dongmei; Tang, Yawen

    2015-08-01

    We successfully synthesize carbon nanotubes (CNTs) supported cerium dioxide and platinum (Pt/CeO2/CNTs) nanohybrids via layer-by-layer assembly. The composition, morphology and structure of the as-prepared Pt/CeO2/CNTs nanohybrids are characterized by transmission electron microscopy (TEM), energy-dispersive X-ray spectrometer (EDX), selected-area electron diffraction (SAED), X-ray diffraction (XRD), thermogravimetric analysis (TGA), and inductively coupled plasma atomic emission spectrometry (ICP-AES). By comparison of the electrocatalytic properties of the Pt/CeO2/CNTs with the Pt/CNTs, we systematically investigate the promotion effect of CeO2 on the Pt/CeO2/CNTs catalysts towards methanol oxidation. It is found that the introduction of CeO2 not only enhances the electrocatalytic activity and stability of the Pt/CeO2/CNTs catalyst for methanol oxidation but also minimizes the CO poisoning, probably accounting for the good oxygen carrying capacity of CeO2 and its high stability in acidic solution.

  10. Comparison of the Mechanism of Toxicity of Zinc Oxide and Cerium Oxide Nanoparticles Based on Dissolution and Oxidative Stress Properties

    PubMed Central

    Xia, Tian; Kovochich, Michael; Liong, Monty; Mädler, Lutz; Gilbert, Benjamin; Shi, Haibin; Yeh, Joanne I.; Zink, Jeffrey I.; Nel, Andre E.

    2014-01-01

    Nanomaterials (NM) exhibit novel physicochemical properties that determine their interaction with biological substrates and processes. Three metal oxides nanoparticles that are currently being produced in high tonnage, TiO2, ZnO and CeO2, were synthesized by flame spray pyrolysis process and compared in a mechanistic study to elucidate the physicochemical characteristics that determine cellular uptake, subcellular localization, and toxic effects based on a test paradigm that was originally developed for oxidative stress and cytotoxicity in RAW 264.7 and BEAS-2B cell lines. ZnO induced toxicity in both cells, leading to the generation of reactive oxygen species (ROS), oxidant injury, excitation of inflammation and cell death. Using ICP-MS and fluorescent-labeled ZnO, it is found that ZnO dissolution could happen in culture medium and endosomes. Non-dissolved ZnO nanoparticles enter caveolae in BEAS-2B, but enter lysosomes in RAW 264.7 cells in which smaller particle remnants dissolve. In contrast, fluorescent-labeled CeO2 nanoparticles were taken up intact into caveolin-1 and LAMP-1 positive endosomal compartments, respectively, in BEAS-2B and RAW 264.7 cells, without inflammation or cytotoxicity. Instead, CeO2 suppressed ROS production and induced cellular resistance to an exogenous source of oxidative stress. Fluorescent-labeled TiO2 was processed by the same uptake pathways as CeO2 but did not elicit any adverse or protective effects. These results demonstrate that metal oxide nanoparticles induce a range of biological responses that vary from cytotoxic to cytoprotective and can only be properly understood by using a tiered test strategy such as we developed for oxidative stress and adapted to study other aspects of nanoparticle toxicity. PMID:19206459

  11. Nanocasted synthesis of magnetic mesoporous iron cerium bimetal oxides (MMIC) as an efficient heterogeneous Fenton-like catalyst for oxidation of arsenite.

    PubMed

    Wen, Zhipan; Zhang, Yalei; Dai, Chaomeng; Sun, Zhen

    2015-04-28

    Magnetic mesoporous iron cerium bimetal oxides (MMIC) with large surface area and pore volume was synthesized via the hard template approach. This obtained MMIC was easily separated from aqueous solution with an external magnetic field and was proposed as a heterogeneous Fenton-like catalyst for oxidation of As(III). The MMIC presented excellent catalytic activity for the oxidation of As(III), achieving almost complete oxidation of 1000ppb As(III) after 60min and complete removal of arsenic species after 180min with reaction conditions of 0.4g/L catalyst, pH of 3.0 and 0.4mM H2O2. Kinetics analysis showed that arsenic removal followed the pseudo-first order, and the pseudo-first-order rate constants increased from 0.0014min(-1) to 0.0548min(-1) as the H2O2 concentration increased from 0.04mM to 0.4mM. On the basis of the effects of XPS analysis and reactive oxidizing species, As(III) in aqueous solution was mainly oxidized by OH radicals, including the surface-bound OHads generated on the MMIC surface which were involved in Fe(2+) and Ce(3+), and free OHfree generation by soluble iron ions which were released from the MMIC into the bulk solution, and the generated As(V) was finally removed by MMIC through adsorption.

  12. Polyacrylic acid-coated cerium oxide nanoparticles: An oxidase mimic applied for colorimetric assay to organophosphorus pesticides.

    PubMed

    Zhang, Shi-Xiang; Xue, Shi-Fan; Deng, Jingjing; Zhang, Min; Shi, Guoyue; Zhou, Tianshu

    2016-11-15

    It is important and urgent to develop reliable and highly sensitive methods that can provide on-site and rapid detection of extensively used organophosphorus pesticides (OPs) for their neurotoxicity. In this study, we developed a novel colorimetric assay for the detection of OPs based on polyacrylic acid-coated cerium oxide nanoparticles (PAA-CeO2) as an oxidase mimic and OPs as inhibitors to suppress the activity of acetylcholinesterase (AChE). Firstly, highly dispersed PAA-CeO2 was prepared in aqueous solution, which could catalyze the oxidation of TMB to produce a color reaction from colorless to blue. And the enzyme of AChE was used to catalyze the substrate of acetylthiocholine (ATCh) to produce thiocholine (TCh). As a thiol-containing compound with reducibility, TCh can decrease the oxidation of TMB catalyzed by PAA-CeO2. Upon incubated with OPs, the enzymatic activity of AChE was inhibited to produce less TCh, resulting in more TMB catalytically oxidized by PAA-CeO2 to show an increasing blue color. The two representative OPs, dichlorvos and methyl-paraoxon, were tested using our proposed assay. The novel assay showed notable color change in a concentration-dependent manner, and as low as 8.62 ppb dichlorvos and 26.73 ppb methyl-paraoxon can be readily detected. Therefore, taking advantage of such oxidase-like activity of PAA-CeO2, our proposed colorimetric assay can potentially be a screening tool for the precise and rapid evaluation of the neurotoxicity of a wealth of OPs.

  13. Polyacrylic acid-coated cerium oxide nanoparticles: An oxidase mimic applied for colorimetric assay to organophosphorus pesticides.

    PubMed

    Zhang, Shi-Xiang; Xue, Shi-Fan; Deng, Jingjing; Zhang, Min; Shi, Guoyue; Zhou, Tianshu

    2016-11-15

    It is important and urgent to develop reliable and highly sensitive methods that can provide on-site and rapid detection of extensively used organophosphorus pesticides (OPs) for their neurotoxicity. In this study, we developed a novel colorimetric assay for the detection of OPs based on polyacrylic acid-coated cerium oxide nanoparticles (PAA-CeO2) as an oxidase mimic and OPs as inhibitors to suppress the activity of acetylcholinesterase (AChE). Firstly, highly dispersed PAA-CeO2 was prepared in aqueous solution, which could catalyze the oxidation of TMB to produce a color reaction from colorless to blue. And the enzyme of AChE was used to catalyze the substrate of acetylthiocholine (ATCh) to produce thiocholine (TCh). As a thiol-containing compound with reducibility, TCh can decrease the oxidation of TMB catalyzed by PAA-CeO2. Upon incubated with OPs, the enzymatic activity of AChE was inhibited to produce less TCh, resulting in more TMB catalytically oxidized by PAA-CeO2 to show an increasing blue color. The two representative OPs, dichlorvos and methyl-paraoxon, were tested using our proposed assay. The novel assay showed notable color change in a concentration-dependent manner, and as low as 8.62 ppb dichlorvos and 26.73 ppb methyl-paraoxon can be readily detected. Therefore, taking advantage of such oxidase-like activity of PAA-CeO2, our proposed colorimetric assay can potentially be a screening tool for the precise and rapid evaluation of the neurotoxicity of a wealth of OPs. PMID:27208478

  14. Toxicity assessment of aggregated/agglomerated cerium oxide nanoparticles in an in vitro 3D airway model: the influence of mucociliary clearance.

    PubMed

    Frieke Kuper, C; Gröllers-Mulderij, Mariska; Maarschalkerweerd, Thérèse; Meulendijks, Nicole M M; Reus, Astrid; van Acker, Frédérique; Zondervan-van den Beuken, Esther K; Wouters, Mariëlle E L; Bijlsma, Sabina; Kooter, Ingeborg M

    2015-03-01

    We investigated the toxicity of aggregated nanoparticles of cerium oxide (CeO2) using an in vitro 3D human bronchial epithelial model that included a mucociliary apparatus (MucilAir™). CeO2 was dispersed in saline and applied to the apical surface of the model. CeO2 did not induce distinct effects in the model, whereas it did in BEAS-2B and A549 cell cultures. The absence of effects of CeO2 was not because of the model's insensitivity. Nanoparticles of zinc oxide (ZnO) elicited positive responses in the toxicological assays. Respiratory mucus (0.1% and 1%) added to dispersions increased aggregation/agglomeration to such an extent that most CeO2 sedimented within a few minutes. Also, the mucociliary apparatus of the model removed CeO2 from the central part of the apical surface to the borders. This 'clearance' may have prevented the majority of CeO2 from reaching the epithelial cells. Chemical analysis of cerium in the basal tissue culture medium showed only minimal translocation of cerium across the 3D barrier. In conclusion, mucociliary defence appeared to prevent CeO2 reaching the respiratory epithelial cells in this 3D in vitro model. This model and approach can be used to study compounds of specific toxicological concern in airway defence mechanisms in vitro. PMID:25448805

  15. Cellular uptake and reactive oxygen species modulation of cerium oxide nanoparticles in human monocyte cell line U937.

    PubMed

    Lord, Megan S; Jung, MoonSun; Teoh, Wey Yang; Gunawan, Cindy; Vassie, James A; Amal, Rose; Whitelock, John M

    2012-11-01

    Cerium oxide nanoparticles (nanoceria) are promising materials for intracellular oxygen free radical scavenging providing a potential therapy for reactive oxygen species (ROS)-mediated inflammatory processes. In this study rhombohedral-shaped nanoceria were synthesized by flame spray pyrolysis with tuneable particle diameters between 3 and 94 nm by changing the liquid precursor flow rate. Monocytes and macrophages are major players in inflammatory processes as their production of ROS species has important downstream effects on cell signalling. Therefore, this study examined the ability of the nanoceria to be internalised by the human monocytic cell line, U937, and scavenge intracellular ROS. U937 cells activated in the presence of phorbol 12-myristate 13-acetate (PMA) were found to be more responsive to the nanoceria than U937 cells, which may not be surprising given the role of monocyte/macrophages in phagocytosing foreign material. The smaller particles were found to contain more crystal lattice defects with which to scavenge ROS, however a greater proportion of both the U937 and activated U937 cell populations responded to the larger particles. Hence all nanoceria particle sizes examined in this study were equally effective in scavenging intracellular ROS. PMID:22841920

  16. Transport of cerium oxide nanoparticles in saturated silica media: influences of operational parameters and aqueous chemical conditions

    PubMed Central

    Zhang, Zhaohan; Gao, Peng; Qiu, Ye; Liu, Guohong; Feng, Yujie; Wiesner, Mark

    2016-01-01

    This paper aimed to investigate the influences of operational parameters and aqueous chemical conditions on transport behaviors of cerium oxides nanoparticles (CeO2-NPs) in saturated silica media. Results indicated that increasing rates of attachment efficiency (α) were related with cationic types, and critical deposition concentration (CDC) for divalent cation (Ca2+ and Mg2+) were more than 31-fold of that for monovalent cation (Na+ and K+). Increase or reduction of electrolyte pH could both promote the mobility of CeO2-NPs in glass beads, while influence was more evident at alkaline conditions. α increased linearly with NPs concentrations, while decreased linearly with flow velocity in the column, and effects were related with electrolyte contents. Presence of surfactants could sharply decreased α, and SDS was more effective to facilitate CeO2-NPs transport than Triton X–100. With DOMs concentrations increasing, α firstly kept constant, then sharply declined, and finally reduced very slowly. The influence of DOMs on NPs deposition was in order of SA > HA > TA >  BSA. Overall, this study revealed that aqueous chemical conditions was crucial to NPs transport in porous media, and would provide significant information for our understanding on the fate and transport of nanoparticles in natural environment. PMID:27694968

  17. Transport of cerium oxide nanoparticles in saturated silica media: influences of operational parameters and aqueous chemical conditions

    NASA Astrophysics Data System (ADS)

    Zhang, Zhaohan; Gao, Peng; Qiu, Ye; Liu, Guohong; Feng, Yujie; Wiesner, Mark

    2016-10-01

    This paper aimed to investigate the influences of operational parameters and aqueous chemical conditions on transport behaviors of cerium oxides nanoparticles (CeO2-NPs) in saturated silica media. Results indicated that increasing rates of attachment efficiency (α) were related with cationic types, and critical deposition concentration (CDC) for divalent cation (Ca2+ and Mg2+) were more than 31-fold of that for monovalent cation (Na+ and K+). Increase or reduction of electrolyte pH could both promote the mobility of CeO2-NPs in glass beads, while influence was more evident at alkaline conditions. α increased linearly with NPs concentrations, while decreased linearly with flow velocity in the column, and effects were related with electrolyte contents. Presence of surfactants could sharply decreased α, and SDS was more effective to facilitate CeO2-NPs transport than Triton X–100. With DOMs concentrations increasing, α firstly kept constant, then sharply declined, and finally reduced very slowly. The influence of DOMs on NPs deposition was in order of SA > HA > TA >  BSA. Overall, this study revealed that aqueous chemical conditions was crucial to NPs transport in porous media, and would provide significant information for our understanding on the fate and transport of nanoparticles in natural environment.

  18. The Degradation Mitigation Effect of Cerium Oxide in Polymer Electrolyte Membranes in Extended Fuel Cell Durability Tests

    SciTech Connect

    Pearman, Benjamin P; Mohajeri, Nahid; Brooker, R. Paul; Rodgers, Marianne; Slattery, Darlene; Hampton, Michael; Cullen, David A; Seal, Sudipta

    2013-01-01

    In this work, two formulations of single-crystal cerium oxide nanoparticles of varying particle sizes were incorporated into perfluorosulfonic acid membrane electrode assemblies (MEAs) and their ability to improve the in-situ membrane durability was studied by subjecting them to 94 and 500 hours open-circuit voltage hold accelerated durability tests . In the shorter test the open circuit voltage decay rate was reduced by half and the fluoride emission by at least one order of magnitude, though no effect on hydrogen crossover or performance of the baseline MEAs was measured. The presence of the additive increased the particle size but decreased the number of platinum catalyst particles that were deposited in the membrane. The main Pt band was found at the predicted location; however, the incorporation of ceria caused a broadening with particles reaching further into the membrane. In 500 h tests, ceria-containing MEAs demonstrated a seven-fold decrease in open-circuit voltage decay and three order of magnitude reduction in fluoride emission rates with unchanged performance and hydrogen crossover, remaining effectively pristine whilst the baseline MEA underwent catastrophic failure.

  19. Fate of engineered cerium oxide nanoparticles in an aquatic environment and their toxicity toward 14 ciliated protist species.

    PubMed

    Zhang, Wei; Pu, Zhichao; Du, Songyan; Chen, Yongsheng; Jiang, Lin

    2016-05-01

    The potential environmental impacts of engineered cerium oxide nanoparticles (CeO2 NPs) on aquatic organisms have remained largely unknown. Therefore, the laboratory study featured herein was performed to determine the fate of CeO2 NPs in an aquatic environment and their toxicity towards 14 different ciliated protist species at a specified population level. An investigation of 48 h aggregation kinetics in the Dryl's solution showed the CeO2 NPs to be relatively stable. The pH values in three test medium were too far away from PZC, which explained the stability of CeO2 NPs. CeO2 NPs generally elicited more toxicity with increasing NP concentration, following certain dose-response relationships. Nano-CeO2 resulted in greater toxicity in a particle state than when added as bulk material. LC50 values showed a negative correlation with the surface-to-volume ratio for these protists, suggesting that surface adsorption of CeO2 NPs might contribute to the observed toxicity. Additionally, acute toxic responses of 14 ciliated protist species to CeO2 NPs were not significantly phylogenetically conserved. The results of these observations provide a better insight into the potential risks of CeO2 NPs in an aquatic environment.

  20. Fate of engineered cerium oxide nanoparticles in an aquatic environment and their toxicity toward 14 ciliated protist species.

    PubMed

    Zhang, Wei; Pu, Zhichao; Du, Songyan; Chen, Yongsheng; Jiang, Lin

    2016-05-01

    The potential environmental impacts of engineered cerium oxide nanoparticles (CeO2 NPs) on aquatic organisms have remained largely unknown. Therefore, the laboratory study featured herein was performed to determine the fate of CeO2 NPs in an aquatic environment and their toxicity towards 14 different ciliated protist species at a specified population level. An investigation of 48 h aggregation kinetics in the Dryl's solution showed the CeO2 NPs to be relatively stable. The pH values in three test medium were too far away from PZC, which explained the stability of CeO2 NPs. CeO2 NPs generally elicited more toxicity with increasing NP concentration, following certain dose-response relationships. Nano-CeO2 resulted in greater toxicity in a particle state than when added as bulk material. LC50 values showed a negative correlation with the surface-to-volume ratio for these protists, suggesting that surface adsorption of CeO2 NPs might contribute to the observed toxicity. Additionally, acute toxic responses of 14 ciliated protist species to CeO2 NPs were not significantly phylogenetically conserved. The results of these observations provide a better insight into the potential risks of CeO2 NPs in an aquatic environment. PMID:26986089

  1. Effect of nano-sized cerium-zirconium oxide solid solution on far-infrared emission properties of tourmaline powders

    NASA Astrophysics Data System (ADS)

    Guo, Bin; Yang, Liqing; Hu, Weijie; Li, Wenlong; Wang, Haojing

    2015-10-01

    Far-infrared functional nanocomposites were prepared by the co-precipitation method using natural tourmaline (XY3Z6Si6O18(BO3)3V3W, where X is Na+, Ca2+, K+, or vacancy; Y is Mg2+, Fe2+, Mn2+, Al3+, Fe3+, Mn3+, Cr3+, Li+, or Ti4+; Z is Al3+, Mg2+, Cr3+, or V3+; V is O2-, OH-; and W is O2-, OH-, or F-) powders, ammonium cerium(IV) nitrate and zirconium(IV) nitrate pentahydrate as raw materials. The reference sample, tourmaline modified with ammonium cerium(IV) nitrate alone was also prepared by a similar precipitation route. The results of Fourier transform infrared spectroscopy show that tourmaline modified with Ce and Zr has a better far-infrared emission property than tourmaline modified with Ce alone. Through characterization by transmission electron microscopy (TEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS), the mechanism for oxygen evolution during the heat process in the two composite materials was systematically studied. The XPS spectra show that Fe3+ ratio inside tourmaline modified with Ce alone can be raised by doping Zr. Moreover, it is showed that there is a higher Ce3+ ratio inside the tourmaline modified with Ce and Zr than tourmaline modified with Ce alone. In addition, XRD results indicate the formation of CeO2 and Ce1-xZrxO2 crystallites during the heat treatment and further TEM observations show they exist as nanoparticles on the surface of tourmaline powders. Based on these results, we attribute the improved far-infrared emission properties of Ce-Zr doped tourmaline to the enhanced unit cell shrinkage of the tourmaline arisen from much more oxidation of Fe2+ to Fe3+ inside the tourmaline caused by the change in the catalyst redox properties of CeO2 brought about by doping with Zr4+. In all samples, tourmaline modified with 7.14 wt.% Ce and 1.86 wt.% Zr calcined at 800∘C for 5 h has the best far-infrared emission property with the maximum emissivity value of 98%.

  2. Method of applying a cerium diffusion coating to a metallic alloy

    DOEpatents

    Jablonski, Paul D.; Alman, David E.

    2009-06-30

    A method of applying a cerium diffusion coating to a preferred nickel base alloy substrate has been discovered. A cerium oxide paste containing a halide activator is applied to the polished substrate and then dried. The workpiece is heated in a non-oxidizing atmosphere to diffuse cerium into the substrate. After cooling, any remaining cerium oxide is removed. The resulting cerium diffusion coating on the nickel base substrate demonstrates improved resistance to oxidation. Cerium coated alloys are particularly useful as components in a solid oxide fuel cell (SOFC).

  3. Effects of Cerium and Titanium Oxide Nanoparticles in Soil on the Nutrient Composition of Barley (Hordeum vulgare L.) Kernels

    PubMed Central

    Pošćić, Filip; Mattiello, Alessandro; Fellet, Guido; Miceli, Fabiano; Marchiol, Luca

    2016-01-01

    The implications of metal nanoparticles (MeNPs) are still unknown for many food crops. The purpose of this study was to evaluate the effects of cerium oxide (nCeO2) and titanium oxide (nTiO2) nanoparticles in soil at 0, 500 and 1000 mg·kg−1 on the nutritional parameters of barley (Hordeum vulgare L.) kernels. Mineral nutrients, amylose, β-glucans, amino acid and crude protein (CP) concentrations were measured in kernels. Whole flour samples were analyzed by ICP-AES/MS, HPLC and Elemental CHNS Analyzer. Results showed that Ce and Ti accumulation under MeNPs treatments did not differ from the control treatment. However, nCeO2 and nTiO2 had an impact on composition and nutritional quality of barley kernels in contrasting ways. Both MeNPs left β-glucans unaffected but reduced amylose content by approximately 21%. Most amino acids and CP increased. Among amino acids, lysine followed by proline saw the largest increase (51% and 37%, respectively). Potassium and S were both negatively impacted by MeNPs, while B was only affected by 500 mg nCeO2·kg−1. On the contrary Zn and Mn concentrations were improved by 500 mg nTiO2·kg−1, and Ca by both nTiO2 treatments. Generally, our findings demonstrated that kernels are negatively affected by nCeO2 while nTiO2 can potentially have beneficial effects. However, both MeNPs have the potential to negatively impact malt and feed production. PMID:27294945

  4. Influence of a Cerium surface treatment on the oxidation behavior of type 347 stainless steel

    SciTech Connect

    Alman, D.E.; Jablonski, P.D.

    2007-04-01

    A surface treatment was applied to the surface of Type 347 stainless steel to enhance oxidation resistance. The treatment consisted of dip coating coupons in a CeO2 and halide activator slurry, followed by a thermal treatment at 900C in an inert atmosphere for 12 hours. Cyclical oxidation tests were conducted at 800C in either dry air or air+3%H2O. In dry air, the treatment reduced the oxidation rate (reduced the magnitude of weight gain) of the alloy by a factor of three. Protective chromium based oxide and spinel ((Mn,Cr)3O4 and (Cr,Fe)2O3) phases formed on the surface of the untreated and treated alloy. More significantly, the treatment suppressed the oxide scale spallation that occurred upon cyclical exposure of this alloy to moist air. In moist air, less protective chromite (FeCr2O4), magnetite (Fe+2Fe2+3O4), and hematite (Fe2O3) formed as oxide products on the surface of the base alloy. The treated alloy did not spall during exposure to moist air, and interestingly, the treated alloy possessed similar oxidation rates (magnitude of weight gain) in both moist and dry air. The same protective chromium based oxide and spinel ((Mn,Cr)3O4 and (Cr,Fe)2O3) phases formed on the surface of the treated alloy exposed to both moist and dry air. In the aggressive moist environment, the Ce surface treatment suppressed the formation of less protective iron-oxides, and concomitant oxide scale spallation during thermal cycling.

  5. Storage capacity and oxygen mobility in mixed oxides from transition metals promoted by cerium

    NASA Astrophysics Data System (ADS)

    Perdomo, Camilo; Pérez, Alejandro; Molina, Rafael; Moreno, Sonia

    2016-10-01

    The oxygen mobility and storage capacity of Ce-Co/Cu-MgAl or Ce-MgAl mixed oxides, obtained by hydrotalcite precursors, were evaluated using Toluene-temperature-programmed-reaction, 18O2 isotopic exchange and O2-H2 titration. The presence of oxygen vacancies-related species was evaluated by means of Electron Paramagnetic Resonance. A correlation was found between the studied properties and the catalytic activity of the oxides in total oxidation processes. It was evidenced that catalytic activity depends on two related processes: the facility with which the solid can be reduced and its ability to regenerate itself in the presence of molecular oxygen in the gas phase. These processes are enhanced by Cu-Co cooperative effect in the mixed oxides. Additionally, the incorporation of Ce in the Co-Cu catalysts improved their oxygen transport properties.

  6. A nitrilo-tri-acetic-acid/acetic acid route for the deposition of epitaxial cerium oxide films as high temperature superconductor buffer layers

    SciTech Connect

    Thuy, T.T.; Lommens, P.; Narayanan, V.; Van de Velde, N.; De Buysser, K.; Herman, G.G.; Cloet, V.; Van Driessche, I.

    2010-09-15

    A water based cerium oxide precursor solution using nitrilo-tri-acetic-acid (NTA) and acetic acid as complexing agents is described in detail. This precursor solution is used for the deposition of epitaxial CeO{sub 2} layers on Ni-5at%W substrates by dip-coating. The influence of the complexation behavior on the formation of transparent, homogeneous solutions and gels has been studied. It is found that ethylenediamine plays an important role in the gelification. The growth conditions for cerium oxide films were Ar-5% gas processing atmosphere, a solution concentration level of 0.25 M, a dwell time of 60 min at 900 {sup o}C and 5-30 min at 1050 {sup o}C. X-ray diffraction (XRD), scanning electron microscope (SEM), atomic force microscopy (AFM), pole figures and spectroscopic ellipsometry were used to characterize the CeO{sub 2} films with different thicknesses. Attenuated total reflection-Fourier transform infrared (ATR-FTIR) was used to determine the carbon residue level in the surface of the cerium oxide film, which was found to be lower than 0.01%. Textured films with a thickness of 50 nm were obtained. - Graphical abstract: Study of the complexation and hydrolysis behavior of Ce{sup 4+} ions in the presence of nitrilo-tri-acetic acid and the subsequent development of an aqueous chemical solution deposition route suited for the processing of textured CeO{sub 2} buffer layers on Ni-W tapes.

  7. Characteristics and mechanism study of cerium oxide based random access memories

    SciTech Connect

    Hsieh, Cheng-Chih; Roy, Anupam; Rai, Amritesh; Chang, Yao-Feng; Banerjee, Sanjay K.

    2015-04-27

    In this work, low operating voltage and high resistance ratio of different resistance states of binary transition metal oxide based resistive random access memories (RRAMs) are demonstrated. Binary transition metal oxides with high dielectric constant have been explored for RRAM application for years. However, CeO{sub x} is considered as a relatively new material to other dielectrics. Since research on CeO{sub x} based RRAM is still at preliminary stage, fundamental characteristics of RRAM such as scalability and mechanism studies need to be done before moving further. Here, we show very high operation window and low switching voltage of CeO{sub x} RRAMs and also compare electrical performance of Al/CeO{sub x}/Au system between different thin film deposition methods and discuss characteristics and resistive switching mechanism.

  8. A comparative study of the oxides of lanthanum, cerium, praseodymium, and samarium as catalysts for the oxidative dehydrogenation of methane in the presence and absence of carbon tetrachloride

    SciTech Connect

    Sugiyama, Shigeru; Matsumura, Yasuyuki; Moffat, J.B. )

    1993-02-01

    The catalytic oxidative coupling of methane to ethane and ethene has been investigated on the rare earth oxides, i.e., La[sub 2]O[sub 3], CeO[sub 2], Pr[sub 6]O[sub 11], and Sm[sub 2]O[sub 3]. Addition of a small amount of tetrachloromethane (TCM) to the reactant stream improves the catalytic activity of these oxides. In particular, the praseodymium catalyst yields high selectivity to the C[sub 2] compounds comparable to La[sub 2]O[sub 3] or Sm[sub 2]O[sub 3] when TCM is present in the feedstream. The X-ray diffraction patterns for these catalysts after the reaction with TCM show the presence of the oxychlorides in the catalysts except for the cerium catalyst, for which the selectivity to C[sub 2] compounds is very low even in the presence of TCM. The oxychlorides can be generated on La[sub 2]O[sub 3], Sm[sub 2]O[sub 3], or Pr[sub 6]O[sub 11] by preheating under a stream including TCM. The product distribution of the reaction with these catalysts in the absence of TCM is similar to that with the oxides in the presence of TCM, while Pr[sub 6]O[sub 11] pretreated with TCM is unstable with no TCM in the feedstream. It appears that the improvement of the activity of the rare earth catalysts with TCM in the feedstream is primarily due to the formation of the oxychlorides during the reaction. 49 refs., 6 figs., 5 tabs.

  9. Cerium ion conducting solid electrolyte

    NASA Astrophysics Data System (ADS)

    Hasegawa, Yasunori; Imanaka, Nobuhito; Adachi, Gin-ya

    2003-02-01

    A cerium ion conducting solid electrolyte, (Ce xZr 1- x) 4/4- xNb(PO 4) 3, was successfully realized with the NASICON-type structure which possesses a three-dimensional network, especially suitable for bulky ion migration. The cerium ion conductivity exceeds approximately one order of magnitude in comparison to that of the rare-earth ion conducting R2(WO 4) 3 and R1/3Zr 2(PO 4) 3 ( R=Sc, Y, Eu-Lu) series and the value is in the range between typical oxide anion conductors of yttria stabilized zirconia (YSZ) and calcia stabilized zirconia (CSZ). Since cerium ion has been demonstrated to be another migrating ion species in solid electrolyte field, a promising application for various functional materials is greatly expected.

  10. Effect of cerium oxide nanoparticles on inflammation in vascular endothelial cells

    PubMed Central

    Gojova, Andrea; Lee, Jun-Tae; Jung, Heejung S.; Guo, Bing; Barakat, Abdul I.; Kennedy, Ian M.

    2010-01-01

    Because vascular endothelial cell inflammation is critical in the development of cardiovascular pathology, we hypothesized that direct exposure of human aortic endothelial cells (HAECs) to ultrafine particles induces an inflammatory response. To test the hypothesis, we incubated HAECs for 4 h with different concentrations (0.001–50 μg/ml) of CeO2 nanoparticles and subsequently measured mRNA levels of the three inflammatory markers intercellular adhesion molecule 1 (ICAM-1), interleukin (IL)-8, and monocyte chemotactic protein (MCP-1) using real-time polymerase chain reaction (PCR). Ceria nanoparticles caused very little inflammatory response in HAECs, even at the highest dose. This material is apparently rather benign in comparison with Y2O3 and ZnO nanoparticles that we have studied previously. These results suggest that inflammation in HAECs following acute exposure to metal oxide nanoparticles depends strongly on particle composition. PMID:19558244

  11. Pilot demonstration of cerium oxide coated anodes. Final report, April 1990--October 1992

    SciTech Connect

    Gregg, J.S.; Frederick, M.S.; Shingler, M.J.; Alcorn, T.R.

    1992-10-01

    Cu cermet anodes were tested for 213 to 614 hours with an in-situ deposited CEROX coating in a pilot cell operated by Reynolds Manufacturing Technology Laboratory. At high bath ratio ({approximately}1.5) and low current density (0.5 A/cm{sup 2}), a {ge}1 mm thick dense CEROX coating was deposited on the anodes. At lower bath ratios and higher current density, the CEROX coating was thinner and less dense, but no change in corrosion rate was noted. Regions of low current density on the anodes and sides adjacent to the carbon anode sometimes had thin or absent CEROX coatings. Problems with cracking and oxidation of the cermet substrates led to higher corrosion rates in a pilot cell than would be anticipated from lab scale results.

  12. A rapid solvothermal synthesis of cerium oxide hollow spheres and characterization

    SciTech Connect

    Kempaiah Devaraju, Murukanahally; Liu, Xiangwen; Yin, Shu; Sato, Tsugio

    2012-10-15

    An easy and size controlled solvothermal synthesis of CeO{sub 2} hollow spheres is still a challenge in the area of materials synthesis. Here, CeO{sub 2} hollow spheres have been synthesized using PVA500 as a surfactant via solvothermal reaction followed by calcinations. The size of CeO{sub 2} hollow spheres could be controlled from 500 to 150 nm by changing the amounts of Ce(NO{sub 3}){sub 3}{center_dot}6H{sub 2}O and PVA500. The possible growth mechanism of CeO{sub 2} hollow sphere was explained. The CO oxidation catalytic activity of the CeO{sub 2} hollow spheres were superior to that of the commercial CeO{sub 2} powder due to the high specific surface area and small crystallite size. - Graphical abstract: A rapid and easy way to prepare CeO{sub 2} hollow sphere with 150-500 nm in diameter was successfully achieved by solvothermal reaction. The prepared particles showed hollowness due to Ostwald ripening process. An improved catalytic activity was observed and discussed. Highlights: A rapid synthesis of CeO{sub 2} hollow spheres with diameter size from 15 to 500 nm. Black-Right-Pointing-Pointer Cheap surfactant was used to prepare hollow spheres. Black-Right-Pointing-Pointer Effect of temperature and surfactant ratio were investigated. Black-Right-Pointing-Pointer Systematic characterization by XRD, FESEM, TEM, TG, FTIR and UV. Black-Right-Pointing-Pointer CO oxidation analysis results showed better catalytic activity.

  13. Cerium oxidation state in silicate melts: Combined fO2, temperature and compositional effects

    NASA Astrophysics Data System (ADS)

    Smythe, Duane J.; Brenan, James M.

    2015-12-01

    To quantify the relative proportions of Ce3+ and Ce4+ in natural magmas, we have synthesized a series of Ce doped glasses ranging in composition from basalt to rhyolite (±H2O) at 0.001 and 1 GPa, under fO2 conditions varying from FMQ -4.0 to FMQ +8.4, and temperatures from 1200 to 1500 °C. The Ce4+/Ce3+ ratio in the experimental run products was determined both potentiometrically and in situ, using Ce M4,5-edge X-ray absorption near-edge structure (XANES) spectroscopy. For a given melt composition, the change in Ce4+/Ce3+ ratio with fO2 follows the trend predicted from the reaction stoichiometry assuming simple oxides as melt species. In addition to fO2, melt composition and water content have been found to be secondary controls on Ce4+/Ce3+, with more depolymerized melts and hydrous compositions favoring the stabilization of Ce3+. The Ce4+/Ce3+ ratio can be expressed through the equation,

  14. Studies on Synthesis, Microstructure and Transport Properties of Doped Cerium Oxides

    NASA Astrophysics Data System (ADS)

    Handal, Hala Talaat Abd El-Samei

    Acceptor-doped ceria exhibits mixed ionic electronic conduction in reducing conditions and chemical stability against sulfur poisoning and coking. This thesis's primary goal is to explore new anode materials based on ceria--solid solutions for solid oxide fuel cells (SOFCs). The physicochemical and electrochemical performance of Ce0.9-xY 0.1MnxO2-delta ( x = 0 to 15 mol%) (CYMO) and Ce0.87Y0.1Mn 0.01N0.02O2-delta (N = Mg or Ca) were studied. Among the materials investigated in this study, Ce0.89Y 0.1Mn0.01Mg0.02O2-delta (Mg-CYMO) showed the highest total conductivity of 0.2 S cm-1 at 700°C in H2. An area specific polarization resistance of 0.23 O cm2 was observed for both Mg-CYMO and Ce0.8Y 0.1Mn0.1O2-delta (10CYMO) at 800°C, in wet H2. Chronoamperometric measurement for the symmetrical cell configuration based on 10CYMO electrodes showed stable performance upon exposure to 10 ppm H2S/H2. In a full cell configuration, 10CYMO (anode)/YSZ (electrolyte)/La0.8Sr0.2MnO3 (LSM)-YSZ cathode, polarization resistance of 1.4 O cm2 and power density of 75 mW/cm2 were obtained at 800°C in wet H2. The main challenge of employing proton-conducting electrolytes in SOFC is their poor chemical stability in the presence of steam and hydrocarbon fuels. Another goal of this thesis is to develop a chemically stable proton-conducting electrolyte for SOFCs. The effects of Fe and Co substitution on the electrical and physicochemical properties of BaCe0.9Sm0.1O 3-delta (BCS) were evaluated. Thermogravimetric analysis showed that incorporation of 5 to 10 mol% Fe or Co in BCS did not improve the chemical stability in CO2 at elevated temperatures. The BCSC10 sample sintering at 1400°C showed the highest electrical conductivity of 0.02 S cm -1 at 600°C in air, but it did not show any appreciable proton mobility under humidified atmosphere.

  15. Properties of cerium-zirconium mixed oxides partially substituted by neodymium: Comparison with Zr-Ce-Pr-O ternary oxides

    SciTech Connect

    Mikulova, Jana; Rossignol, Sylvie . E-mail: Sylvie.rossignol@univ-poitiers.fr; Gerard, Francois; Mesnard, Danielle; Kappenstein, Charles; Duprez, Daniel

    2006-08-15

    CeO{sub 2} doped with praseodymium, neodymium and/or zirconium atoms were prepared by coprecipitation and by the sol-gel method. Structural properties were investigated by in situ XRD and Raman spectroscopy while oxygen storage capacity (OSC) was measured by transient CO oxidation. All the compounds, except pure Nd{sub 2}O{sub 3}, have a fluorite-type structure as well as a Raman band at 560 cm{sup -1} characteristic of the oxygen vacancies involving non-stoichiometric oxides. The lattice parameter under hydrogen, being dependent on the temperature, revealed two reduction mechanisms: one at a low temperature at the surface and another at a high temperature in the bulk. Ce-Nd binary oxides show a strong tendency towards crystallite aggregation, which reduces accessibility to gases and OSC properties. Zirconium improves the thermal resistance to sintering of both Ce-Nd and Ce-Pr oxides. The Zr-Ce-Pr-O followed by Zr-Ce-Nd-O compounds displaying high oxygen mobility at a low temperature, appear to be very promising for practical applications such as OSC materials. - Graphical abstract: Variation of oxygen vacancies under hydrogen on ternary oxides.

  16. Oxidation-state sensitive imaging of cerium dioxide by atomic-resolution low-angle annular dark field scanning transmission electron microscopy.

    PubMed

    Johnston-Peck, Aaron C; Winterstein, Jonathan P; Roberts, Alan D; DuChene, Joseph S; Qian, Kun; Sweeny, Brendan C; Wei, Wei David; Sharma, Renu; Stach, Eric A; Herzing, Andrew A

    2016-03-01

    Low-angle annular dark field (LAADF) scanning transmission electron microscopy (STEM) imaging is presented as a method that is sensitive to the oxidation state of cerium ions in CeO2 nanoparticles. This relationship was validated through electron energy loss spectroscopy (EELS), in situ measurements, as well as multislice image simulations. Static displacements caused by the increased ionic radius of Ce(3+) influence the electron channeling process and increase electron scattering to low angles while reducing scatter to high angles. This process manifests itself by reducing the high-angle annular dark field (HAADF) signal intensity while increasing the LAADF signal intensity in close proximity to Ce(3+) ions. This technique can supplement STEM-EELS and in so doing, relax the experimental challenges associated with acquiring oxidation state information at high spatial resolutions. PMID:26744830

  17. Oxidation-state sensitive imaging of cerium dioxide by atomic-resolution low-angle annular dark field scanning transmission electron microscopy.

    PubMed

    Johnston-Peck, Aaron C; Winterstein, Jonathan P; Roberts, Alan D; DuChene, Joseph S; Qian, Kun; Sweeny, Brendan C; Wei, Wei David; Sharma, Renu; Stach, Eric A; Herzing, Andrew A

    2016-03-01

    Low-angle annular dark field (LAADF) scanning transmission electron microscopy (STEM) imaging is presented as a method that is sensitive to the oxidation state of cerium ions in CeO2 nanoparticles. This relationship was validated through electron energy loss spectroscopy (EELS), in situ measurements, as well as multislice image simulations. Static displacements caused by the increased ionic radius of Ce(3+) influence the electron channeling process and increase electron scattering to low angles while reducing scatter to high angles. This process manifests itself by reducing the high-angle annular dark field (HAADF) signal intensity while increasing the LAADF signal intensity in close proximity to Ce(3+) ions. This technique can supplement STEM-EELS and in so doing, relax the experimental challenges associated with acquiring oxidation state information at high spatial resolutions.

  18. Exposure to Cerium Oxide Nanoparticles Is Associated With Activation of Mitogen-activated Protein Kinases Signaling and Apoptosis in Rat Lungs

    PubMed Central

    Rice, Kevin M.; Nalabotu, Siva K.; Manne, Nandini D.P.K.; Kolli, Madhukar B.; Nandyala, Geeta; Arvapalli, Ravikumar; Ma, Jane Y.; Blough, Eric R.

    2015-01-01

    Objectives: With recent advances in nanoparticle manufacturing and applications, potential exposure to nanoparticles in various settings is becoming increasing likely. No investigation has yet been performed to assess whether respiratory tract exposure to cerium oxide (CeO2) nanoparticles is associated with alterations in protein signaling, inflammation, and apoptosis in rat lungs. Methods: Specific-pathogen-free male Sprague-Dawley rats were instilled with either vehicle (saline) or CeO2 nanoparticles at a dosage of 7.0 mg/kg and euthanized 1, 3, 14, 28, 56, or 90 days after exposure. Lung tissues were collected and evaluated for the expression of proteins associated with inflammation and cellular apoptosis. Results: No change in lung weight was detected over the course of the study; however, cerium accumulation in the lungs, gross histological changes, an increased Bax to Bcl-2 ratio, elevated cleaved caspase-3 protein levels, increased phosphorylation of p38 MAPK, and diminished phosphorylation of ERK-1/2-MAPK were detected after CeO2 instillation (p<0.05). Conclusions: Taken together, these data suggest that high-dose respiratory exposure to CeO2 nanoparticles is associated with lung inflammation, the activation of signaling protein kinases, and cellular apoptosis, which may be indicative of a long-term localized inflammatory response. PMID:26081650

  19. Role of tetrachloromethane as a gas-phase additive in the oxidative dehydrogenation of propane over cerium oxide

    SciTech Connect

    Sugiyama, Shigeru; Iizuka, Y.; Nitta, E.; Hayashi, H.; Moffat, J.B.

    2000-01-01

    In the absence of tetrachloromethane (TCM) carbon dioxide is the principal product formed in the oxidation of propane on ceria. The introduction of small partial pressures of TCM increases the conversion of propane with selectivities to propene up to 80%. Except under special circumstances no evidence of chlorinated species from TCM is found in the bulk structure while the surface region is shown to contain chlorine, although its form is not known. The enhancement of conversion and selectivity to propene is shown to be dependent upon the presence of chlorine, in whatever form, in the surface region of the catalyst.

  20. Determining the Source of Water Vapor in a Cerium Oxide Electrochemical Oxygen Separator to Achieve Aviator Grade Oxygen

    NASA Technical Reports Server (NTRS)

    Graf, John; Taylor, Dale; Martinez, James

    2014-01-01

    More than a metric ton of water is transported to the International Space Station (ISS) each year to provide breathing oxygen for the astronauts. Water is a safe and compact form of stored oxygen. The water is electrolyzed on ISS and ambient pressure oxygen is delivered to the cabin. A much smaller amount of oxygen is used each year in spacesuits to conduct Extra Vehicular Activities (EVAs). Space suits need high pressure (>1000 psia) high purity oxygen (must meet Aviator Breathing Oxygen "ABO" specifications, >99.5% O2). The water / water electrolysis system cannot directly provide high pressure, high purity oxygen, so oxygen for EVAs is transported to ISS in high pressure gas tanks. The tanks are relatively large and heavy, and the majority of the system launch weight is for the tanks and not the oxygen. Extracting high purity oxygen from cabin air and mechanically compressing the oxygen might enable on-board production of EVA grade oxygen using the existing water / water electrolysis system. This capability might also benefit human spaceflight missions, where oxygen for EVAs could be stored in the form of water, and converted into high pressure oxygen on-demand. Cerium oxide solid electrolyte-based ion transport membranes have been shown to separate oxygen from air, and a supported monolithic wafer form of the CeO2 electrolyte membrane has been shown to deliver oxygen at pressures greater than 300 psia. These supported monolithic wafers can withstand high pressure differentials even though the membrane is very thin, because the ion transport membrane is supported on both sides (Fig 1). The monolithic supported wafers have six distinct layers, each with matched coefficients of thermal expansion. The wafers are assembled into a cell stack which allows easy air flow across the wafers, uniform current distribution, and uniform current density (Fig 2). The oxygen separation is reported to be "infinitely selective" to oxygen [1] with reported purity of 99.99% [2

  1. Stability of Commercial Small-Sized Cerium Oxide in the Presence of Biological Material: Dilucidating Relationships between Reactivity and Toxicity of Nanomaterials

    NASA Astrophysics Data System (ADS)

    Cervini-Silva, J.; Gilbert, B.; Fernandez-Lomelin, P.; Guzman-Mendoza, J.; Chavira, E.

    2007-05-01

    Cerium is the most abundant lanthanide and generally the only one to undergo redox reactions at the Earth's surface. Although rarely studied in natural environments, the redox chemistry of cerium may regulate metal toxicity. Unlike Ce(III) or other lanthanide ions, Ce(IV) has shown a remarkably efficacy to hydrolyze DNA. While Ce(IV) has been recognized as an important candidate to occupy peptidases catalytic centers, Ce(III) is virtually inactive for peptide hydrolysis. The selectivity of Ce as Ce(IV) relates to the specific coordination of water molecules and their orientation. Ce(IV) may bind selectivity to biomolecules to instigate conformation changes or cleavage of complexes, which affect metabolic pathways pivotal to growth and survival. For instance, Ce(IV) promotes the selective cleavage of RNA-type substrates, cyclic monophosphates, peptides, or monocleotides such as AMP, leading to mixtures of nucleosides and nucleobases. Association constants for Ce(IV)-DNA complexes are reported to be higher in magnitude for single stranded than double stranded DNA, while cleavage rates for either complexes are comparable. Complexation of Ce(IV) with mitoxantrone results in the intercalation of such complex into DNA, enabling mitoxantrone to bind effectively with DNA, along with concomitant conformational changes in the DNA double helix and inhibition of DNA synthesis. To the authors' knowledge, however, little information is available on the reactivity as it relates to toxicity of Ce-bearing nanoparticles widely used in nanotechnological applications. Here, we study molecular interactions between small-sized CeO2 and biomolecules(e.g., DNA, RNA, proteins) using carbon and cerium spectroscopy. Suspension stability as determined by aggregation kinetics was studied by Dynamic Light Scattering (DSL) and UV. In addition, acidophiles and fungi cultures were analyzed by nephelometry to estimate population density and growth rate values. Results show a progressive increase in

  2. Corrosion resistance and durability of superhydrophobic surface formed on magnesium alloy coated with nanostructured cerium oxide film and fluoroalkylsilane molecules in corrosive NaCl aqueous solution.

    PubMed

    Ishizaki, Takahiro; Masuda, Yoshitake; Sakamoto, Michiru

    2011-04-19

    The corrosion resistant performance and durability of the superhydrophobic surface on magnesium alloy coated with nanostructured cerium oxide film and fluoroalkylsilane molecules in corrosive NaCl aqueous solution were investigated using electrochemical and contact angle measurements. The durability of the superhydrophobic surface in corrosive 5 wt% NaCl aqueous solution was elucidated. The corrosion resistant performance of the superhydrophobic surface formed on magnesium alloy was estimated by electrochemical impedance spectroscopy (EIS) measurements. The EIS measurements and appropriate equivalent circuit models revealed that the superhydrophobic surface considerably improved the corrosion resistant performance of magnesium alloy AZ31. American Society for Testing and Materials (ASTM) standard D 3359-02 cross cut tape test was performed to investigate the adhesion of the superhydrophobic film to the magnesium alloy surface. The corrosion formation mechanism of the superhydrophobic surface formed on the magnesium alloy was also proposed.

  3. Study of the cerium(IV)-picrate system in acetonitrile.

    PubMed

    Kratochvil, B; Tipler, M; McKay, B

    1966-07-01

    A potentiometric and spectrophotometric study has been made of the reaction between hexanitratocerate and picrate in dry acetonitrile. Several cerium(IV)-picrate complexes are formed; the formation constant for the first is estimated to be 4 from spectrophotometric measurements. The catalytic effect of picrate on hydroquinone oxidation by nitratocerate is postulated to be due to more rapid electron transfer by cerium picrate complexes.

  4. Cerium anomaly at microscale in fossils.

    PubMed

    Gueriau, Pierre; Mocuta, Cristian; Bertrand, Loïc

    2015-09-01

    Patterns in rare earth element (REE) concentrations are essential instruments to assess geochemical processes in Earth and environmental sciences. Excursions in the "cerium anomaly" are widely used to inform on past redox conditions in sediments. This proxy resources to the specificity of cerium to adopt both the +III and +IV oxidation states, while most rare earths are purely trivalent and share very similar reactivity and transport properties. In practical terms, the level of cerium anomaly is established through elemental point quantification and profiling. All these models rely on a supposed homogeneity of the cerium oxidation state within the samples. However, this has never been demonstrated, whereas the cerium concentration can significantly vary within a sample, as shown for fossils, which would vastly complicate interpretation of REE patterns. Here, we report direct micrometric mapping of Ce speciation through synchrotron X-ray absorption spectroscopy and production of local rare earth patterns in paleontological fossil tissues through X-ray fluorescence mapping. The sensitivity of the approach is demonstrated on well-preserved fishes and crustaceans from the Late Cretaceous (ca. 95 million years (Myr) old). The presence of Ce under the +IV form within the fossil tissues is attributed to slightly oxidative local conditions of burial and agrees well with the limited negative cerium anomaly observed in REE patterns. The [Ce(IV)]/[Ce(tot)] ratio appears remarkably stable at the microscale within each fossil and is similar between fossils from the locality. Speciation maps were obtained from an original combination of synchrotron microbeam X-ray fluorescence, absorption spectroscopy, and diffraction, together with light and electron microscopy. This work also highlights the need for more systematic studies of cerium geochemistry at the microscale in paleontological contexts, in particular across fossil histologies.

  5. Cerium anomaly at microscale in fossils.

    PubMed

    Gueriau, Pierre; Mocuta, Cristian; Bertrand, Loïc

    2015-09-01

    Patterns in rare earth element (REE) concentrations are essential instruments to assess geochemical processes in Earth and environmental sciences. Excursions in the "cerium anomaly" are widely used to inform on past redox conditions in sediments. This proxy resources to the specificity of cerium to adopt both the +III and +IV oxidation states, while most rare earths are purely trivalent and share very similar reactivity and transport properties. In practical terms, the level of cerium anomaly is established through elemental point quantification and profiling. All these models rely on a supposed homogeneity of the cerium oxidation state within the samples. However, this has never been demonstrated, whereas the cerium concentration can significantly vary within a sample, as shown for fossils, which would vastly complicate interpretation of REE patterns. Here, we report direct micrometric mapping of Ce speciation through synchrotron X-ray absorption spectroscopy and production of local rare earth patterns in paleontological fossil tissues through X-ray fluorescence mapping. The sensitivity of the approach is demonstrated on well-preserved fishes and crustaceans from the Late Cretaceous (ca. 95 million years (Myr) old). The presence of Ce under the +IV form within the fossil tissues is attributed to slightly oxidative local conditions of burial and agrees well with the limited negative cerium anomaly observed in REE patterns. The [Ce(IV)]/[Ce(tot)] ratio appears remarkably stable at the microscale within each fossil and is similar between fossils from the locality. Speciation maps were obtained from an original combination of synchrotron microbeam X-ray fluorescence, absorption spectroscopy, and diffraction, together with light and electron microscopy. This work also highlights the need for more systematic studies of cerium geochemistry at the microscale in paleontological contexts, in particular across fossil histologies. PMID:26239283

  6. PLUTONIUM-CERIUM ALLOY

    DOEpatents

    Coffinberry, A.S.

    1959-01-01

    An alloy is presented for use as a reactor fuel. The binary alloy consists essentially of from about 5 to 90 atomic per cent cerium and the balance being plutonium. A complete phase diagram for the cerium--plutonium system is given.

  7. Inhibition of MAP kinase/NF-kB mediated signaling and attenuation of lipopolysaccharide induced severe sepsis by cerium oxide nanoparticles

    PubMed Central

    Selvaraj, Vellaisamy; Nepal, Niraj; Rogers, Steven; Manne, Nandini D.P.K.; Arvapalli, Ravikumar; Rice, Kevin M.; Asano, Shinichi; Fankhanel, Erin; Ma, Jane J.; Shokuhfar, Tolou; Maheshwari, Mani; Blough, Eric R.

    2015-01-01

    Sepsis is a life threatening disease that is associated with high mortality. Existing treatments have failed to improve survivability in septic patients. The purpose of this present study is to evaluate whether cerium oxide nanoparticles (CeO2NPs) can prevent lipopolysaccharide (LPS) induced severe sepsis mortality by preventing hepatic dysfunction in male Sprague Dawley rats. Administration of a single dose (0.5 mg/kg) of CeO2NPs intravenously to septic rats significantly improved survival rates and functioned to restore body temperature, respiratory rate and blood pressure towards baseline. Treatment-induced increases in animal survivability were associated with decreased hepatic damage along with reductions in serum cytokines/chemokines, and diminished inflammatory related signaling. Kupffer cells and macrophage cells exposed to CeO2NPs exhibited decreases in LPS-induced cytokine release (TNF-α, IL-1β, IL-6, HMGB1) which were associated with diminished cellular ROS, reduced levels of nitric oxide synthase (iNOS), cyclooxygenase 2 (COX-2), and decreased nuclear factor-kappa light chain enhancer of activated B cells (NF-kB) transcriptional activity. The findings of this study indicate that CeO2NPs may be useful as a therapeutic agent for sepsis. PMID:25968464

  8. Cerium oxide nanoparticles alter the antioxidant capacity but do not impact tuber ionome in Raphanus sativus (L).

    PubMed

    Corral-Diaz, Baltazar; Peralta-Videa, Jose R; Alvarez-Parrilla, Emilio; Rodrigo-García, Joaquin; Morales, Maria Isabel; Osuna-Avila, Pedro; Niu, Genhua; Hernandez-Viezcas, Jose A; Gardea-Torresdey, Jorge L

    2014-11-01

    The effects of nCeO2 on food quality are not well known yet. This research was performed to determine the impact of nCeO2 on radish (Raphanus sativus L.). Plants were cultivated to full maturity in potting soil treated with nCeO2 at concentrations of 0, 62.5, 125, 250, and 500 mg/kg. Germination, growth, photosynthesis, ionome, and antioxidants were evaluated at different growth stages. Results showed that at 500 mg/kg, nCeO2 significantly retarded seed germination but did not reduce the number of germinated seeds. None of the treatments affected gas exchange, photosynthesis, growth, phenols, flavonoids, and nutrients' accumulation in tubers and leaves of adult plants. However, tubers' antioxidant capacity, expressed as FRAP, ABTS(•-) and DPPH, increased by 30%, 32%, and 85%, respectively, in plants treated with 250 mg nCeO2kg(-1) soil. In addition, cerium accumulation in tubers of plants treated with 250 and 500 mg/kg reached 72 and 142 mg/kg d wt, respectively. This suggests that nCeO2 could improve the radical scavenging potency of radish but it might introduce nCeO2 into the food chain with unknown consequences. PMID:25439500

  9. Methane Activation Mediated by a Series of Cerium-Vanadium Bimetallic Oxide Cluster Cations: Tuning Reactivity by Doping.

    PubMed

    Ma, Jia-Bi; Meng, Jing-Heng; He, Sheng-Gui

    2016-04-18

    The reactions of cerium-vanadium cluster cations Cex Vy Oz (+) with CH4 are investigated by time-of-flight mass spectrometry and density functional theory calculations. (CeO2 )m (V2 O5 )n (+) clusters (m=1,2, n=1-5; m=3, n=1-4) with dimensions up to nanosize can abstract one hydrogen atom from CH4 . The theoretical study indicates that there are two types of active species in (CeO2 )m (V2 O5 )n (+) , V[(Ot )2 ](.) and [(Ob )2 CeOt ](.) (Ot and Ob represent terminal and bridging oxygen atoms, respectively); the former is less reactive than the latter. The experimentally observed size-dependent reactivities can be rationalized by considering the different active species and mechanisms. Interestingly, the reactivity of the (CeO2 )m (V2 O5 )n (+) clusters falls between those of (CeO2 )2-4 (+) and (V2 O5 )1-5 (+) in terms of C-H bond activation, thus the nature of the active species and the cluster reactivity can be effectively tuned by doping.

  10. Cerium oxide nanoparticles alter the antioxidant capacity but do not impact tuber ionome in Raphanus sativus (L).

    PubMed

    Corral-Diaz, Baltazar; Peralta-Videa, Jose R; Alvarez-Parrilla, Emilio; Rodrigo-García, Joaquin; Morales, Maria Isabel; Osuna-Avila, Pedro; Niu, Genhua; Hernandez-Viezcas, Jose A; Gardea-Torresdey, Jorge L

    2014-11-01

    The effects of nCeO2 on food quality are not well known yet. This research was performed to determine the impact of nCeO2 on radish (Raphanus sativus L.). Plants were cultivated to full maturity in potting soil treated with nCeO2 at concentrations of 0, 62.5, 125, 250, and 500 mg/kg. Germination, growth, photosynthesis, ionome, and antioxidants were evaluated at different growth stages. Results showed that at 500 mg/kg, nCeO2 significantly retarded seed germination but did not reduce the number of germinated seeds. None of the treatments affected gas exchange, photosynthesis, growth, phenols, flavonoids, and nutrients' accumulation in tubers and leaves of adult plants. However, tubers' antioxidant capacity, expressed as FRAP, ABTS(•-) and DPPH, increased by 30%, 32%, and 85%, respectively, in plants treated with 250 mg nCeO2kg(-1) soil. In addition, cerium accumulation in tubers of plants treated with 250 and 500 mg/kg reached 72 and 142 mg/kg d wt, respectively. This suggests that nCeO2 could improve the radical scavenging potency of radish but it might introduce nCeO2 into the food chain with unknown consequences.

  11. Methane Activation Mediated by a Series of Cerium-Vanadium Bimetallic Oxide Cluster Cations: Tuning Reactivity by Doping.

    PubMed

    Ma, Jia-Bi; Meng, Jing-Heng; He, Sheng-Gui

    2016-04-18

    The reactions of cerium-vanadium cluster cations Cex Vy Oz (+) with CH4 are investigated by time-of-flight mass spectrometry and density functional theory calculations. (CeO2 )m (V2 O5 )n (+) clusters (m=1,2, n=1-5; m=3, n=1-4) with dimensions up to nanosize can abstract one hydrogen atom from CH4 . The theoretical study indicates that there are two types of active species in (CeO2 )m (V2 O5 )n (+) , V[(Ot )2 ](.) and [(Ob )2 CeOt ](.) (Ot and Ob represent terminal and bridging oxygen atoms, respectively); the former is less reactive than the latter. The experimentally observed size-dependent reactivities can be rationalized by considering the different active species and mechanisms. Interestingly, the reactivity of the (CeO2 )m (V2 O5 )n (+) clusters falls between those of (CeO2 )2-4 (+) and (V2 O5 )1-5 (+) in terms of C-H bond activation, thus the nature of the active species and the cluster reactivity can be effectively tuned by doping. PMID:26714587

  12. Evaluation of the role of oxidative stress, inflammation and apoptosis in the pulmonary and the hepatic toxicity induced by cerium oxide nanoparticles following intratracheal instillation in male Sprague-Dawley rats

    NASA Astrophysics Data System (ADS)

    Nalabotu, Siva Krishna

    The field of nanotechnology is rapidly progressing with potential applications in the automobile, healthcare, electronics, cosmetics, textiles, information technology, and environmental sectors. Nanomaterials are engineered structures with at least one dimension of 100 nanometers or less. With increased applications of nanotechnology, there are increased chances of exposure to manufactured nanomaterials. Recent reports on the toxicity of engineered nanomaterials have given scientific and regulatory agencies concerns over the safety of nanomaterials. Specifically, the Organization for Economic Co-operation and Development (OECD) has identified fourteen high priority nanomaterials for study. Cerium oxide (CeO2) nanoparticles are one among the high priority group. Recent data suggest that CeO2 nanoparticles may be toxic to lung cell lines in vitro and lung tissues in vivo. Other work has proposed that oxidative stress may play an important role in the toxicity; however, the exact mechanism of the toxicity, has to our knowledge, not been investigated. Similarly, it is not clear whether CeO2 nanoparticles exhibit systemic toxicity. Here, we investigate whether pulmonary exposure to CeO2 nanoparticles is associated with oxidative stress, inflammation and apoptosis in the lungs and liver of adult male Sprague-Dawley rats. Our data suggest that the intratracheal instillation of CeO2 nanoparticles can cause an increased lung weight to body weight ratio. Changes in lung weights were associated with the accumulation of cerium in the lungs, elevations in serum inflammatory markers, an increased Bax to Bcl-2 ratio, elevated caspase-3 protein levels, increased phosphorylation of p38-MAPK and diminished phosphorylation of ERK1/2-MAPK. Our findings from the study evaluating the possible translocation of CeO2 nanoparticles from the lungs to the liver suggest that CeO 2 nanoparticle exposure was associated with increased liver ceria levels, elevations in serum alanine transaminase

  13. [application of the analytical transmission electron microscopy techniques for detection, identification and visualization of localization of nanoparticles of titanium and cerium oxides in mammalian cells].

    PubMed

    Shebanova, A S; Bogdanov, A G; Ismagulova, T T; Feofanov, A V; Semenyuk, P I; Muronets, V I; Erokhina, M V; Onishchenko, G E; Kirpichnikov, M P; Shaitan, K V

    2014-01-01

    This work represents the results of the study on applicability of the modern methods of analytical transmission electron microscopy for detection, identification and visualization of localization of nanoparticles of titanium and cerium oxides in A549 cell, human lung adenocarcinoma cell line. A comparative analysis of images of the nanoparticles in the cells obtained in the bright field mode of transmission electron microscopy, under dark-field scanning transmission electron microscopy and high-angle annular dark field scanning transmission electron was performed. For identification of nanoparticles in the cells the analytical techniques, energy-dispersive X-ray spectroscopy and electron energy loss spectroscopy, were compared when used in the mode of obtaining energy spectrum from different particles and element mapping. It was shown that the method for electron tomography is applicable to confirm that nanoparticles are localized in the sample but not coated by contamination. The possibilities and fields of utilizing different techniques for analytical transmission electron microscopy for detection, visualization and identification of nanoparticles in the biological samples are discussed.

  14. Effects of pH and fulvic acids concentration on the stability of fulvic acids--cerium (IV) oxide nanoparticle complexes.

    PubMed

    Oriekhova, Olena; Stoll, Serge

    2016-02-01

    The behavior of cerium (IV) oxide nanoparticles has been first investigated at different pH conditions. The point of zero charge was determined as well as the stability domains using dynamic light scattering, nanoparticle tracking analysis and scanning electron microscopy. A baseline hydrodynamic diameter of 180 nm was obtained indicating that individual CeO2 nanoparticles are forming small aggregates. Then we analyzed the particle behavior at variable concentrations of fulvic acids for three different pH-electrostatic scenarios corresponding to positive, neutral and negative CeO2 surface charges. The presence of fulvic acids was found to play a key role on the CeO2 stability via the formation of electrostatic complexes. It was shown that a small amount of fulvic acids (2 mg L(-1)), representative of environmental fresh water concentrations, is sufficient to stabilize CeO2 nanoparticles (50 mg L(-1)). When electrostatic complexes are formed between negatively charged FAs and positively charged CeO2 NPs the stability of such complexes is obtained with time (up to 7 weeks) as well as in pH changing conditions. Based on zeta potential variations we also found that the fulvic acids are changing the CeO2 acid-base surface properties. Obtained results presented here constitute an important outcome in the domain of risk assessment, transformation and removal of engineered nanomaterials released into the environment. PMID:26347935

  15. Mixed cerium-platinum oxides: Electronic structure of [CeO]Ptn (n = 1, 2) and [CeO2]Pt complex anions and neutrals.

    PubMed

    Ray, Manisha; Kafader, Jared O; Topolski, Josey E; Jarrold, Caroline Chick

    2016-07-28

    The electronic structures of several small Ce-Pt oxide complexes were explored using a combination of anion photoelectron (PE) spectroscopy and density functional theory calculations. Pt and Pt2 both accept electron density from CeO diatomic molecules, in which the cerium atom is in a lower-than-bulk oxidation state (+2 versus bulk +4). Neutral [CeO]Pt and [CeO]Pt2 complexes are therefore ionic, with electronic structures described qualitatively as [CeO(+2)]Pt(-2) and [CeO(+)]Pt2 (-), respectively. The associated anions are described qualitatively as [CeO(+)]Pt(-2) and [CeO(+)]Pt2 (-2), respectively. In both neutrals and anions, the most stable molecular structures determined by calculations feature a distinct CeO moiety, with the positively charged Ce center pointing toward the electron rich Pt or Pt2 moiety. Spectral simulations based on calculated spectroscopic parameters are in fair agreement with the spectra, validating the computationally determined structures. In contrast, when Pt is coupled with CeO2, which has no Ce-localized electrons that can readily be donated to Pt, the anion is described as [CeO2]Pt(-). The molecular structure predicted computationally suggests that it is governed by charge-dipole interactions. The neutral [CeO2]Pt complex lacks charge-dipole stabilizing interactions, and is predicted to be structurally very different from the anion, featuring a single Pt-O-Ce bridge bond. The PE spectra of several of the complexes exhibit evidence of photodissociation with Pt(-) daughter ion formation. The electronic structures of these complexes are related to local interactions in Pt-ceria catalyst-support systems.

  16. Mixed cerium-platinum oxides: Electronic structure of [CeO]Ptn (n = 1, 2) and [CeO2]Pt complex anions and neutrals

    NASA Astrophysics Data System (ADS)

    Ray, Manisha; Kafader, Jared O.; Topolski, Josey E.; Jarrold, Caroline Chick

    2016-07-01

    The electronic structures of several small Ce-Pt oxide complexes were explored using a combination of anion photoelectron (PE) spectroscopy and density functional theory calculations. Pt and Pt2 both accept electron density from CeO diatomic molecules, in which the cerium atom is in a lower-than-bulk oxidation state (+2 versus bulk +4). Neutral [CeO]Pt and [CeO]Pt2 complexes are therefore ionic, with electronic structures described qualitatively as [CeO+2]Pt-2 and [CeO+]Pt2-, respectively. The associated anions are described qualitatively as [CeO+]Pt-2 and [CeO+]Pt2-2, respectively. In both neutrals and anions, the most stable molecular structures determined by calculations feature a distinct CeO moiety, with the positively charged Ce center pointing toward the electron rich Pt or Pt2 moiety. Spectral simulations based on calculated spectroscopic parameters are in fair agreement with the spectra, validating the computationally determined structures. In contrast, when Pt is coupled with CeO2, which has no Ce-localized electrons that can readily be donated to Pt, the anion is described as [CeO2]Pt-. The molecular structure predicted computationally suggests that it is governed by charge-dipole interactions. The neutral [CeO2]Pt complex lacks charge-dipole stabilizing interactions, and is predicted to be structurally very different from the anion, featuring a single Pt-O-Ce bridge bond. The PE spectra of several of the complexes exhibit evidence of photodissociation with Pt- daughter ion formation. The electronic structures of these complexes are related to local interactions in Pt-ceria catalyst-support systems.

  17. Virus removal by biogenic cerium.

    PubMed

    De Gusseme, Bart; Du Laing, Gijs; Hennebel, Tom; Renard, Piet; Chidambaram, Dev; Fitts, Jeffrey P; Bruneel, Els; Van Driessche, Isabel; Verbeken, Kim; Boon, Nico; Verstraete, Willy

    2010-08-15

    The rare earth element cerium has been known to exert antifungal and antibacterial properties in the oxidation states +III and +IV. This study reports on an innovative strategy for virus removal in drinking water by the combination of Ce(III) on a bacterial carrier matrix. The biogenic cerium (bio-Ce) was produced by addition of aqueous Ce(III) to actively growing cultures of either freshwater manganese-oxidizing bacteria (MOB) Leptothrix discophora or Pseudomonas putida MnB29. X-ray absorption spectroscopy results indicated that Ce remained in its trivalent state on the bacterial surface. The spectra were consistent with Ce(III) ions associated with the phosphoryl groups of the bacterial cell wall. In disinfection assays using a bacteriophage as model, it was demonstrated that bio-Ce exhibited antiviral properties. A 4.4 log decrease of the phage was observed after 2 h of contact with 50 mg L(-1) bio-Ce. Given the fact that virus removal with 50 mg L(-1) Ce(III) as CeNO(3) was lower, the presence of the bacterial carrier matrix in bio-Ce significantly enhanced virus removal. PMID:20704235

  18. Virus Removal by Biogenic Cerium

    SciTech Connect

    De Gusseme, B.; Du Laing, G; Hennebel, T; Renard, P; Chidambaram, D; Fitts, J; Bruneel, E; Van Driessche, I; Verbeken, K; et. al.

    2010-01-01

    The rare earth element cerium has been known to exert antifungal and antibacterial properties in the oxidation states +III and +IV. This study reports on an innovative strategy for virus removal in drinking water by the combination of Ce(III) on a bacterial carrier matrix. The biogenic cerium (bio-Ce) was produced by addition of aqueous Ce(III) to actively growing cultures of either freshwater manganese-oxidizing bacteria (MOB) Leptothrix discophora or Pseudomonas putida MnB29. X-ray absorption spectroscopy results indicated that Ce remained in its trivalent state on the bacterial surface. The spectra were consistent with Ce(III) ions associated with the phosphoryl groups of the bacterial cell wall. In disinfection assays using a bacteriophage as model, it was demonstrated that bio-Ce exhibited antiviral properties. A 4.4 log decrease of the phage was observed after 2 h of contact with 50 mg L{sup -1} bio-Ce. Given the fact that virus removal with 50 mg L{sup -1} Ce(III) as CeNO{sub 3} was lower, the presence of the bacterial carrier matrix in bio-Ce significantly enhanced virus removal.

  19. Antimony promoted bismuth cerium molybdate catalysts

    SciTech Connect

    Brazdil, J.F.; Glaeser, L.C.; Grasselli, R.K.

    1990-05-01

    This patent describes an improvement in antimony-promoted bismuth cerium molybdate whereby the tendency of the catalyst to lose efectiveness over time is significantly reduced. This patent describes new catalysts which are also useful in other oxidation-type reactions such as the oxidation of acrolein and methacrolein to produce the corresponding unsaturated aldehydes and acids and the oxydehydrogenation of various olefins such as isoamylenes to produce the corresponding diolefins such as isoprene.

  20. Humic Substances-dependent Aggregation and Transport of Cerium Oxide Nanoparticles in Porous Media at Different pHs and Ionic Strengths

    NASA Astrophysics Data System (ADS)

    Mu, L.; Jacobson, A. R.; Darnault, C. J. G.

    2015-12-01

    Cerium oxide nanoparticles (CeO2 NPs) are commonly used in several fields and industries, such as chemical and pharmaceutical, due to both their physical and chemical properties. For example, they are employed in the manufacturing of catalysts, as fuel additives, and as polishing agents. The release and exposure to CeO2 NPs can occur during their fabrication, application, and waste disposal, as well as through their life-cycle and accidents. Therefore, the assessment of the dynamic nature of CeO2 NPs stability and mobilty in the environment is of paramount importance to establish the environmental and public health risks associated with their inevitable release in the environment. Humic substances are a key element of soils and have been revealed to possibly affect the fate and transport of nanoparticles in soils. Consequently, our present research aims at investigating the influence that different pHs, monovalent and divalent cations, Suwannee River humic acid, and Suwanee River fulvic acid have on the aggregation, transport, and deposition of CeO2 NPs. Batch studies performed with different concentrations of humic and fulvic acids associated with a wide spectrum of pHs and ionic strengths were examined. Key variables from these batch studies were then examined to simulate experimental conditions commonly encountered in the soil-water system to conduct column transport experiments in order to establish the fate and transport of CeO2 NPs in saturated porous media, which is a critical phase in characterizing the behavior of CeO2 NPs in subsurface environmental systems.

  1. Partial oxidation of 4-tert-butyltoluene catalyzed by homogeneous cobalt and cerium acetate catalysts in the Br-/H2O2/acetic acid system: insights into selectivity and mechanism.

    PubMed

    van de Water, Leon G A; Kaza, Arati; Beattie, James K; Masters, Anthony F; Maschmeyer, Thomas

    2007-01-01

    The partial oxidation of 4-tert-butyltoluene to 4-tert-butylbenzaldehyde by hydrogen peroxide in glacial acetic acid, catalyzed by bromide ions in combination with cobalt(II) acetate or cerium(III) acetate, has been studied in detail. Based on the observed differences in reaction rates and product distributions for the different catalysts, a reaction mechanism involving two independent pathways is proposed. After the initial formation of a benzylic radical species, either oxidation of this intermediate by the metal catalyst or reaction with bromine generated in situ occurs, depending on which catalyst is used. The first pathway leads to the exclusive formation of 4-tert-butylbenzaldehyde, whereas reaction of the radical intermediate with bromine leads to formation of the observed side products 4-tert-butylbenzyl bromide and its hydrolysis and solvolysis products 4-tert-butylbenzyl alcohol and 4-tert-butylbenzyl acetate, respectively. The cobalt(II) catalysts Co(OAc)(2) and Co(acac)(2) are able to quickly oxidize the radical intermediate, thereby largely preventing the bromination reaction (i.e., side-product formation) from occurring, and yield the aldehyde product with 75-80 % selectivity. In contrast, the cerium catalyst studied here exhibits an aldehyde selectivity of around 50 % due to the competing bromination reaction. Addition of extra hydrogen peroxide leads to an increased product yield of 72 % (cerium(III) acetate) or 58 % (cobalt(II) acetate). Product inhibition and the presence of increasing amounts of water in the reaction mixture do not play a role in the observed low incremental yields.

  2. Novel cerium-tungsten mixed oxide catalyst for the selective catalytic reduction of NO(x) with NH3.

    PubMed

    Shan, Wenpo; Liu, Fudong; He, Hong; Shi, Xiaoyan; Zhang, Changbin

    2011-07-28

    A novel Ce-W mixed oxide catalyst prepared by homogeneous precipitation method presented nearly 100% NO(x) conversion in a wide temperature range from 250 to 425 °C for the selective catalytic reduction of NO(x) with NH(3) under an extremely high GHSV of 500,000 h(-1).

  3. Influence of a Cerium Surface Treatment on the Oxidation Behavior of Cr2O3-Forming Alloys (title on slides varies: Oxidation Behavior of Cerium Surface Treated Chromia Forming Alloys)

    SciTech Connect

    Alman, D.E.; Holcomb, G.R.; Adler, T.A.; Jablonski, P.D.

    2007-04-01

    Current goals of the U.S. Department of Energy’s Advanced Power Systems Initiatives include coal generation at 60% efficiency, which would require steam temperatures of up to 760°C. This temperature will require the construction of boiler and turbine components from austenitic stainless steels and nickel alloys. Many of the alloys being considered for use are primarily Cr2O3 forming alloys [1-4]. It is well known that the addition of a small amount of reactive elements, such as the rare earths elements Ce, La, and Y, can significantly improve the high temperature oxidation resistance of both iron- and nickel- base alloys. A list of the benefits of the reactive element effect include: (i) slowing scale growth, (ii) enhancing scale adhesion; and (iii) stabilizing Cr2O3 formation at lower Cr levels. The incorporation of the reactive element can be made in the melt or through a surface infusion or surface coating. Surface modifications allow for the concentration of the reactive element at the surface where it can provide the most benefit. This paper will detail a Ce surface treatment developed at NETL that improves the high temperature oxidation resistance of Cr2O3 forming alloys. The treatment consists of painting, dip coating, or spraying the alloy surface with a slurry containing CeO2 and a halide activator followed by a thermal treatment in a mild (x10-3 Torr) vacuum. During treatment the CeO2 reacts with the alloy to for a thin CrCeO3-type scale on the alloy surface. Upon subsequent oxidation, scale growth occurs at a reduced rate on alloys in the surface treated condition compared to those in the untreated condition.

  4. Pharmacological potential of cerium oxidenanoparticles

    NASA Astrophysics Data System (ADS)

    Celardo, Ivana; Pedersen, Jens Z.; Traversa, Enrico; Ghibelli, Lina

    2011-04-01

    Nanotechnology promises a revolution in pharmacology to improve or create ex novo therapies. Cerium oxidenanoparticles (nanoceria), well-known as catalysts, possess an astonishing pharmacological potential due to their antioxidant properties, deriving from a fraction of Ce3+ ions present in CeO2. These defects, compensated by oxygen vacancies, are enriched at the surface and therefore in nanosized particles. Reactions involving redox cycles between the Ce3+ and Ce4+oxidation states allow nanoceria to react catalytically with superoxide and hydrogen peroxide, mimicking the behavior of two key antioxidant enzymes, superoxide dismutase and catalase, potentially abating all noxious intracellularreactive oxygen species (ROS) via a self-regenerating mechanism. Hence nanoceria, apparently well tolerated by the organism, might fight chronic inflammation and the pathologies associated with oxidative stress, which include cancer and neurodegeneration. Here we review the biological effects of nanoceria as they emerge from in vitro and in vivo studies, considering biocompatibility and the peculiar antioxidant mechanisms.

  5. A cerium oxide nanoparticle-based device for the detection of chronic inflammation via optical and magnetic resonance imaging

    NASA Astrophysics Data System (ADS)

    Kaittanis, Charalambos; Santra, Santimukul; Asati, Atul; Perez, J. Manuel

    2012-03-01

    Monitoring of microenvironmental parameters is critical in healthcare and disease management. Harnessing the antioxidant activity of nanoceria and the imaging capabilities of iron oxide nanoparticles in a device setup, we were able to image changes in the device's aqueous milieu. The device was able to convey and process changes in the microenvironment's pH and reactive oxygen species' concentration, distinguishing physiological from abnormal levels. As a result under physiological and transient inflammatory conditions, the device's fluorescence and magnetic resonance signals, emanating from multimodal iron oxide nanoparticles, were similar. However, under chronic inflammatory conditions that are usually associated with high local concentrations of reactive oxygen species and pH decrease, the device's output was considerably different. Specifically, the device's fluorescence emission significantly decreased, while the magnetic resonance signal T2 increased. Further studies identified that the changes in the device's output are attributed to inactivation of the sensing component's nanoceria that prevents it from successfully scavenging the generated free radicals. Interestingly, the buildup of free radical excess led to polymerization of the iron oxide nanoparticle's coating, with concomitant formation of micron size aggregates. Our studies indicate that a nanoceria-based device can be utilized for the monitoring of pro-inflammatory biomarkers, having important applications in the management of numerous ailments while eliminating nanoparticle toxicity issues.Monitoring of microenvironmental parameters is critical in healthcare and disease management. Harnessing the antioxidant activity of nanoceria and the imaging capabilities of iron oxide nanoparticles in a device setup, we were able to image changes in the device's aqueous milieu. The device was able to convey and process changes in the microenvironment's pH and reactive oxygen species' concentration

  6. Strain Field in Ultrasmall Gold Nanoparticles Supported on Cerium-Based Mixed Oxides. Key Influence of the Support Redox State.

    PubMed

    López-Haro, Miguel; Yoshida, Kenta; Del Río, Eloy; Pérez-Omil, José A; Boyes, Edward D; Trasobares, Susana; Zuo, Jian-Min; Gai, Pratibha L; Calvino, José J

    2016-05-01

    Using a method that combines experimental and simulated Aberration-Corrected High Resolution Electron Microscopy images with digital image processing and structure modeling, strain distribution maps within gold nanoparticles relevant to real powder type catalysts, i.e., smaller than 3 nm, and supported on a ceria-based mixed oxide have been determined. The influence of the reduction state of the support and particle size has been examined. In this respect, it has been proven that reduction even at low temperatures induces a much larger compressive strain on the first {111} planes at the interface. This increase in compression fully explains, in accordance with previous DFT calculations, the loss of CO adsorption capacity of the interface area previously reported for Au supported on ceria-based oxides.

  7. Tuning Reactivity and Electronic Properties through Ligand Reorganization within a Cerium Heterobimetallic Framework

    SciTech Connect

    Robinson, Jerome R.; Gordon, Zachary; Booth, Corwin H.; Carroll, Patrick J.; Walsh, Patrick J.; Schelter, Eric J.

    2014-06-24

    Cerium compounds have played vital roles in organic, inorganic, and materials chemistry due to their reversible redox chemistry between trivalent and tetravalent oxidation states. However, attempts to rationally access molecular cerium complexes in both oxidation states have been frustrated by unpredictable reactivity in cerium(III) oxidation chemistry. Such oxidation reactions are limited by steric saturation at the metal ion, which can result in high energy activation barriers for electron transfer. An alternative approach has been realized using a rare earth/alkali metal/1,1'-BINOLate (REMB) heterobimetallic framework, which uses redox-inactive metals within the secondary coordination sphere to control ligand reorganization. The rational syntheses of functionalized cerium(IV) products and a mechanistic examination of the role of ligand reorganization in cerium(III) oxidation are presented.

  8. Redox Reactivity of Cerium Oxide Nanoparticles Induces the Formation of Disulfide Bridges in Thiol-Containing Biomolecules.

    PubMed

    Rollin-Genetet, Françoise; Seidel, Caroline; Artells, Ester; Auffan, Mélanie; Thiéry, Alain; Vidaud, Claude

    2015-12-21

    The redox state of disulfide bonds is implicated in many redox control systems, such as the cysteine-cystine couple. Among proteins, ubiquitous cysteine-rich metallothioneins possess thiolate metal binding groups susceptible to metal exchange in detoxification processes. CeO2 NPs are commonly used in various industrial applications due to their redox properties. These redox properties that enable dual oxidation states (Ce(IV)/Ce(III)) to exist at their surface may act as oxidants for biomolecules. The interaction among metallothioneins, cysteine, and CeO2 NPs was investigated through various biophysical approaches to shed light on the potential effects of the Ce(4+)/Ce(3+) redox system on the thiol groups of these biomolecules. The possible reaction mechanisms include the formation of a disulfide bridge/Ce(III) complex resulting from the interaction between Ce(IV) and the thiol groups, leading to metal unloading from the MTs, depending on their metal content and cluster type. The formation of stable Ce(3+) disulfide complexes has been demonstrated via their fluorescence properties. This work provides the first evidence of thiol concentration-dependent catalytic oxidation mechanisms between pristine CeO2 NPs and thiol-containing biomolecules. PMID:26566067

  9. Cerium oxide nanoparticles, combining antioxidant and UV shielding properties, prevent UV-induced cell damage and mutagenesis

    NASA Astrophysics Data System (ADS)

    Caputo, Fanny; de Nicola, Milena; Sienkiewicz, Andrzej; Giovanetti, Anna; Bejarano, Ignacio; Licoccia, Silvia; Traversa, Enrico; Ghibelli, Lina

    2015-09-01

    Efficient inorganic UV shields, mostly based on refracting TiO2 particles, have dramatically changed the sun exposure habits. Unfortunately, health concerns have emerged from the pro-oxidant photocatalytic effect of UV-irradiated TiO2, which mediates toxic effects on cells. Therefore, improvements in cosmetic solar shield technology are a strong priority. CeO2 nanoparticles are not only UV refractors but also potent biological antioxidants due to the surface 3+/4+ valency switch, which confers anti-inflammatory, anti-ageing and therapeutic properties. Herein, UV irradiation protocols were set up, allowing selective study of the extra-shielding effects of CeO2vs. TiO2 nanoparticles on reporter cells. TiO2 irradiated with UV (especially UVA) exerted strong photocatalytic effects, superimposing their pro-oxidant, cell-damaging and mutagenic action when induced by UV, thereby worsening the UV toxicity. On the contrary, irradiated CeO2 nanoparticles, via their Ce3+/Ce4+ redox couple, exerted impressive protection on UV-treated cells, by buffering oxidation, preserving viability and proliferation, reducing DNA damage and accelerating repair; strikingly, they almost eliminated mutagenesis, thus acting as an important tool to prevent skin cancer. Interestingly, CeO2 nanoparticles also protect cells from the damage induced by irradiated TiO2, suggesting that these two particles may also complement their effects in solar lotions. CeO2 nanoparticles, which intrinsically couple UV shielding with biological and genetic protection, appear to be ideal candidates for next-generation sun shields.

  10. Comparison of the high-pressure behavior of the cerium oxides Ce2O3 and CeO2

    DOE PAGESBeta

    Lipp, M. J.; Jeffries, J. R.; Cynn, H.; Park Klepeis, J. -H.; Evans, W. J.; Mortensen, D. R.; Seidler, G. T.; Xiao, Y.; Chow, P.

    2016-02-09

    We studied the high-pressure behavior of Ce2O3 using angle-dispersive x-ray diffraction to 70 GPa and compared with that of CeO2. Up to the highest pressure Ce2O3 remains in the hexagonal phase (space group 164, P ¯32/m1) typical for the lanthanide sesquioxides. We did not observe a theoretically predicted phase instability for 30 GPa. The isothermal bulk modulus and its pressure derivative for the quasihydrostatic case are B0 = 111 ± 2 GPa, B'0 = 4.7 ± 0.3, and for the case without pressure-transmitting medium B0 = 104 ±4 GPa, B'0 = 6.5 ± 0.4. Starting from ambient-pressure magnetic susceptibility measurementsmore » for both oxides in highly purified form,we find that the Ce atom in Ce2O3 behaves like a trivalent Ce3+ ion (2.57μB per Ce atom) in contrast to previously published data. Since x-ray emission spectroscopy of the Lγ (4d3/2 → 2p1/2) transition is sensitive to the 4f -electron occupancy, we also followed the high-pressure dependence of this line for both oxides up to 50 GPa. We observed no change of the respective line shape, indicating that the 4f -electron configuration is stable for both materials. We posit from this data that the 4f electrons do not drive the volume collapse of CeO2 from the high-symmetry, low-pressure fluorite structure to the lower-symmetry orthorhombic phase.« less

  11. Multi-wall carbon nanotubes as support of copper-cerium composite for preferential oxidation of carbon monoxide

    NASA Astrophysics Data System (ADS)

    Zeng, Shanghong; Zhang, Lu; Jiang, Nan; Gao, Meiyi; Zhao, Xiaozhou; Yin, Yueling; Su, Haiquan

    2015-10-01

    The CuxO/MWCNTs, CeO2/MWCNTs and CuxO-CeO2/MWCNTs catalysts were synthesized by a simple impregnation method, and characterized via X-ray diffraction, N2 adsorption-desorption, Fourier transformed infrared spectroscopy, transmission electron microscopy, H2 temperature-programmed reduction and X-ray photoelectron spectra. The catalytic performance for preferential CO oxidation was carried out in the hydrogen-rich gasses. It is found that the hydrophilic functional groups of hydroxyl and carboxyl in the samples are favorable for the incorporation of CuxO and CeO2 into the tubes of the MWCNTs. Most of CuxO particles and CeO2 nanowires are filled in the tubes of MWCNTs, and a small amount of nanoparticles are deposited on the surface of MWCNTs. The MWCNTs have high BET surface area, which is helpful for the dispersion of CuxO and CeO2 to expose more active surface for CO-PROX reaction over the CuxO-CeO2/MWCNTs catalysts. The CuxO-CeO2/MWCNTs-C catalyst shows good catalytic activity and the temperature window of CO total conversion is from 135 °C to 175 °C. MWCNTs with high BET surface area weaken poisoning effect of H2O and CO2 after 135 °C.

  12. Direct Quantification of Rare Earth Elements Concentrations in Urine of Workers Manufacturing Cerium, Lanthanum Oxide Ultrafine and Nanoparticles by a Developed and Validated ICP-MS.

    PubMed

    Li, Yan; Yu, Hua; Zheng, Siqian; Miao, Yang; Yin, Shi; Li, Peng; Bian, Ying

    2016-03-22

    Rare earth elements (REEs) have undergone a steady spread in several industrial, agriculture and medical applications. With the aim of exploring a sensitive and reliable indicator of estimating exposure level to REEs, a simple, accurate and specific ICP-MS method for simultaneous direct quantification of 15 REEs ((89)Y, (139)La, (140)Ce, (141)Pr, (146)Nd, (147)Sm, (153)Eu, (157)Gd, (159)Tb, (163)Dy, (165)Ho, (166)Er, (169)Tm, (172)Yb and (175)Lu) in human urine has been developed and validated. The method showed good linearity for all REEs in human urine in the concentrations ranging from 0.001-1.000 μg ∙ L(-1) with r² > 0.997. The limits of detection and quantification for this method were in the range of 0.009-0.010 μg ∙ L(-1) and 0.029-0.037 μg ∙ L(-1), the recoveries on spiked samples of the 15 REEs ranged from 93.3% to 103.0% and the relative percentage differences were less than 6.2% in duplicate samples, and the intra- and inter-day variations of the analysis were less than 1.28% and less than 0.85% for all REEs, respectively. The developed method was successfully applied to the determination of 15 REEs in 31 urine samples obtained from the control subjects and the workers engaged in work with manufacturing of ultrafine and nanoparticles containing cerium and lanthanum oxide. The results suggested that only the urinary levels of La (1.234 ± 0.626 μg ∙ L(-1)), Ce (1.492 ± 0.995 μg ∙ L(-1)), Nd (0.014 ± 0.009 μg ∙ L(-1)) and Gd (0.023 ± 0.010 μg ∙ L(-1)) among the exposed workers were significantly higher (p < 0.05) than the levels measured in the control subjects. From these, La and Ce were the primary components, and accounted for 88% of the total REEs. Lanthanum comprised 27% of the total REEs while Ce made up the majority of REE content at 61%. The remaining elements only made up 1% each, with the exception of Dy which was not detected. Comparison with the previously published data, the levels of urinary La and Ce in workers and

  13. Direct Quantification of Rare Earth Elements Concentrations in Urine of Workers Manufacturing Cerium, Lanthanum Oxide Ultrafine and Nanoparticles by a Developed and Validated ICP-MS

    PubMed Central

    Li, Yan; Yu, Hua; Zheng, Siqian; Miao, Yang; Yin, Shi; Li, Peng; Bian, Ying

    2016-01-01

    Rare earth elements (REEs) have undergone a steady spread in several industrial, agriculture and medical applications. With the aim of exploring a sensitive and reliable indicator of estimating exposure level to REEs, a simple, accurate and specific ICP-MS method for simultaneous direct quantification of 15 REEs (89Y, 139La, 140Ce, 141Pr, 146Nd, 147Sm, 153Eu, 157Gd, 159Tb, 163Dy, 165Ho, 166Er, 169Tm, 172Yb and 175Lu) in human urine has been developed and validated. The method showed good linearity for all REEs in human urine in the concentrations ranging from 0.001–1.000 μg∙L−1 with r2 > 0.997. The limits of detection and quantification for this method were in the range of 0.009–0.010 μg∙L−1 and 0.029–0.037 μg∙L−1, the recoveries on spiked samples of the 15 REEs ranged from 93.3% to 103.0% and the relative percentage differences were less than 6.2% in duplicate samples, and the intra- and inter-day variations of the analysis were less than 1.28% and less than 0.85% for all REEs, respectively. The developed method was successfully applied to the determination of 15 REEs in 31 urine samples obtained from the control subjects and the workers engaged in work with manufacturing of ultrafine and nanoparticles containing cerium and lanthanum oxide. The results suggested that only the urinary levels of La (1.234 ± 0.626 μg∙L−1), Ce (1.492 ± 0.995 μg∙L−1), Nd (0.014 ± 0.009 μg∙L−1) and Gd (0.023 ± 0.010 μg∙L−1) among the exposed workers were significantly higher (p < 0.05) than the levels measured in the control subjects. From these, La and Ce were the primary components, and accounted for 88% of the total REEs. Lanthanum comprised 27% of the total REEs while Ce made up the majority of REE content at 61%. The remaining elements only made up 1% each, with the exception of Dy which was not detected. Comparison with the previously published data, the levels of urinary La and Ce in workers and the control subjects show a higher trend

  14. Assigning the Cerium Oxidation State for CH2CeF2 and OCeF2 Based on Multireference Wave Function Analysis.

    PubMed

    Mooßen, Oliver; Dolg, Michael

    2016-06-01

    The geometric and electronic structure of the recently experimentally studied molecules ZCeF2 (Z = CH2, O) was investigated by density functional theory (DFT) and wave function-based ab initio methods. Special attention was paid to the Ce-Z metal-ligand bonding, especially to the nature of the interaction between the Ce 4f and the Z 2p orbitals and the possible multiconfigurational character arising from it, as well as to the assignment of an oxidation state of Ce reflecting the electronic structure. Complete active space self-consistent field (CASSCF) calculations were performed, followed by orbital rotations in the active orbital space. The methylene compound CH2CeF2 has an open-shell singlet ground state, which is characterized by a two-configurational wave function in the basis of the strongly mixed natural CASSCF orbitals. The system can also be described in a very compact way by the dominant Ce 4f(1) C 2p(1) configuration, if nearly pure Ce 4f and C 2p orbitals are used. In the basis of these localized orbitals, the molecule is almost monoconfigurational and should be best described as a Ce(III) system. The singlet ground state of the oxygen OCeF2 complex is of closed-shell character when a monoconfigurational wave function with very strongly mixed Ce 4f and O 2p CASSCF natural orbitals is used for the description. The transformation to orbitals localized on the cerium and oxygen atoms leads to a multiconfigurational wave function and reveals characteristics of a mixed valent Ce(IV)/Ce(III) compound. Additionally, the interactions of the localized active orbitals were analyzed by evaluating the expectation values of the charge fluctuation operator and the local spin operator. The Ce 4f and C 2p orbital interaction of the CH2CeF2 compound is weakly covalent and resembles the interaction of the H 1s orbitals in a stretched hydrogen dimer. In contrast, the interaction of the localized active orbitals for OCeF2 shows ionic character. Calculated vibrational Ce

  15. Continuous-flow IRMS technique for determining the 17O excess of CO2 using complete oxygen isotope exchange with cerium oxide

    NASA Astrophysics Data System (ADS)

    Mrozek, D. J.; van der Veen, C.; Kliphuis, M.; Kaiser, J.; Wiegel, A. A.; Röckmann, T.

    2015-02-01

    This paper presents an analytical system for analysis of all single substituted isotopologues (12C16O17O, 12C16O18O, 13C16O16O) in nanomolar quantities of CO2 extracted from stratospheric air samples. CO2 is separated from bulk air by gas chromatography and CO2 isotope ratio measurements (ion masses 45 / 44 and 46 / 44) are performed using isotope ratio mass spectrometry (IRMS). The 17O excess (Δ17O) is derived from isotope measurements on two different CO2 aliquots: unmodified CO2 and CO2 after complete oxygen isotope exchange with cerium oxide (CeO2) at 700 °C. Thus, a single measurement of Δ17O requires two injections of 1 mL of air with a CO2 mole fraction of 390 μmol mol-1 at 293 K and 1 bar pressure (corresponding to 16 nmol CO2 each). The required sample size (including flushing) is 2.7 mL of air. A single analysis (one pair of injections) takes 15 minutes. The analytical system is fully automated for unattended measurements over several days. The standard deviation of the 17O excess analysis is 1.7‰. Multiple measurements on an air sample reduce the measurement uncertainty, as expected for the statistical standard error. Thus, the uncertainty for a group of 10 measurements is 0.58‰ for Δ 17O in 2.5 h of analysis. 100 repeat analyses of one air sample decrease the standard error to 0.20‰. The instrument performance was demonstrated by measuring CO2 on stratospheric air samples obtained during the EU project RECONCILE with the high-altitude aircraft Geophysica. The precision for RECONCILE data is 0.03‰ (1σ) for δ13C, 0.07‰ (1σ) for δ18O and 0.55‰ (1σ) for δ17O for a sample of 10 measurements. This is sufficient to examine stratospheric enrichments, which at altitude 33 km go up to 12‰ for δ17O and up to 8‰ for δ18O with respect to tropospheric CO2 : δ17O ~ 21‰ Vienna Standard Mean Ocean Water (VSMOW), δ18O ~ 41‰ VSMOW (Lämmerzahl et al., 2002). The samples measured with our analytical technique agree with available data for

  16. Hydrocarbon-based polymer electrolyte cerium composite membranes for improved proton exchange membrane fuel cell durability

    NASA Astrophysics Data System (ADS)

    Lee, Hyejin; Han, Myungseong; Choi, Young-Woo; Bae, Byungchan

    2015-11-01

    Hydrocarbon-based cerium composite membranes were prepared for proton exchange membrane fuel cell applications to increase oxidative stability. Different amounts of cerium ions were impregnated in sulfonated poly(arylene ether sulfone) (SPES) membranes and their physicochemical properties were investigated according to the cerium content. Field-emission scanning electron microscopy and inductively coupled plasma analyses confirmed the presence of cerium ions in the composite membranes and 1H NMR indicated the successful coordination of sulfonic acid groups with the metal ions. Increasing amounts of cerium ions resulted in decreases in the proton conductivity and water uptake, but enhanced oxidative stability. The oxidative stability of the composite membranes was proven via a hydrogen peroxide exposure experiment which mimicked fuel cell operating conditions. In addition, more than 2200 h was achieved with the composite membrane under in situ accelerated open circuit voltage (OCV) durability testing (DOE protocol), whereas the corresponding pristine SPES membrane attained only 670 h.

  17. Ultrathin, epitaxial cerium dioxide on silicon

    NASA Astrophysics Data System (ADS)

    Flege, Jan Ingo; Kaemena, Björn; Höcker, Jan; Bertram, Florian; Wollschläger, Joachim; Schmidt, Thomas; Falta, Jens

    2014-03-01

    It is shown that ultrathin, highly ordered, continuous films of cerium dioxide may be prepared on silicon following substrate prepassivation using an atomic layer of chlorine. The as-deposited, few-nanometer-thin Ce2O3 film may very effectively be converted at room temperature to almost fully oxidized CeO2 by simple exposure to air, as demonstrated by hard X-ray photoemission spectroscopy and X-ray diffraction. This post-oxidation process essentially results in a negligible loss in film crystallinity and interface abruptness.

  18. Ultrathin, epitaxial cerium dioxide on silicon

    SciTech Connect

    Flege, Jan Ingo Kaemena, Björn; Höcker, Jan; Schmidt, Thomas; Falta, Jens; Bertram, Florian; Wollschläger, Joachim

    2014-03-31

    It is shown that ultrathin, highly ordered, continuous films of cerium dioxide may be prepared on silicon following substrate prepassivation using an atomic layer of chlorine. The as-deposited, few-nanometer-thin Ce{sub 2}O{sub 3} film may very effectively be converted at room temperature to almost fully oxidized CeO{sub 2} by simple exposure to air, as demonstrated by hard X-ray photoemission spectroscopy and X-ray diffraction. This post-oxidation process essentially results in a negligible loss in film crystallinity and interface abruptness.

  19. Study of preparation method and oxidization/reduction effect on the performance of nickel-cerium oxide catalysts for aqueous-phase reforming of ethanol

    NASA Astrophysics Data System (ADS)

    Roy, B.; Leclerc, C. A.

    2015-12-01

    The effect of preparation method and oxidation state of the active metal on the catalytic activity of Ni-Ce-O catalysts was studied for aqueous phase reforming of ethanol. A sol-gel (SG) route and a solution combustion synthesis (SCS) method were used for the preparation of 10 wt% Ni loaded catalysts. The catalytic activity of three groups of catalysts; reduced at 425 °C (HR, metallic Ni), reduced at 1000 °C (FR, metallic Ni), and not reduced (NR, as NiO) were tested at different operating conditions. The difference in the metal particle sizes, governed by the preparation method, affects the catalytic efficiency most, not the reduced or oxidized state of Ni. The SG samples were superior for ethanol conversion and selectivity for H2 and CO2 compared to the SCS samples. The X-ray photoelectron spectroscopy (XPS) analysis of the samples demonstrated that the relative ratio of Ce2O3 to CeO2 increased inside the reactor. While Ni doping increases oxygen mobility in the Ce-O lattice, Ce3+ converts Ni2+ to metallic Ni inside the reactor. This can explain why the reduction stage for Ni-Ce-O system in APR is irrelevant. Higher oxygen mobility through the support helps oxidation of CO to CO2 leading to improved catalytic performance.

  20. Genesis of a Cerium Oxide-Supported Gold Catalyst for CO Oxidation: Transformation of Mononuclear Gold Complexes into Clusters as Characterized by X-Ray Absorption Spectroscopy

    SciTech Connect

    Aguilar-Guerrero, V.; Lobo-Lapidus, R; Gates, B

    2009-01-01

    CeO{sub 2}-supported mononuclear gold species synthesized from Au(CH{sub 3}){sub 2}(acac) catalyzed CO oxidation at 353 K, with a turnover frequency of 6.5 x 10{sup -3} molecules of CO (Au atom s){sup -1} at CO and O{sub 2} partial pressures of 1.0 and 0.5 kPa, respectively. As the catalyst functioned in a flow reactor, the activity increased markedly so that within about 10 h the conversion of CO had increased from about 1% to almost 100%. Activated catalyst samples were characterized by X-ray absorption spectroscopy and found to incorporate clusters of gold, which increased in size, undergoing reduction, with increasing time of operation. The X-ray absorption near-edge structure spectrum of the catalyst used for the longest period was indistinguishable from that characterizing gold foil. Extended X-ray absorption fine structure data characterizing the catalyst after the longest period of operation indicated the presence of clusters of approximately 30 Au atoms each, on average. The evidence that the catalytic activity increased as the clusters grew is contrasted with earlier reports pointing to increasing activity of supported gold clusters as they were made smallerin a cluster size range largely exceeding ours.

  1. Potential for recovery of cerium contained in automotive catalytic converters

    USGS Publications Warehouse

    Bleiwas, Donald I.

    2013-01-01

    Catalytic converters (CATCONs) are required by Federal law to be installed in nearly all gasoline- and diesel-fueled onroad vehicles used in the United States. About 85 percent of the light-duty vehicles and trucks manufactured worldwide are equipped with CATCONs. Portions of the CATCONs (called monoliths) are recycled for their platinum-group metal (PGM) content and for the value of the stainless steel they contain. The cerium contained in the monoliths, however, is disposed of along with the slag produced from the recycling process. Although there is some smelter capacity in the United States to treat the monoliths in order to recover the PGMs, a great percentage of monoliths is exported to Europe and South Africa for recycling, and a lesser amount is exported to Japan. There is presently no commercial-scale capacity in place domestically to recover cerium from the monoliths. Recycling of cerium or cerium compounds from the monoliths could help ensure against possible global supply shortages by increasing the amount that is available in the supply chain as well as the number and geographic distribution of the suppliers. It could also reduce the amount of material that goes into landfills. Also, the additional supply could lower the price of the commodity. This report analyzes how much cerium oxide is contained in CATCONs and how much could be recovered from used CATCONs.

  2. Thermodynamic Calculation among Cerium, Oxygen, and Sulfur in Liquid Iron

    PubMed Central

    Pan, Fei; Zhang, Jian; Chen, Hao-Long; Su, Yen-Hsun; Su, Yen-Hao; Hwang, Weng-Sing

    2016-01-01

    Thermodynamic calculation has been applied to predict the inclusion formation in molten SS400 steel. When the Cerium addition in liquid iron is 70 ppm and the initial Oxygen and Sulphur are both 110 ppm, the formation of oxides containing Cerium would experience the transformation from Ce2O3 to CeO2 and also the formation of sulfides containing Cerium would experience the transformation from CeS to Ce2S3 and then to Ce3S4. Below 2000 K the most thermodynamic stable matter is CeO2 and the less thermodynamic stable inclusion is CeS. Only when the amount of [O] is extremely low and the amount of [S] and [Ce] is relatively high, Ce2S3 has the possibility to form. PMID:27767092

  3. Cerium doped red mud catalytic ozonation for bezafibrate degradation in wastewater: Efficiency, intermediates, and toxicity.

    PubMed

    Xu, Bingbing; Qi, Fei; Sun, Dezhi; Chen, Zhonglin; Robert, Didier

    2016-03-01

    In this study, the performance of bezafibrate (BZF) degradation and detoxification in the aqueous phase using cerium-modified red mud (RM) catalysts prepared using different cerium sources and synthesis methods were evaluated. Experimental results showed that the surface cerium modification was responsible for the development of the catalytic activity of RM and this was influenced by the cerium source and the synthesis method. Catalyst prepared from cerium (IV) by precipitation was found to show the best catalytic activity in BZF degradation and detoxification. Reactive oxygen species including peroxides, hydroxyl radicals, and super oxide ions were identified in all reactions and we proposed the corresponding catalytic reaction mechanism for each catalyst that prepared from different cerium source and method. This was supported by the intermediates profiles that were generated upon BZF degradation. The surface and the structural properties of cerium-modified RM were characterized in detail by several analytical methods. Two interesting findings were made: (1) the surface texture (specific surface area and mesoporous volume) influenced the catalytic reaction pathway; and (2) Ce(III) species and oxygen vacancies were generated on the surface of the catalyst after cerium modification. This plays an important role in the development of the catalytic activity. PMID:26706928

  4. Microstructure of surface cerium hydride growth sites

    SciTech Connect

    Brierley, Martin; Knowles, John; Montgomery, Neil; Preuss, Michael

    2014-05-15

    Samples of cerium were exposed to hydrogen under controlled conditions causing cerium hydride sites to nucleate and grow on the surface. The hydriding rate was measured in situ, and the hydrides were characterised using secondary ion mass spectrometry, scanning electron microscopy, and optical microscopy. The results show that the hydriding rate proceeded more quickly than earlier studies. Characterisation confirmed that the hydrogen is confined to the sites. The morphology of the hydrides was confirmed to be oblate, and stressed material was observed surrounding the hydride, in a number of cases lathlike features were observed surrounding the hydride sites laterally with cracking in the surface oxide above them. It is proposed that during growth the increased lattice parameter of the CeH{sub 2} induces a lateral compressive stress around the hydride, which relieves by the ca. 16% volume collapse of the γ-Ce to α-Ce pressure induced phase transition. Cracking of the surface oxide above the laths reduces the diffusion barrier to hydrogen reaching the metal/oxide interface surrounding the hydride site and contributes to the anisotropic growth of the hydrides.

  5. Cerium compounds as scintillators

    SciTech Connect

    Wojtowicz, A.J.; Berman, E.; Koepke, C.; Lempicki, A.

    1991-01-01

    Stoichiometric Ce-materials with negligible Ce-Ce interactions should have superior scintillator properties. We present two materials: CeF{sub 3} and Ce{sub x}La{sub 1-x}P{sub 5}O{sub 14}. While cerium trifluoride is a known scintillator, pentaphosphate is of a limited usefulness, except as a remarkable model material. We show that quenching in fluoride is responsible for loss of 50% of the light output and is the cause of the, so-called, ultra fast component (2 ns). Light output of fluoride (about 50% of BGO) could be significantly improved. Deeper understanding of Ce-systems is needed to fully exploit their potentials. 10 figs., 6 refs.

  6. Cerium compounds as scintillators

    SciTech Connect

    Wojtowicz, A.J.; Berman, E.; Koepke, C.; Lempicki, A.

    1991-12-31

    Stoichiometric Ce-materials with negligible Ce-Ce interactions should have superior scintillator properties. We present two materials: CeF{sub 3} and Ce{sub x}La{sub 1-x}P{sub 5}O{sub 14}. While cerium trifluoride is a known scintillator, pentaphosphate is of a limited usefulness, except as a remarkable model material. We show that quenching in fluoride is responsible for loss of 50% of the light output and is the cause of the, so-called, ultra fast component (2 ns). Light output of fluoride (about 50% of BGO) could be significantly improved. Deeper understanding of Ce-systems is needed to fully exploit their potentials. 10 figs., 6 refs.

  7. Purification of cerium, neodymium and gadolinium for low background experiments

    NASA Astrophysics Data System (ADS)

    Boiko, R. S.; Barabash, A. S.; Belli, P.; Bernabei, R.; Cappella, F.; Cerulli, R.; Danevich, F. A.; Incicchitti, A.; Laubenstein, M.; Mokina, V. M.; Nisi, S.; Poda, D. V.; Polischuk, O. G.; Tretyak, V. I.

    2014-01-01

    Cerium, neodymium and gadolinium contain double beta active isotopes. The most interesting are 150Nd and 160Gd (promising for 0ν2β search), 136Ce (2β+ candidate with one of the highest Q2β). The main problem of compounds containing lanthanide elements is their high radioactive contamination by uranium, radium, actinium and thorium. The new generation 2β experiments require development of methods for a deep purification of lanthanides from the radioactive elements. A combination of physical and chemical methods was applied to purify cerium, neodymium and gadolinium. Liquid-liquid extraction technique was used to remove traces of Th and U from neodymium, gadolinium and for purification of cerium from Th, U, Ra and K. Co-precipitation and recrystallization methods were utilized for further reduction of the impurities. The radioactive contamination of the samples before and after the purification was tested by using ultra-low-background HPGe gamma spectrometry. As a result of the purification procedure the radioactive contamination of gadolinium oxide (a similar purification efficiency was reached also with cerium and neodymium oxides) was decreased from 0.12 Bq/kg to 0.007 Bq/kg in 228Th, from 0.04 Bq/kg to <0.006 Bq/kg in 226Ra, and from 0.9 Bq/kg to 0.04 Bq/kg in 40K. The purification methods are much less efficient for chemically very similar radioactive elements like actinium, lanthanum and lutetium.

  8. Preparation of cerium halide solvate complexes

    DOEpatents

    Vasudevan, Kalyan V; Smith, Nickolaus A; Gordon, John C; McKigney, Edward A; Muenchaussen, Ross E

    2013-08-06

    Crystals of a solvated cerium(III) halide solvate complex resulted from a process of forming a paste of a cerium(III) halide in an ionic liquid, adding a solvent to the paste, removing any undissolved solid, and then cooling the liquid phase. Diffusing a solvent vapor into the liquid phase also resulted in crystals of a solvated cerium(III) halide complex.

  9. PLUTONIUM-CERIUM-COBALT AND PLUTONIUM-CERIUM-NICKEL ALLOYS

    DOEpatents

    Coffinberry, A.S.

    1959-08-25

    >New plutonium-base teroary alloys useful as liquid reactor fuels are described. The alloys consist of 10 to 20 atomic percent cobalt with the remainder plutonium and cerium in any desired proportion, with the plutonium not in excess of 88 atomic percent; or, of from 10 to 25 atomic percent nickel (or mixture of nickel and cobalt) with the remainder plutonium and cerium in any desired proportion, with the plutonium not in excess of 86 atomic percent. The stated advantages of these alloys over unalloyed plutonium for reactor fuel use are a lower melting point and a wide range of permissible plutonium dilution.

  10. High-permitivity cerium oxide prepared by molecular beam deposition as gate dielectric and passivation layer and applied to AlGaN/GaN power high electron mobility transistor devices

    NASA Astrophysics Data System (ADS)

    Chiu, Yu Sheng; Liao, Jen Ting; Lin, Yueh Chin; Chien Liu, Shin; Lin, Tai Ming; Iwai, Hiroshi; Kakushima, Kuniyuki; Chang, Edward Yi

    2016-05-01

    High-κ cerium oxide (CeO2) was applied to AlGaN/GaN high-electron-mobility transistors (HEMTs) as a gate insulator and a passivation layer by molecular beam deposition (MBD) for high-power applications. From capacitance-voltage (C-V) measurement results, the dielectric constant of the CeO2 film was 25.2. The C-V curves showed clear accumulation and depletion behaviors with a small hysteresis (20 mV). Moreover, the interface trap density (D it) was calculated to be 5.5 × 1011 eV-1 cm-2 at 150 °C. A CeO2 MOS-HEMT was fabricated and demonstrated a low subthreshold swing (SS) of 87 mV/decade, a high ON/OFF drain current ratio (I ON/I OFF) of 1.14 × 109, and a low gate leakage current density (J leakage) of 2.85 × 10-9 A cm-2 with an improved dynamic ON-resistance (R ON), which is about one order of magnitude lower than that of a conventional HEMT.

  11. An investigation on the influence of milling time and calcination temperature on the characterization of nano cerium oxide powder synthesized by mechanochemical route

    SciTech Connect

    Aminzare, M.; Amoozegar, Z.; Sadrnezhaad, S.K.

    2012-11-15

    Highlights: ► Synthesis of nanosized CeO{sub 2} was carried out using mechanochemical reactions plus sequential calcinations procedure. ► The effect of milling time and calcinations procedure on crystallite size and surface area of the as-synthesized powders was investigated. ► The extended milling times were exposed to result in the smaller crystallite size, and hence higher surface area for the as-synthesized powder. ► Higher calcinations temperatures, on the other hand, led to the as-synthesized powder with a larger crystallite size and therefore, lower surface area. ► Activation energy for nanocrystallite growth was calculated during the calcinations procedure and the aforementioned crystallite growth was found to be conducted in the light of interfacial reactions. -- Abstract: The synthesis of nano-sized CeO{sub 2} powder was investigated via mechanochemical reactions between hydrate cerium chloride and sodium hydroxide as the starting materials. The process was followed by a subsequent calcination procedure. Characterization of as-synthesized powder was performed using X-ray diffraction, FTIR spectroscopy, Brunner–Emmett–Teller (BET) nitrogen gas absorption, scanning electron microscopy (SEM) and particle size analyzer (PSA). The precursors were milled for different milling times and then were subjected to different heat treatment procedure at variable temperatures from 100 to 700 °C. According to the results, milling time and calcination temperatures induce paramountal effects on crystallite size and surface area of as-synthesized powders. In addition, the average activation energy for the growth of nanocrystals during calcination was determined to be about 12.53 kJ/mol, suggesting the influence of interfacial reactions on the crystallite growth during the calcination procedure.

  12. Cyclic thermochemical process for producing hydrogen using cerium-titanium compounds

    DOEpatents

    Bamberger, Carlos E.

    1980-01-01

    A thermochemical cyclic process for producing hydrogen employs the reaction between ceric oxide and titanium dioxide to form cerium titanate and oxygen. The titanate is treated with an alkali metal hydroxide to give hydrogen, ceric oxide, an alkali metal titanate and water. Alkali metal titanate and water are boiled to give titanium dioxide which, along with ceric oxide, is recycled.

  13. Cyclic thermochemical process for producing hydrogen using cerium-titanium compounds

    DOEpatents

    Bamberger, C.E.

    A thermochemical cyclic process for producing hydrogen employs the reaction between ceric oxide and titanium dioxide to form cerium titanate and oxygen. The titanate is treated with an alkali metal hydroxide to give hydrogen, ceric oxide, an alkali metal titanate and water. Alkali metal titanate and water are boiled to give titanium dioxide which, along with ceric oxide, is recycled.

  14. Catalysts with Cerium in a Membrane Reactor for the Removal of Formaldehyde Pollutant from Water Effluents.

    PubMed

    Gutiérrez-Arzaluz, Mirella; Noreña-Franco, Luis; Ángel-Cuevas, Saúl; Mugica-Álvarez, Violeta; Torres-Rodríguez, Miguel

    2016-01-01

    We report the synthesis of cerium oxide, cobalt oxide, mixed cerium, and cobalt oxides and a Ce-Co/Al₂O₃ membrane, which are employed as catalysts for the catalytic wet oxidation (CWO) reaction process and the removal of formaldehyde from industrial effluents. Formaldehyde is present in numerous waste streams from the chemical industry in a concentration low enough to make its recovery not economically justified but high enough to create an environmental hazard. Common biological degradation methods do not work for formaldehyde, a highly toxic but refractory, low biodegradability substance. The CWO reaction is a recent, promising alternative that also permits much lower temperature and pressure conditions than other oxidation processes, resulting in economic benefits. The CWO reaction employing Ce- and Co-containing catalysts was carried out inside a slurry batch reactor and a membrane reactor. Experimental results are reported. Next, a mixed Ce-Co oxide film was supported on an γ-alumina membrane used in a catalytic membrane reactor to compare formaldehyde removal between both types of systems. Catalytic materials with cerium and with a relatively large amount of cerium favored the transformation of formaldehyde. Cerium was present as cerianite in the catalytic materials, as indicated by X-ray diffraction patterns. PMID:27231888

  15. PLUTONIUM-CERIUM-COPPER ALLOYS

    DOEpatents

    Coffinberry, A.S.

    1959-05-12

    A low melting point plutonium alloy useful as fuel is a homogeneous liquid metal fueled nuclear reactor is described. Vessels of tungsten or tantalum are useful to contain the alloy which consists essentially of from 10 to 30 atomic per cent copper and the balance plutonium and cerium. with the plutontum not in excess of 50 atomic per cent.

  16. Cerium as a surrogate in the plutonium immobilization waste form

    NASA Astrophysics Data System (ADS)

    Marra, James Christopher

    In the aftermath of the Cold War, approximately 50 tonnes (MT) of weapons useable plutonium (Pu) has been identified as excess. The U.S. Department of Energy (DOE) has decided that at least a portion of this material will be immobilized in a titanate-based ceramic for final disposal in a geologic repository. The baseline formulation was designed to produce a ceramic consisting primarily of a highly substituted pyrochlore with minor amounts of brannerite and hafnia-substituted rutile. Since development studies with actual actinide materials is difficult, surrogates have been used to facilitate testing. Cerium has routinely been used as an actinide surrogate in actinide chemistry and processing studies. Although cerium appeared as an adequate physical surrogate for powder handling and general processing studies, cerium was found to act significantly different from a chemical perspective in the Pu ceramic form. The reduction of cerium at elevated temperatures caused different reaction paths toward densification of the respective forms resulting in different phase assemblages and microstructural features. Single-phase fabrication studies and cerium oxidation state analyses were performed to further quantify these behavioral differences. These studies indicated that the major phases in the final phase assemblages contained point defects likely leading to their stability. Additionally, thermochemical arguments predicted that the predominant pyrochlore phase in the ceramic was metastable. The apparent metastabilty associated with primary phase in the Pu ceramic form indicated that additional studies must be performed to evaluate the thermodynamic properties of these compounds. Moreover, the metastability of this predominant phase must be considered in assessment of long-term behavior (e.g. radiation stability) of this ceramic.

  17. Oxidation of alginate and pectate biopolymers by cerium(IV) in perchloric and sulfuric acid solutions: A comparative kinetic and mechanistic study.

    PubMed

    Fawzy, Ahmed

    2016-03-15

    The kinetics of oxidation of alginate (Alg) and pectate (Pec) carbohydrate biopolymers was studied by spectrophotometry in aqueous perchloric and sulfuric acid solutions at fixed ionic strengths and temperature. In both acids, the reactions showed a first order dependence on [Ce(IV)], whereas the orders with respect to biopolymer concentrations are less than unity. In perchloric acid, the reactions exhibited less than unit orders with respect to [H(+)] whereas those proceeded in sulfuric acid showed negative fractional-first order dependences on [H(+)]. The effect of ionic strength and dielectric constant was studied. Probable mechanistic schemes for oxidation reactions were proposed. In both acids, the final oxidation products were characterized as mono-keto derivatives of both biopolymers. The activation parameters with respect to the slow step of the mechanisms were computed and discussed. The rate laws were derived and the reaction constants involved in the different steps of the mechanisms were calculated. PMID:26794772

  18. Oxidation of alginate and pectate biopolymers by cerium(IV) in perchloric and sulfuric acid solutions: A comparative kinetic and mechanistic study.

    PubMed

    Fawzy, Ahmed

    2016-03-15

    The kinetics of oxidation of alginate (Alg) and pectate (Pec) carbohydrate biopolymers was studied by spectrophotometry in aqueous perchloric and sulfuric acid solutions at fixed ionic strengths and temperature. In both acids, the reactions showed a first order dependence on [Ce(IV)], whereas the orders with respect to biopolymer concentrations are less than unity. In perchloric acid, the reactions exhibited less than unit orders with respect to [H(+)] whereas those proceeded in sulfuric acid showed negative fractional-first order dependences on [H(+)]. The effect of ionic strength and dielectric constant was studied. Probable mechanistic schemes for oxidation reactions were proposed. In both acids, the final oxidation products were characterized as mono-keto derivatives of both biopolymers. The activation parameters with respect to the slow step of the mechanisms were computed and discussed. The rate laws were derived and the reaction constants involved in the different steps of the mechanisms were calculated.

  19. Grain Growth in Cerium Metal

    NASA Astrophysics Data System (ADS)

    Cooley, Jason; Katz, Martha; Mielke, Charles; Montalvo, Joel

    We report on grain growth in forged and rolled cerium plate for temperatures from 350 to 700 degrees C and times from 30 to 120 minutes. The cerium was made by arc-melting into a 25 mm deep by 80 mm diameter copper mold. The resulting disk was forged at room temperature to a 25% reduction of thickness four times with a 350 degree C strain relief heat treatment for 60 minutes between forging steps. The resulting 8 mm thick plate was clock rolled at room temperature to a 25% reduction of thickness three times with a 350 C strain relief heat treatment between steps resulting in a plate approximately 3 mm thick. 5 x 10 mm coupons were cut from the plate for the grain growth study.

  20. Monomers, Dimers, and Helices: Complexities of Cerium and Plutonium Phenanthrolinecarboxylates.

    PubMed

    Cary, Samantha K; Ferrier, Maryline G; Baumbach, Ryan E; Silver, Mark A; Lezama Pacheco, Juan; Kozimor, Stosh A; La Pierre, Henry S; Stein, Benjamin W; Arico, Alexandra A; Gray, Danielle L; Albrecht-Schmitt, Thomas E

    2016-05-01

    The reaction of Ce(III) or Pu(III) with 1,10-phenanthroline-2,9-dicarboxylic acid (PDAH2) results in the formation of new f-element coordination complexes. In the case of cerium, Ce(PDA)(H2O)2Cl·H2O (1) or [Ce(PDAH)(PDA)]2[Ce(PDAH)(PDA)] (2) was isolated depending on the Ce/ligand ratio in the reaction. The structure of 2 is composed of two distinct substructures that are constructed from the same monomer. This monomer is composed of a Ce(III) cation bound by one PDA(2-) dianionic ligand and one PDAH(-) monoanionic ligand, both of which are tetradentate. Bridging by the carboxylate moieties leads to either [Ce(PDAH)(PDA)]2 dimers or [Ce(PDAH)(PDA)]1∞ helical chains. For plutonium, Pu(PDA)2 (3) was the only product isolated regardless of the Pu/ligand ratio employed in the reaction. During the reaction of plutonium with PDAH2, Pu(III) is oxidized to Pu(IV), generating 3. This assignment is consistent with structural metrics and the optical absorption spectrum. Ambiguity in the assignment of the oxidation state of cerium in 1 and 2 from UV-vis-near-IR spectra invoked the use of Ce L3,2-edge X-ray absorption near-edge spectroscopy, magnetic susceptibility, and heat capacity measurements. These experiments support the assignment of Ce(III) in both compounds. The bond distances and coordination numbers are also consistent with these assignments. 3 contains 8-coordinate Pu(IV), whereas the cerium centers in 1 and 2 are 9- and/or 10-coordinate, which correlates with the increased size of Ce(III) versus Pu(IV). Taken together, these data provide an example of a system where the differences in the redox behavior between these f elements creates more complex chemistry with cerium than with plutonium. PMID:27070401

  1. Catalytic conversion of carbon dioxide into dimethyl carbonate using reduced copper-cerium oxide catalysts as low as 353 K and 1.3 MPa and the reaction mechanism

    PubMed Central

    Wada, Seiki; Oka, Kazuki; Watanabe, Kentaro; Izumi, Yasuo

    2013-01-01

    Synthesis of dimethyl carbonate (DMC) from CO2 and methanol under milder reaction conditions was performed using reduced cerium oxide catalysts and reduced copper-promoted Ce oxide catalysts. Although the conversion of methanol was low (0.005–0.11%) for 2 h of reaction, DMC was synthesized as low as 353 K and at total pressure of as low as 1.3 MPa using reduced Cu–CeO2 catalyst (0.5 wt% of Cu). The apparent activation energy was 120 kJ mol−1 and the DMC synthesis rates were proportional to the partial pressure of CO2. An optimum amount of Cu addition to CeO2 was 0.1 wt% for DMC synthesis under the conditions at 393 K and total pressure of 1.3 MPa for 2 h (conversion of methanol: 0.15%) due to the compromise of two effects of Cu: the activation of H2 during reduction prior to the kinetic tests and the block (cover) of the surface active site. The reduction effects in H2 were monitored through the reduction of Ce4+ sites to Ce3+ based on the shoulder peak intensity at 5727 eV in the Ce L3-edge X-ray absorption near-edge structure (XANES). The Ce3+ content was 10% for reduced CeO2 catalyst whereas it increased to 15% for reduced Cu–CeO2 catalyst (0.5 wt% of Cu). Moreover, the content of reduced Ce3+ sites (10%) associated with the surface O vacancy (defect sites) decreased to 5% under CO2 at 290 K for reduced Cu–CeO2 catalyst (0.1 wt% of Cu). The adsorption step of CO2 on the defect sites might be the key step in DMC synthesis and thus the DMC synthesis rate dependence on the partial pressure of CO2 was proportional. Subsequent H atom subtraction steps from methanol at the neighboring surface Lewis base sites should combine two methoxy species to the adsorbed CO2 to form DMC, water, and restore the surface O vacancy. PMID:24790937

  2. Catalytic conversion of carbon dioxide into dimethyl carbonate using reduced copper-cerium oxide catalysts as low as 353 K and 1.3 MPa and the reaction mechanism

    NASA Astrophysics Data System (ADS)

    Wada, Seiki; Oka, Kazuki; Watanabe, Kentaro; Izumi, Yasuo

    2013-06-01

    Synthesis of dimethyl carbonate (DMC) from CO2 and methanol under milder reaction conditions was performed using reduced cerium oxide catalysts and reduced copper-promoted Ce oxide catalysts. Although the conversion of methanol was low (0.005-0.11%) for 2 h of reaction, DMC was synthesized as low as 353 K and at total pressure of as low as 1.3 MPa using reduced Cu-CeO2 catalyst (0.5 wt% of Cu). The apparent activation energy was 120 kJ mol-1 and the DMC synthesis rates were proportional to the partial pressure of CO2. An optimum amount of Cu addition to CeO2 was 0.1 wt% for DMC synthesis under the conditions at 393 K and total pressure of 1.3 MPa for 2 h (conversion of methanol: 0.15%) due to the compromise of two effects of Cu: the activation of H2 during reduction prior to the kinetic tests and the block (cover) of the surface active site. The reduction effects in H2 were monitored through the reduction of Ce4+ sites to Ce3+ based on the shoulder peak intensity at 5727 eV in the Ce L3-edge X-ray absorption near-edge structure (XANES). The Ce3+ content was 10% for reduced CeO2 catalyst whereas it increased to 15% for reduced Cu-CeO2 catalyst (0.5wt% of Cu). Moreover, the content of reduced Ce3+ sites (10%) associated with the surface O vacancy (defect sites) decreased to 5% under CO2 at 290 K for reduced Cu-CeO2 catalyst (0.1wt% of Cu). The adsorption step of CO2 on the defect sites might be the key step in DMC synthesis and thus the DMC synthesis rate dependence on the partial pressure of CO2 was proportional. Subsequent H atom subtraction steps from methanol at the neighboring surface Lewis base sites should combine two methoxy species to the adsorbed CO2 to form DMC, water, and restore the surface O vacancy.

  3. Exposure and Health Effects Review of Engineered Nanoscale Cerium and Cerium Dioxide Associated with its Use as a Fuel Additive - NOW IN PRINT IN THE JOURNAL

    EPA Science Inventory

    Advances of nanoscale science have produced nanomaterials with unique physical and chemical properties at commercial levels that are now incorporated into over 1000 products. Nanoscale cerium (di) oxide (Ce02) has recently gained a wide range of applications which includes coatin...

  4. A model cerium oxide matrix composite reinforced with a homogeneous dispersion of silver particulate - prepared using the glycine-nitrate process

    SciTech Connect

    Weil, K. Scott; Hardy, John S.

    2005-01-31

    Recently a new method of ceramic brazing has been developed. Based on a two-phase liquid composed of silver and copper oxide, brazing is conducted directly in air without the need of an inert cover gas or the use of surface reactive fluxes. Because the braze displays excellent wetting characteristics on a number ceramic surfaces, including alumina, various perovskites, zirconia, and ceria, we were interested in investigating whether a metal-reinforced ceramic matrix composite (CMC) could be developed with this material. In the present study, two sets of homogeneously mixed silver/copper oxide/ceria powders were synthesized using a combustion synthesis technique. The powders were compacted and heat treated in air above the liquidus temperature for the chosen Ag-CuO composition. Metallographic analysis indicates that the resulting composite microstructures are extremely uniform with respect to both the size of the metallic reinforcement as well as its spatial distribution within the ceramic matrix. The size, morphology, and spacing of the metal particulate in the densified composite appears to be dependent on the original size and the structure of the starting combustion synthesized powders.

  5. ADSORPTION OF CERIUM VALUES FROM AQUEOUS SOLUTIONS

    DOEpatents

    Roberts, F.P.

    1963-08-13

    Cerium can be removed from aqueous nitric acid (2 to 13 M) solutions by passing the latter over a PbO/sub 2/-containing anion exchange resin. The cerium is taken up by the resin, while any lanthanides, yttrium, and strontium present remain in the solution. (AEC)

  6. Interfacial redox reaction-directed synthesis of silver@cerium oxide core-shell nanocomposites as catalysts for rechargeable lithium-air batteries

    NASA Astrophysics Data System (ADS)

    Liu, Ying; Wang, Man; Cao, Lu-Jie; Yang, Ming-Yang; Ho-Sum Cheng, Samson; Cao, Chen-Wei; Leung, Kwan-Lan; Chung, Chi-Yuen; Lu, Zhou-Guang

    2015-07-01

    A facile oxidation-reduction reaction method has been implemented to prepare pomegranate-like Ag@CeO2 multicore-shell structured nanocomposites. Under Ar atmosphere, redox reaction automatically occurs between AgNO3 and Ce(NO3)3 in an alkaline solution, where Ag+ is reduced to Ag nanopartilces and Ce3+ is simultaneously oxidized to form CeO2, followed by the self-assembly to form the pomegranate-like multicore-shell structured Ag@CeO2 nanocomposites driven by thermodynamic equilibrium. No other organic amines or surfactants are utilized in the whole reaction system and only NaOH instead of organic reducing agent is used to prevent the introduction of a secondary reducing byproduct. The as-obtained pomegranate-like Ag@CeO2 multicore-shell structured nanocomposites have been characterized as electro-catalysts for the air cathode of lithium-air batteries operated in a simulated air environment. Superior electrochemical performance with high discharge capacity of 3415 mAh g-1 at 100 mA g-1, stable cycling and small charge/discharge polarization voltage is achieved, which is much better than that of the CeO2 or simple mixture of CeO2 and Ag. The enhanced properties can be primarily attributed to the synergy effect between the Ag core and the CeO2 shell resulting from the unique pomegranate-like multicore-shell nanostructures possessing plenty of active sites to promote the facile formation and decomposition of Li2O2.

  7. Oxidative mobilization of cerium and uranium and enhanced release of "immobile" high field strength elements from igneous rocks in the presence of the biogenic siderophore desferrioxamine B

    NASA Astrophysics Data System (ADS)

    Kraemer, Dennis; Kopf, Sebastian; Bau, Michael

    2015-09-01

    Polyvalent trace elements such as the high field strength elements (HFSE) are commonly considered rather immobile during low-temperature water-rock interaction. Hence, they have become diagnostic tools that are widely applied in geochemical studies. We present results of batch leaching experiments focused on the mobilization of certain HFSE (Y, Zr, Hf, Th, U and rare earth elements) from mafic, intermediate and felsic igneous rocks in the presence and absence, respectively, of the siderophore desferrioxamine B (DFOB). Our data show that DFOB strongly enhances the mobility of these trace elements during low-temperature water-rock interaction. The presence of DFOB produces two distinct features in the Rare Earths and Yttrium (REY) patterns of leaching solutions, regardless of the mineralogical and chemical composition or the texture of the rock type studied. Bulk rock-normalized REY patterns of leaching solutions with DFOB show (i) a very distinct positive Ce anomaly and (ii) depletion of La and other light REY relative to the middle REY, with a concave downward pattern between La and Sm. These features are not observed in experiments with hydrochloric acid, acetic acid or deionized water. In DFOB-bearing leaching solutions Ce and U are decoupled from and selectively enriched relative to light REY and Th, respectively, due to oxidation to Ce(IV) and U(VI). Oxidation of Ce3+ and U4+ is promoted by the significantly higher stability of the Ce(IV) and U(VI) DFOB complexes as compared to the Ce(III) and U(IV) DFOB complexes. This is similar to the relationship between the Ce(IV)- and Ce(III)-pentacarbonate complexes that cause positive Ce anomalies in alkaline lakes. However, while formation of Ce(IV) carbonate complexes is confined to alkaline environments, Ce(IV) DFOB complexes may produce positive Ce anomalies even in mildly acidic and near-neutral natural waters. Siderophore-promoted dissolution processes also significantly enhance mobility of other 'immobile' HFSE

  8. Cerium and niobium doped SrCoO3-δ as a potential cathode for intermediate temperature solid oxide fuel cells

    NASA Astrophysics Data System (ADS)

    Huang, Shouguo; Feng, Shuangjiu; Lu, Qiliang; Li, Yide; Wang, Hong; Wang, Chunchang

    2014-04-01

    Sr0.9Ce0.1Co0.9Nb0.1O3-δ (SCCN) has been synthesized using solid state reaction, and investigated as a new cathode material for intermediate temperature solid oxide fuel cells (ITSOFCs). SCCN material exhibits sufficiently high electronic conductivity and excellent chemical compatibility with SDC electrolyte. Highly charged Ce4+ and Nb5+ successfully stabilize the perovskite structure to avoid order-disorder phase transition. The electrical conductivity reaches a high value of 516 S cm-1 at 300 °C in air. The area specific resistances of the SCCN-50 wt.% Ce0.8Sm0.2O1.9 (SDC) cathode are as low as 0.027, 0.049, and 0.094 Ω cm2 at 700, 650, and 600 °C, respectively, with the corresponding peak power densities of 1074, 905, and 589 mW cm-2. A relatively low thermal expansion coefficient of SCCN-SDC is 14.3 × 10-6 K-1 in air. All these results imply that SCCN holds tremendous promise as a cathode material for ITSOFCs.

  9. Remarkable changes in the photoluminescent properties of Y2Ce2O7:Eu(3+) red phosphors through modification of the cerium oxidation states and oxygen vacancy ordering.

    PubMed

    Raj, Athira K V; Prabhakar Rao, P; Sreena, T S; Sameera, S; James, Vineetha; Renju, U A

    2014-11-21

    A new series of red phosphors based on Eu(3+)-doped yttrium cerate [Y1.9Ce2O7:0.1Eu(3+), Y2Ce1.9O7:0.1Eu(3+) and Y2Ce2-xO7:xEu(3+) (x = 0.05, 0.10, 0.15, 0.20, 0.25 and 0.50)] was prepared via a conventional solid-state method. The influence of the substitution of Eu(3+) at the aliovalent site on the photoluminescent properties was determined by powder X-ray diffraction, FT Raman spectroscopy, X-ray photoelectron spectroscopy, transmission electron microscopy, scanning electron microscopy with energy-dispersive spectroscopy, UV-visible absorption spectroscopy, photoluminescence spectroscopy and lifetime measurements. The substitution of Eu(3+) at the Ce(4+) site induces a structural transition from a defect fluorite to a C-type structure, which increases the oxygen vacancy ordering and the distortion of the Eu(3+) environment, and decreases the formation of Ce(3+) states. In contrast, phosphors with isovalent substitution at the Y(3+) site exhibit the biphasic nature of defect fluorite and a C-type structure, thereby increasing the number of Ce(3+) oxidation states. These modifications resulted in remarkable changes in the photoluminescent properties of Y2Ce1.9O7:0.1Eu(3+) red phosphors, with emission intensities 3.8 times greater than those of the Ce0.9O2:0.1Eu(3+) and Y1.9Ce2O7:0.1Eu(3+). The photoluminescent properties of Y2Ce2-xO7:xEu(3+) were studied at different Eu(3+) concentrations under excitation with blue light. These phosphors emit intense red light due to the (5)D0-(7)F2 transition under excitation at 466 nm and no concentration quenching is observed with up to 50 mol% Eu(3+). They show increased lifetimes in the range 0.62-0.72 ms at Eu(3+) concentrations. The cation ordering linked to the oxygen vacancy ordering led to the uniform distribution of Eu(3+) ions in the lattice, thus allowing higher doping concentrations without quenching and consequently increasing the lifetime of the (5)D0 states. Our results demonstrate that significant improvements in

  10. The effects of cerium doping on the size, morphology, and optical properties of α-hematite nanoparticles for ultraviolet filtration

    SciTech Connect

    Cardillo, Dean; Konstantinov, Konstantin; Devers, Thierry

    2013-11-15

    Highlights: • Possible application of cerium-doped α-hematite as ultraviolet filter. • Nanoparticles obtained through co-precipitation technique using various cerium doping levels followed by annealing. • Comprehensive materials characterisation utilizing XRD, DSC/TGA, STEM, UV–vis spectroscopy. • Increasing cerium content reduces particle sizing and alters morphology. • Solubility of cerium in hematite seen between 5 and 10% doping, 10% cerium doping greatly enhances attenuation in ultraviolet region and increases optical bandgap. - Abstract: Metal oxide nanoparticles have potential use in energy storage, electrode materials, as catalysts and in the emerging field of nanomedicine. Being able to accurately tailor the desirable properties of these nanoceramic materials, such as particle size, morphology and optical bandgap (E{sub g}) is integral in the feasibility of their use. In this study we investigate the altering of both the structure and physical properties through the doping of hematite (α-Fe{sub 2}O{sub 3}) nanocrystals with cerium at a range of concentrations, synthesised using a one-pot co-precipitation method. This extremely simple synthesis followed by thermal treatment results in stable Fe{sub 2−x}Ce{sub x}O{sub y} nanoceramics resulting from the burning of any unreacted precursors and transformation of goethite-cerium doped nanoparticle intermediate. The inclusion of Ce into the crystal lattice of these α-Fe{sub 2}O{sub 3} nanoparticles causes a significantly large reduction in mean crystalline size and alteration in particle morphology with increasing cerium content. Finally we report an increase optical semiconductor bandgap, along with a substantial increase in the ultraviolet attenuation found for a 10% Ce-doping concentration which shows the potential application of cerium-doped hematite nanocrystals to be used as a pigmented ultraviolet filter for cosmetic products.

  11. Synthesis and characterization of cerium and yttrium alkoxide complexes supported by ferrocene-based chelating ligands.

    PubMed

    Broderick, Erin M; Thuy-Boun, Peter S; Guo, Neng; Vogel, Carola S; Sutter, Jörg; Miller, Jeffrey T; Meyer, Karsten; Diaconescu, Paula L

    2011-04-01

    Two series of Schiff base metal complexes were investigated, where each series was supported by an ancillary ligand incorporating a ferrocene backbone and different N=X functionalities. One ligand is based on an imine, while the other is based on an iminophosphorane group. Cerium(IV), cerium(III), and yttrium(III) alkoxide complexes supported by the two ligands were synthesized. All metal complexes were characterized by cyclic voltammetry. Additionally, NMR, Mössbauer, X-ray absorption near-edge structure (XANES), and absorption spectroscopies were used. The experimental data indicate that iron remains in the +2 oxidation state and that cerium(IV) does not engage in a redox behavior with the ancillary ligand.

  12. Growth of transition metals on cerium tungstate model catalyst layers

    NASA Astrophysics Data System (ADS)

    Skála, T.; Tsud, N.; Stetsovych, V.; Mysliveček, J.; Matolín, V.

    2016-10-01

    Two model catalytic metal/oxide systems were investigated by photoelectron spectroscopy and scanning tunneling microscopy. The mixed-oxide support was a cerium tungstate epitaxial thin layer grown in situ on the W(1 1 0) single crystal. Active particles consisted of palladium and platinum 3D islands deposited on the tungstate surface at 300 K. Both metals were found to interact weakly with the oxide support and the original chemical state of both support and metals was mostly preserved. Electronic and morphological changes are discussed during the metal growth and after post-annealing at temperatures up to 700 K. Partial transition-metal coalescence and self-cleaning from the CO and carbon impurities were observed.

  13. Growth of transition metals on cerium tungstate model catalyst layers.

    PubMed

    Skála, T; Tsud, N; Stetsovych, V; Mysliveček, J; Matolín, V

    2016-10-01

    Two model catalytic metal/oxide systems were investigated by photoelectron spectroscopy and scanning tunneling microscopy. The mixed-oxide support was a cerium tungstate epitaxial thin layer grown in situ on the W(1 1 0) single crystal. Active particles consisted of palladium and platinum 3D islands deposited on the tungstate surface at 300 K. Both metals were found to interact weakly with the oxide support and the original chemical state of both support and metals was mostly preserved. Electronic and morphological changes are discussed during the metal growth and after post-annealing at temperatures up to 700 K. Partial transition-metal coalescence and self-cleaning from the CO and carbon impurities were observed. PMID:27494195

  14. Pulmonary toxicity in mice following exposure to cerium chloride.

    PubMed

    Hong, Jie; Yu, Xiaohong; Pan, Xiaoyu; Zhao, Xiaoyang; Sheng, Lei; Sang, Xuezi; Lin, Anan; Zhang, Chi; Zhao, Yue; Gui, Suxin; Sun, Qingqing; Wang, Ling; Hong, Fashui

    2014-06-01

    The widespread application of lanthanoids (Lns) in manufacturing industries has raised occupational and environmental health concerns about the possible increased health risks to humans exposed to Lns in their working and living environments. Numerous studies have shown that exposures to Ln cause pulmonary injury in animals, but very little is known about the molecular mechanisms of the pulmonary inflammation caused by cerium chloride (CeCl3) exposure. In this study, we evaluated the oxidative stress and molecular mechanism underlying with the pulmonary inflammation associated with chronic lung toxicity in mice treated with nasally instilled CeCl3 for 90 consecutive days. Our findings suggest that significant cerium accumulated in the lung, leading the obvious increase of the lung indices, significant increases in inflammatory cells and levels of lactate dehydrogenase, alkaline phosphate, and total protein, overproduction of reactive oxygen species and peroxidation of lipids, reduced antioxidant capacity, and pulmonary inflammation. CeCl3 exposure also activated nuclear factor κB, increased the expression of tumor necrosis factor α, cyclooxygenase-2, heme oxygenase 1, interleukin 2, interleukin 4, interleukin 6, interleukin 8, interleukin 10, interleukin 18, interleukin 1β, and CYP1A1. However, CeCl3 reduced the expression of nuclear factor κB (NF-κB)-inhibiting factor and heat shock protein 70. These findings suggest that the pulmonary inflammation caused by CeCl3 in mice is closely associated with oxidative stress and inflammatory cytokine expression. PMID:24736977

  15. α-Radioactivity of cerium-142

    USGS Publications Warehouse

    Senftle, F.E.; Stern, T.W.; Alekna, V.P.

    1959-01-01

    JOHNSON AND NIER1 have measured the atomic masses of some of the rare-earth isotopes and have shown that the mass difference cerium-142—(barium-138 + helium-4) is equivalent to 1.68 ± 0.10 MeV. Similar results for the naturally occurring samarium and neodymium isotopes show that the α-active isotope of each element is the one having the largest possible decay energy. Rasmussen and others2 suggest that the two or three neutrons just beyond the closed shell of 82 neutrons have decreased binding energies and hence the α-energy has a maximum about 84 neutrons. Johnson and Nier suggest that the α-decay of cerium-142 may take place with enough energy to be experimentally observable. Porschen and Riezler3 examined a sample of un-enriched cerium ammonium citrate using nuclear track plates sensitive to α-particles. No α-activity was observed after a 30-day exposure of 1.2 mgm. of the cerium salt. In 1957 Riezler and Kauw4 reported an alpha activity for an enriched sample of cerium-142. From their results they calculated a half-life of 5.1 × 1015 years with an uncertainty factor of 2.

  16. Production of CeO2 Nanoparticles by Method of Laser Ablation of Bulk Metallic Cerium Targets in Liquid

    NASA Astrophysics Data System (ADS)

    Svetlichnyi, V. A.; Lapin, I. N.

    2016-03-01

    The method of pulsed laser ablation in liquid was used to synthesize dispersions of cerium oxide nanoparticles when subjecting a metallic cerium target in water and alcohol to basic frequency radiation of the nanosecond Nd:YAG laser (1064 nm, 7 ns, 20 Hz). Researchers have studied the effect of laser radiation parameters, duration of impact, and optical scheme of experiment on the ablation process. The average rate of nanoparticle production was 50 mg/h in water and 25 mg/h in alcohol. Researchers have studied the size characteristics and crystalline structure of the nanoparticles produced. The particles have bimodal size distribution with 6 nm and 25 nm maximums. The average crystallite size is 17-19 nm. The crystalline structure of nanoparticles, namely cubic cerium oxide (fluorite structure), space group Fm-3m, is confirmed by the X-ray diffraction data, as well as optical absorption spectra and Raman spectroscopy.

  17. Divalent fluoride doped cerium fluoride scintillator

    DOEpatents

    Anderson, David F.; Sparrow, Robert W.

    1991-01-01

    The use of divalent fluoride dopants in scintillator materials comprising cerium fluoride is disclosed. The preferred divalent fluoride dopants are calcium fluoride, strontium fluoride, and barium fluoride. The preferred amount of divalent fluoride dopant is less than about two percent by weight of the total scintillator. Cerium fluoride scintillator crystals grown with the addition of a divalent fluoride have exhibited better transmissions and higher light outputs than crystals grown without the addition of such dopants. These scintillators are useful in radiation detection and monitoring applications, and are particularly well suited for high-rate applications such as positron emission tomography (PET).

  18. Cerium migration during PEM fuel cell accelerated stress testing

    SciTech Connect

    Baker, Andrew M.; Mukundan, Rangachary; Borup, Rodney L.; Spernjak, Dusan; Judge, Elizabeth J.; Advani, Suresh G.; Prasad, Ajay K.

    2016-01-01

    Cerium is a radical scavenger which improves polymer electrolyte membrane (PEM) fuel cell durability. During operation, however, cerium rapidly migrates in the PEM and into the catalyst layers (CLs). In this work, membrane electrode assemblies (MEAs) were subjected to accelerated stress tests (ASTs) under different humidity conditions. Cerium migration was characterized in the MEAs after ASTs using X-ray fluorescence. During fully humidified operation, water flux from cell inlet to outlet generated in-plane cerium gradients. Conversely, cerium profiles were flat during low humidity operation, where in-plane water flux was negligible, however, migration from the PEM into the CLs was enhanced. Humidity cycling resulted in both in-plane cerium gradients due to water flux during the hydration component of the cycle, and significant migration into the CLs. Fluoride and cerium emissions into effluent cell waters were measured during ASTs and correlated, which signifies that ionomer degradation products serve as possible counter-ions for cerium emissions. Fluoride emission rates were also correlated to final PEM cerium contents, which indicates that PEM degradation and cerium migration are coupled. Lastly, it is proposed that cerium migrates from the PEM due to humidification conditions and degradation, and is subsequently stabilized in the CLs by carbon catalyst supports.

  19. Cerium migration during PEM fuel cell accelerated stress testing

    DOE PAGESBeta

    Baker, Andrew M.; Mukundan, Rangachary; Borup, Rodney L.; Spernjak, Dusan; Judge, Elizabeth J.; Advani, Suresh G.; Prasad, Ajay K.

    2016-01-01

    Cerium is a radical scavenger which improves polymer electrolyte membrane (PEM) fuel cell durability. During operation, however, cerium rapidly migrates in the PEM and into the catalyst layers (CLs). In this work, membrane electrode assemblies (MEAs) were subjected to accelerated stress tests (ASTs) under different humidity conditions. Cerium migration was characterized in the MEAs after ASTs using X-ray fluorescence. During fully humidified operation, water flux from cell inlet to outlet generated in-plane cerium gradients. Conversely, cerium profiles were flat during low humidity operation, where in-plane water flux was negligible, however, migration from the PEM into the CLs was enhanced. Humiditymore » cycling resulted in both in-plane cerium gradients due to water flux during the hydration component of the cycle, and significant migration into the CLs. Fluoride and cerium emissions into effluent cell waters were measured during ASTs and correlated, which signifies that ionomer degradation products serve as possible counter-ions for cerium emissions. Fluoride emission rates were also correlated to final PEM cerium contents, which indicates that PEM degradation and cerium migration are coupled. Lastly, it is proposed that cerium migrates from the PEM due to humidification conditions and degradation, and is subsequently stabilized in the CLs by carbon catalyst supports.« less

  20. Cerium oxide as a promoter for the electro-oxidation reaction of ethanol: in situ XAFS characterization of the Pt nanoparticles supported on CeO2 nanoparticles and nanorods.

    PubMed

    Corchado-García, Juan; Betancourt, Luis E; Vélez, Carlos A; Senanayake, Sanjaya D; Stacchiola, Dario; Sasaki, Kotaro; Guinel, Maxime J-F; Zhou, Yunyun; Cheung, Chin Li; Cabrera, Carlos R

    2015-12-28

    In this study we probe the electrocatalytic activity of Pt nanoparticles supported on ceria nanoparticles (NPs) and nanorods (NRs) in the ethanol oxidation reaction (EOR) in alkaline media. The goal of this study was to relate morphology, support structure and composition to the EOR catalytic activity by using in situ X-ray absorption fine structure (XAFS) studies. Cyclic voltammetry experiments showed that both ceria supported catalysts (NP vs. NR) had similar peak current densities at fast scan rates, however at slow scan rates, the ceria NR catalyst showed superior catalytic activity. In situ XAFS studies in KOH showed that both ceria supported catalysts had more electron density in their d-band (with the ceria NR having more electron density overall) than ceria - free Pt/Vulcan standard. However, in an ethanol solution the ceria NR catalyst had the least electron density. We propose that this change is due to the increased charge transfer efficiency between the ceria nanorod support and platinum. In the KOH solution, the increased electron density makes the platinum less electrophilic and hinders Pt-OH bond formation. In the EtOH solution, platinum's increased nucleophilicity facilitates the bond formation between Pt and the electron deficient carbon in ethanol which in turn withdraws the electron density from platinum and increases the white line intensity as observed in the XAS measurements.

  1. Near-road modeling and measurement of cerium-containing particles generated by nanoparticle diesel fuel additive use

    EPA Science Inventory

    Cerium oxide nanoparticles (nCe) are used as a fuel-borne catalyst in diesel engines to reduce particulate emissions, yet the environmental and human health impacts of the exhaust particles are not well understood. To bridge the gap between emission measurements and ambient impac...

  2. Synthesis of Cerium-Doped Titania Nanoparticles and Nanotubes.

    PubMed

    Cao, Wei; Suzuki, Takuya; Elsayed-Ali, Hani E; Abdel-Fattah, Tarek M

    2015-03-01

    Cerium-doped titania nanoparticles and nanotubes were synthesized via hydrothermal processes. X-Ray Diffraction revealed that cerium-doped titania nanoparticles have an anatase crystal structure, while cerium-doped titania nanotubes have an H2Ti3O7-type structure. Scanning electron microscopy and high resolution transmission electron microscopy showed that both types of titania are well crystallized with relatively uniform size distribution. The photocatalytic degradation of methylthioninium chloride known as methylene blue dye was tested and both cerium-doped titania nanoparticles and nanotubes. The preliminary photocatalytic degradation of Methylene Blue data showed significantly improved visible light photocatalytic activities as compared to commercial titania powders.

  3. Thermochemical Modeling of the Uranium-Cerium-Oxygen System

    SciTech Connect

    Voit, Stewart L; Besmann, Theodore M

    2010-10-01

    The objective of the Fuel Cycle R&D Program, Advanced Fuels campaign is to provide the research and development necessary to develop low loss, high quality nuclear fuels for ultra-high burnup reactor operation. Primary work in this area will be focused on the ceramic and metallic fuel systems. The goal of the current work is to enhance the understanding of ceramic nuclear fuel thermochemistry to support fuel research and development efforts. The thermochemical behavior of oxide nuclear fuel under irradiation is dependent on the oxygen to metal ratio (O:M). In fluorite-structured fuel, the actinide metal cation is bonded with {approx}2 oxygen atoms on a crystal lattice and as the metal atoms fission, fission fragments and free oxygen are created. The resulting fission fragments will contain some oxide forming elements, however these are insufficient to bind to all the liberated oxygen and therefore, there is an average increase in O:M with fuel burnup. Some of the fission products also form species that will migrate to and react with the cladding surface in a phenomenon known as Fuel Clad Chemical Interaction (FCCI). Cladding corrosion is life-limiting so it is desirable to understand influencing factors, such as oxide thermochemistry, which can be used to guide the design and fabrication of higher burn up fuel. A phased oxide fuel thermochemical model development effort is underway within the Advanced Fuels Campaign. First models of binary oxide systems are developed. For nuclear fuel system this means U-O and transuranic systems such as Pu-O, Np-O and Am-O. Next, the binary systems will be combined to form pseudobinary systems such as U-Pu-O, etc. The model development effort requires the use of data to allow optimization based on known thermochemical parameters as a function of composition and temperature. Available data is mined from the literature and supplemented by experimental work as needed. Due to the difficulty of performing fuel fabrication development

  4. Variation of electronic transitions and reduction potentials of cerium(IV) complexes.

    PubMed

    Williams, Ursula J; Schneider, David; Dorfner, Walter L; Maichle-Mössmer, Cäcilia; Carroll, Patrick J; Anwander, Reiner; Schelter, Eric J

    2014-11-21

    The trivalent compound K[Ce[N(SiHMe2)2]4] was synthesized and oxidized, providing a convenient route to the reported cerium(IV) compound Ce[N(SiHMe2)2]4. Protonolysis reactions of Ce[N(SiHMe2)2]4 with tert-butanol, substituted benzyl alcohols, and 2,6-diphenylphenol yielded the neutral tetravalent compounds Ce(O(t)Bu)4(py)2, Ce2(OCH2C6R5)8(thf)2 (R = Me, F), and Ce(Odpp)4 (dpp = 2,6-(C6H5)2-C6H3). Spectroscopic and electrochemical characterization of the monometallic cerium(IV) silylamide, alkoxide, and aryloxide compounds revealed variable ligand-to-metal charge transfer transitions and metal-based reduction potentials. Computational bonding analyses were performed to complement the physical characterization of the complexes.

  5. Atomic Transition Probabilities for Neutral Cerium

    NASA Astrophysics Data System (ADS)

    Lawler, J. E.; den Hartog, E. A.; Wood, M. P.; Nitz, D. E.; Chisholm, J.; Sobeck, J.

    2009-10-01

    The spectra of neutral cerium (Ce I) and singly ionized cerium (Ce II) are more complex than spectra of other rare earth species. The resulting high density of lines in the visible makes Ce ideal for use in metal halide (MH) High Intensity Discharge (HID) lamps. Inclusion of cerium-iodide in a lamp dose can improve both the Color Rendering Index and luminous efficacy of a MH-HID lamp. Basic spectroscopic data including absolute atomic transition probabilities for Ce I and Ce II are needed for diagnosing and modeling these MH-HID lamps. Recent work on Ce II [1] is now being augmented with similar work on Ce I. Radiative lifetimes from laser induced fluorescence measurements [2] on neutral Ce are being combined with emission branching fractions from spectra recorded using a Fourier transform spectrometer. A total of 14 high resolution spectra are being analyzed to determine branching fractions for 2000 to 3000 lines from 153 upper levels in neutral Ce. Representative data samples and progress to date will be presented. [4pt] [1] J. E. Lawler, C. Sneden, J. J. Cowan, I. I. Ivans, and E. A. Den Hartog, Astrophys. J. Suppl. Ser. 182, 51-79 (2009). [0pt] [2] E. A. Den Hartog, K. P. Buettner, and J. E. Lawler, J. Phys. B: Atomic, Molecular & Optical Physics 42, 085006 (7pp) (2009).

  6. Coupled redox transformations of catechol and cerium at the surface of a cerium(III) phosphate mineral

    NASA Astrophysics Data System (ADS)

    Cervini-Silva, Javiera; Gilbert, Benjamin; Fakra, Sirine; Friedlich, Stephan; Banfield, Jillian

    2008-05-01

    Highly insoluble Ce-bearing phosphate minerals form by weathering of apatite [Ca5(PO4)3.(OH,F,Cl)], and are important phosphorous repositories in soils. Although these phases can be dissolved via biologically-mediated pathways, the dissolution mechanisms are poorly understood. In this paper we report spectroscopic evidence to support coupling of redox transformations of organic carbon and cerium during the reaction of rhabdophane (CePO4·H2O) and catechol, a ubiquitous biogenic compound, at pH 5. Results show that the oxic-anoxic conditions influence the mineral dissolution behavior. Under anoxic conditions, the release of P and Ce occurs stoichiometrically. In contrast, under oxic conditions, the mineral dissolution behavior is incongruent, with dissolving Ce3+ ions oxidizing to CeO2. Reaction product analysis shows the formation of CO2, polymeric C, and oxalate and malate. The presence of more complex forms of organic carbon was also confirmed. Near edge X-ray absorption fine structure spectroscopy measurements at Ce-M4,5 and C-K absorption edges on reacted CePO4·H2O samples in the absence or presence of catechol and dissolved oxygen confirm that (1) the mineral surface converts to the oxide during this reaction, while full oxidation is limited to the near-surface region only; (2) the Ce valence remains unchanged when the reaction between CePO4·H2O and O2 but in the absence of catechol. Carbon K-edge spectra acquired from rhabdophane reacted with catechol under oxic conditions show spectral features before and after reaction that are considerably different from catechol, indicating the formation of more complex organic molecules. Decreases in intensity of characteristic catechol peaks are accompanied by the appearance of new π∗ resonances due to carbon in carboxyl (ca. 288.5 eV) and carbonyl (ca. 289.3 eV) groups, and the development of broad structure in the σ∗ region characteristic of aliphatic carbon. Evolution of the C K-edge spectra is consistent

  7. Local Structure of Cerium in Aluminophosphate and Silicophosphate Glasses

    SciTech Connect

    Rygel, Jennifer L.; Chen, Yongsheng; Pantano, Carlo G.; Shibata, Tomohiro; Du, Jincheng; Kokou, Leopold; Woodman, Robert; Belcher, James

    2011-09-20

    The local structure of cerium in two systematic compositional series of glasses, nominally CeP{sub 3}O{sub 9}-AlP{sub 3}O{sub 9} and CeP{sub 3}O{sub 9}-SiP{sub 2}O{sub 7}, was interrogated using X-ray photoelectron spectroscopy (XPS) and X-ray absorption fine structure (XAFS) spectroscopy. XPS revealed that, for glasses melted in air, {>=}95% of cerium ions are Ce{sup 3+}. This was independently confirmed using X-ray absorption near edge spectroscopy (XANES). Ce K-edge extended X-ray absorption fine structure (EXAFS) has been used to determine the local structure of Ce{sup 3+}. Near the metaphosphate composition, cerium was found to have an average cerium coordination number of {approx}7.0 and an average cerium-oxygen bond length of 2.41 {angstrom}. The average cerium coordination number and average cerium-oxygen bond distance were found to increase with decreasing cerium concentration in both compositional series. Rare-earth clustering is suggested based on numerical calculations for glasses containing {>=}14 and {>=}15 mol% Ce{sub 2}O{sub 3} for the aluminophosphate and silicophosphate series, respectively.

  8. RECOVERY OF Pu FROM CERIUM TRIFLUORIDE BY FLUORINATION

    DOEpatents

    Brown, H.S.; Bohlmann, E.G.

    1959-02-10

    An improved process is prcsented for selectively recovering plutonium from a solution containing fission products comprising precipitating cerium trifluoride in the solution for effccting carrier precipitation of plutonium. The resulting carrier precipitate is dried and subjected to fluorination at about 600 C. The plutonium forms a volatile fiuoridc and is so separated from the nonvolatile cerium fluoride.

  9. Cerium migration during PEM fuel cell assembly and operation

    SciTech Connect

    Baker, Andrew M.; Torraco, Dennis; Judge, Elizabeth J.; Spernjak, Dusan; Mukundan, Rangachary; Borup, Rod L.; Advani, Suresh G.; Prasad, Ajay K.

    2015-10-02

    Cerium migration between PEM fuel cell components is influenced by potential-driven mobility, ionic diffusion, and gradients in water content. These factors were investigated in ex situ experiments and in operating fuel cells. Potential-induced migration was measured ex situ in hydrated window cells. Cerium-containing MEAs were also fabricated and tested under ASTs. MEA disassembly and subsequent XRF analysis were used to observe rapid cerium migration during cell assembly and operation. During MEA hot pressing, humidification, and low RH operation at OCV, ionic diffusion causes uniform migration from the membrane into the catalyst layers. During high RH operation at OCV, in-plane cerium gradients arise due to variations in water content. These gradients may diminish the scavenging efficacy of cerium by reducing its proximity to generated radicals.

  10. Cerium migration during PEM fuel cell assembly and operation

    SciTech Connect

    Baker, Andrew M.; Torraco, Dennis; Judge, Elizabeth J.; Spernjak, Dusan; Mukundan, Rangachary; Borup, Rod L.; Advani, Suresh G.; Prasad, Ajay K.

    2015-09-14

    Cerium migration between PEM fuel cell components is influenced by potential-driven mobility, ionic diffusion, and gradients in water content. These factors were investigated in ex situ experiments and in operating fuel cells. Potential-induced migration was measured ex situ in hydrated window cells. Cerium-containing MEAs were also fabricated and tested under ASTs. MEA disassembly and subsequent XRF analysis were used to observe rapid cerium migration during cell assembly and operation. During MEA hot pressing, humidification, and low RH operation at OCV, ionic diffusion causes uniform migration from the membrane into the catalyst layers. During high RH operation at OCV, in-plane cerium gradients arise due to variations in water content. These gradients may diminish the scavenging efficacy of cerium by reducing its proximity to generated radicals.

  11. Cerium Biomagnification in a Terrestrial Food Chain: Influence of Particle Size and Growth Stage.

    PubMed

    Majumdar, Sanghamitra; Trujillo-Reyes, Jesica; Hernandez-Viezcas, Jose A; White, Jason C; Peralta-Videa, Jose R; Gardea-Torresdey, Jorge L

    2016-07-01

    Mass-flow modeling of engineered nanomaterials (ENMs) indicates that a major fraction of released particles partition into soils and sediments. This has aggravated the risk of contaminating agricultural fields, potentially threatening associated food webs. To assess possible ENM trophic transfer, cerium accumulation from cerium oxide nanoparticles (nano-CeO2) and their bulk equivalent (bulk-CeO2) was investigated in producers and consumers from a terrestrial food chain. Kidney bean plants (Phaseolus vulgaris var. red hawk) grown in soil contaminated with 1000-2000 mg/kg nano-CeO2 or 1000 mg/kg bulk-CeO2 were presented to Mexican bean beetles (Epilachna varivestis), which were then consumed by spined soldier bugs (Podisus maculiventris). Cerium accumulation in plant and insects was independent of particle size. After 36 days of exposure to 1000 mg/kg nano- and bulk-CeO2, roots accumulated 26 and 19 μg/g Ce, respectively, and translocated 1.02 and 1.3 μg/g Ce, respectively, to shoots. The beetle larvae feeding on nano-CeO2 exposed leaves accumulated low levels of Ce since ∼98% of Ce was excreted in contrast to bulk-CeO2. However, in nano-CeO2 exposed adults, Ce in tissues was higher than Ce excreted. Additionally, Ce content in tissues was biomagnified by a factor of 5.3 from the plants to adult beetles and further to bugs.

  12. Application of Cerium (IV) as an Oxidimetric Agent for the Determination of Ethionamide in Pharmaceutical Formulations

    PubMed Central

    2016-01-01

    Two simple methods are described for the determination of ethionamide (ETM) in bulk drug and tablets using cerium (IV) sulphate as the oxidimetric agent. In both methods, the sample solution is treated with a measured excess of cerium (IV) solution in H2SO4 medium, and after a fixed standing time, the residual oxidant is determined either by back titration with standard iron (II) solution to a ferroin end point in titrimetry or by reacting with o-dianisidine followed by measurement of the absorbance of the orange-red coloured product at 470 nm in spectrophotometry. In titrimetry, the reaction proceeded with a stoichiometry of 1 : 2 (ETM : Ce (IV)) and the amount of cerium (IV) consumed by ETM was related to the latter's amount, and the method was applicable over 1.0–8.0 mg of drug. In spectrophotometry, Beer's law was obeyed over the concentration range of 0.5–5.0 μg/mL ETM with a molar absorptivity value of 2.66 × 104 L/(mol·cm). The limits of detection (LOD) and quantification (LOQ) calculated according to ICH guidelines were 0.013 and 0.043 μg/mL, respectively. The proposed titrimetric and spectrophotometric methods were found to yield reliable results when applied to bulk drug and tablets analysis, and hence they can be applied in quality control laboratories.

  13. The role of hydrogen peroxide in the deposition of cerium-based conversion coatings

    NASA Astrophysics Data System (ADS)

    Scholes, F. H.; Soste, C.; Hughes, A. E.; Hardin, S. G.; Curtis, P. R.

    2006-12-01

    Cerium-based conversion coatings are progressing as an effective alternative to hazardous chromate-based systems used in the treatment of metal surfaces. However, there is still considerable debate over the mechanism by which these coatings are formed. Here, titrations of cerium-based conversion coating solutions were carried out in order to model the reactions that occur at the metal-solution interface during coating, with a particular emphasis on investigating the role of hydrogen peroxide (H 2O 2). The titration curves obtained support the proposed formation of Ce(III) peroxo complexes such as Ce(H 2O 2) 3+ as an initial step, followed by deprotonation, oxidation and precipitation to form peroxo-containing Ce(IV) species such as Ce (IV)(O 2)(OH) 2. The precipitates resulting from titrations were characterised by Raman spectroscopy, X-ray diffraction and thermogravimetric analysis, confirming the presence of peroxo bonds, and nano-sized CeO 2 crystallites that decreased in size with increasing H 2O 2 concentration. Characterisation of cerium conversion coatings on aluminium alloy surfaces confirmed the presence of peroxo species in the coatings, thereby supporting the titration model.

  14. Cerium Regulates Expression of Alternative Methanol Dehydrogenases in Methylosinus trichosporium OB3b

    PubMed Central

    Farhan Ul Haque, Muhammad; Kalidass, Bhagyalakshmi; Bandow, Nathan; Turpin, Erick A.; DiSpirito, Alan A.

    2015-01-01

    Methanotrophs have multiple methane monooxygenases that are well known to be regulated by copper, i.e., a “copper switch.” At low copper/biomass ratios the soluble methane monooxygenase (sMMO) is expressed while expression and activity of the particulate methane monooxygenase (pMMO) increases with increasing availability of copper. In many methanotrophs there are also multiple methanol dehydrogenases (MeDHs), one based on Mxa and another based on Xox. Mxa-MeDH is known to have calcium in its active site, while Xox-MeDHs have been shown to have rare earth elements in their active site. We show here that the expression levels of Mxa-MeDH and Xox-MeDH in Methylosinus trichosporium OB3b significantly decreased and increased, respectively, when grown in the presence of cerium but the absence of copper compared to the absence of both metals. Expression of sMMO and pMMO was not affected. In the presence of copper, the effect of cerium on gene expression was less significant, i.e., expression of Mxa-MeDH in the presence of copper and cerium was slightly lower than in the presence of copper alone, but Xox-MeDH was again found to increase significantly. As expected, the addition of copper caused sMMO and pMMO expression levels to significantly decrease and increase, respectively, but the simultaneous addition of cerium had no discernible effect on MMO expression. As a result, it appears Mxa-MeDH can be uncoupled from methane oxidation by sMMO in M. trichosporium OB3b but not from pMMO. PMID:26296730

  15. Cerium regulates expression of alternative methanol dehydrogenases in Methylosinus trichosporium OB3b.

    PubMed

    Farhan Ul Haque, Muhammad; Kalidass, Bhagyalakshmi; Bandow, Nathan; Turpin, Erick A; DiSpirito, Alan A; Semrau, Jeremy D

    2015-11-01

    Methanotrophs have multiple methane monooxygenases that are well known to be regulated by copper, i.e., a "copper switch." At low copper/biomass ratios the soluble methane monooxygenase (sMMO) is expressed while expression and activity of the particulate methane monooxygenase (pMMO) increases with increasing availability of copper. In many methanotrophs there are also multiple methanol dehydrogenases (MeDHs), one based on Mxa and another based on Xox. Mxa-MeDH is known to have calcium in its active site, while Xox-MeDHs have been shown to have rare earth elements in their active site. We show here that the expression levels of Mxa-MeDH and Xox-MeDH in Methylosinus trichosporium OB3b significantly decreased and increased, respectively, when grown in the presence of cerium but the absence of copper compared to the absence of both metals. Expression of sMMO and pMMO was not affected. In the presence of copper, the effect of cerium on gene expression was less significant, i.e., expression of Mxa-MeDH in the presence of copper and cerium was slightly lower than in the presence of copper alone, but Xox-MeDH was again found to increase significantly. As expected, the addition of copper caused sMMO and pMMO expression levels to significantly decrease and increase, respectively, but the simultaneous addition of cerium had no discernible effect on MMO expression. As a result, it appears Mxa-MeDH can be uncoupled from methane oxidation by sMMO in M. trichosporium OB3b but not from pMMO. PMID:26296730

  16. Optical properties of cerium-codoped high power laser fibers

    NASA Astrophysics Data System (ADS)

    Unger, S.; Schwuchow, A.; Jetschke, S.; Grimm, S.; Scheffel, A.; Kirchhof, J.

    2013-03-01

    The photodarkening resistivity of ytterbium doped alumosilicate fibers can be remarkably improved by cerium codoping. Here we report on systematical investigations of the influence of cerium on an optimized fiber design. Fibers with different ytterbium, aluminium and cerium contents have been prepared both under reducing and oxydizing conditions and characterized concerning refractive index, absorption and emission from UV to NIR. Typical spectral features in the UV and visible range have been analysed with respect to the ratio of Ce3+ / Ce4+. Photodarkening tests have been accomplished in order to correlate the power stability with the Ce content and valency state.

  17. Antibacterial activity of cerium colloids against opportunistic microorganisms in vitro.

    PubMed

    Babenko, L P; Zholobak, N M; Shcherbakov, A B; Voychuk, S I; Lazarenko, L M; Spivak, M Ya

    2012-01-01

    The CeO2 sol with the size of nanoparticles 2-4 nm has been synthesized. It has been determined that the synthesized nanocrystalline cerium has antibacterial activity in vitro against different groups of opportunistic microorganisms: clinical strains of Escherichia coli, Staphylococcus aureus and Candida albicans. The rate of viability depression of test-cultures depends on the concentration of cerium dioxide nanoparticles and time of incubation. It is shown that the sol interacts with the bacterial cell surface. It is suggested that the observed differences of antibacterial action of nanocrystalline cerium dioxide can be related to the structural characteristics of the cell surface.

  18. Blue/pink/purple electroluminescence from metal-oxide-semiconductor devices fabricated by spin-coating of [tantalum:(gadolinium/praseodymium)] and (praseodymium:cerium) organic compounds on silicon

    NASA Astrophysics Data System (ADS)

    Ohzone, Takashi; Matsuda, Toshihiro; Fukuoka, Ryouhei; Hattori, Fumihiro; Iwata, Hideyuki

    2016-08-01

    Blue/pink/purple electroluminescence (EL) from metal-oxide-semiconductor (MOS) devices with an indium tin oxide (ITO)/[Gd/(Ta + Gd/Pr)/(Pr + Ce)-Si-O] insulator layer/n+-Si substrate surface is reported. The insulator layers were fabricated from organic liquid sources of Gd or (Ta + Gd/Pr)/(Pr + Ce) mixtures, which were spin-coated on the n+-Si substrate and annealed at 950 °C for 30 min in air. The EL emission could be observed by the naked eye in the dark in the Fowler-Nordheim (FN) tunnel current regions. Peak wavelengths in the measured EL spectra were independent of the positive current. The EL intensity ratio of ultraviolet (UV) to the visible range varied with the composition ratio of the (Ta + Gd) liquids, and an optimum Ta to Gd ratio existed for the strongest blue emission, which could be attributed to the Ta-related oxide/silicate. The pink EL of the device fabricated with the (\\text{Ta}:\\text{Pr} = 6:4) mixture ratio can be explained by EL emission peaks related to the Pr3+ ions. The purple EL observed from the (\\text{Pr}:\\text{Ce} = 6:4) device corresponds to the strong and broad emission profile near the 357 nm peak, which cannot be assigned to Ce3+ ions. The results suggest that the EL can be attributed to the double-layer oxides with different compositions in the MOS devices. The upper layer consists of various Ta-, Gd-, Pr-, and Ce-related oxides and their silicates, while the lower SiO x -rich layer contributes to the FN current due to the high electric field, and thus the various EL colors.

  19. Influence of Collector Surface Composition and Water Chemistry on the Deposition of Cerium Dioxide Nanoparticles: QCM-D and Column Experiment Approaches

    EPA Science Inventory

    The deposition behavior of cerium dioxide (CeO2) nanoparticles (NPs) in dilute NaCl solutions was investigated as a function of collector surface composition, pH, ionic strength, and organic matter (OM). Sensors coated separately with silica, iron oxide, and alumina were applied ...

  20. Using cerium anomaly as an indicator of redox reactions in constructed wetland

    NASA Astrophysics Data System (ADS)

    Liang, R.

    2013-12-01

    The study area, Chiayi County located in southern Taiwan, has highly developed livestock. The surface water has very low dissolved oxygen and high NH4. Under the situation, constructed wetland becomes the most effective and economic choice to treat the wastewater in the natural waterways. Hebao Island free surface constructed wetland started to operate in late 2006. It covers an area of 0.28 km2 and is subdivided into 3 major cells, which are sedimentation cell, 1st aeration cell with rooted plants and 2nd aeration cell with float plants. The water depth of cells ranges from 0.6 m to 1.2 m. The total hydraulic retention time is about a half day. In this study, the water samples were sequentially collected along the flow path. The results of hydrochemical analysis show that the untreated inflow water can be characterized with enriched NH4 (11 ppm), sulfate (6 ppm) and arsenic (50 ppb). The removal efficiency of NH4 in the first two cells is <15%. However, the efficiency dramatically increases in the 2nd aeration cell, which is over 90%. Simultaneously, almost all of the hydrochemical properties, including EC, Ca, Mg, As Fe, Mn and other heavy metals, decrease while dissolve oxygen increases close to saturated level and aluminum is almost doubled in the exit of constructed wetland. However, the removal of sulfate and phosphate is very weak. It is worth to note that arsenic is still higher than the permissible limits recommended by WHO (10 ppb). The wetland operation should be tuned to take more arsenic away in the future. As demonstrated in the above, oxidation reaction is the most dominant mechanism to remove pollutants from the wastewater; therefore, dissolved oxygen is traditionally considered as an important indicator to evaluate the operation efficiency of wetland. However, it would need longer time to achieve equilibrium state of redox reaction involving dissolved oxygen due to the slower reaction rate. For example, the input water in this study has fairly high

  1. The role of cerium redox state in the SOD mimetic activity of nanoceria

    PubMed Central

    Heckert, Eric; Karakoti, Ajay; Seal, Sudipta; Self, William T.

    2008-01-01

    Cerium oxide nanoparticles (nanoceria) have recently been shown to protect cells against oxidative stress in both cell culture and animal models. Nanoceria has been shown to exhibit superoxide dismutase (SOD) activity using a ferricytochrome C assay, and it is this mimetic activity that has been postulated to be responsible for cellular protection by nanoceria. The nature of nanoceria’s antioxidant properties, specifically what physical characteristics make nanoceria effective at scavenging superoxide anion, is poorly understood. In this study electron paramagnetic resonance (EPR) analysis confirms the reactivity of nanoceria as an SOD mimetic. X-ray photoelectron spectroscopy (XPS) and UV-visible analysis of nanoceria treated with hydrogen peroxide demonstrate that a decrease in the Ce 3+/4+ ratio correlates directly with a loss of SOD mimetic activity. These results strongly suggest that the surface oxidation state of nanoceria plays an integral role in the SOD mimetic activity of nanoceria and that ability of nanoceria to scavenge superoxide is directly related to cerium (III) concentrations at the surface of the particle. PMID:18395249

  2. Cerium migration during PEM fuel cell assembly and operation

    DOE PAGESBeta

    Baker, Andrew M.; Torraco, Dennis; Judge, Elizabeth J.; Spernjak, Dusan; Mukundan, Rangachary; Borup, Rod L.; Advani, Suresh G.; Prasad, Ajay K.

    2015-09-14

    Cerium migration between PEM fuel cell components is influenced by potential-driven mobility, ionic diffusion, and gradients in water content. These factors were investigated in ex situ experiments and in operating fuel cells. Potential-induced migration was measured ex situ in hydrated window cells. Cerium-containing MEAs were also fabricated and tested under ASTs. MEA disassembly and subsequent XRF analysis were used to observe rapid cerium migration during cell assembly and operation. During MEA hot pressing, humidification, and low RH operation at OCV, ionic diffusion causes uniform migration from the membrane into the catalyst layers. During high RH operation at OCV, in-plane ceriummore » gradients arise due to variations in water content. These gradients may diminish the scavenging efficacy of cerium by reducing its proximity to generated radicals.« less

  3. Effects of the Rare Earth Cerium on Escherichia coli

    PubMed Central

    Sobek, Joseph M.; Talburt, Dwight E.

    1968-01-01

    The rare earth cerium was found to bind rapidly to Escherichia coli. Cerium inhibited oxygen uptake in the presence of glucose as well as the endogenous respiration of glucose-grown cells. For a cell concentration of 4 mg per ml, maximal inhibition was obtained at 120 μg per ml. Greater concentrations did not increase the inhibitory effect. Cerium inhibited 14CO2 evolution and 14C uptake from uniformly labeled glucose. Marked changes in the distribution of 14C incorporated into different chemical fractions of the cell were noted. The most striking changes occurred in the alcohol- and alcohol ether-soluble fractions, in which the 14C activity was increased 5- to 20-fold in the presence of cerium. PMID:4866102

  4. SOx removal by calcined MgAlFe hydrotalcite-like materials: effect of the chemical composition and the cerium incorporation method.

    PubMed

    Cantú, Manuel; López-Salinas, Esteban; Valente, Jaime S; Montiel, Ramon

    2005-12-15

    Sulfur oxides are one of the most hazardous atmospheric pollutants since they contribute directly to acid rain formation. Consequently, stringent environmental regulations limit atmospheric SOx emissions, motivating research on efficient ways to reduce them. To supply an alternative to reduce these emissions in fluid catalytic cracking units, this study discloses efficient SOx reducing materials based on calcined MgAlFe hydrotalcite-like compounds (HT's). Thus, HT materials were synthesized by several methods including cerium addition. The adsorption of SO2 was carried out by contacting the calcined solid with a mixture of SO2 (1%) in air at 650 degrees C. It was demonstrated that the isomorphic incorporation of iron increased its reduction capability which was reflected in higher reduction rates and metal sulfate reduction grade at 550 degrees C. Moreover, when cerium was present in the iron-containing materials the saturation rate was improved, because cerium oxide promotes the oxidation of SO2 to SO3. The way cerium is incorporated influences the SO2 adsorption capacity.

  5. Preparation of Carbon-Platinum-Ceria and Carbon-Platinum-Cerium catalysts and its application in Polymer Electrolyte Fuel Cell: Hydrogen, Methanol, and Ethanol

    NASA Astrophysics Data System (ADS)

    Guzman Blas, Rolando Pedro

    This thesis is focused on fuel cells using hydrogen, methanol and ethanol as fuel. Also, in the method of preparation of catalytic material for the anode: Supercritical Fluid Deposition (SFD) and impregnation method using ethylenediaminetetraacetic acid (EDTA) as a chelating agent. The first part of the thesis describes the general knowledge about Hydrogen Polymer Exchange Membrane Fuel Cell (HPEMFC),Direct Methanol Fuel Cell (DMFC) and Direct Ethanol Fuel Cell (DEFC), as well as the properties of Cerium and CeO2 (Ceria). The second part of the thesis describes the preparation of catalytic material by Supercritical Fluid Deposition (SFD). SFD was utilized to deposit Pt and ceria simultaneously onto gas diffusion layers. The Pt-ceria catalyst deposited by SFD exhibited higher methanol oxidation activity compared to the platinum catalyst alone. The linear sweep traces of the cathode made for the methanol cross over study indicate that Pt-Ceria/C as the anode catalyst, due to its better activity for methanol, improves the fuel utilization, minimizing the methanol permeation from anode to cathode compartment. The third and fourth parts of the thesis describe the preparation of material catalytic material Carbon-Platinum-Cerium by a simple and cheap impregnation method using EDTA as a chelating agent to form a complex with cerium (III). This preparation method allows the mass production of the material catalysts without additional significant cost. Fuel cell polarization and power curves experiments showed that the Carbon-Platinum-Cerium anode materials exhibited better catalytic activity than the only Vulcan-Pt catalysts for DMFC, DEFC and HPEMFC. In the case of Vulcan-20%Pt-5%w Cerium, this material exhibits better catalytic activity than the Vulcan-20%Pt in DMFC. In the case of Vulcan-40% Pt-doped Cerium, this material exhibits better catalytic activity than the Vulcan-40% Pt in DMFC, DEFC and HPEMFC. Finally, I propose a theory that explains the reason why the

  6. Predicting Cerium + H2O Cluster Formation with Simulated and Experimental Spectroscopy

    NASA Astrophysics Data System (ADS)

    Topolski, Josey E.; Kafader, Jared O.; Ray, Manisha; Chick Jarrold, Caroline

    2016-06-01

    Ceria (CeO2) has been established as a good support in heterogeneous catalysts for the water gas shift reaction. This study looks into cerium's reactivity with water, a water gas shift reagent, and aims to build an understanding of the three reactions which can occur: direct oxidation, -OH abstraction, and H2O addition. Through the use of anion photoelectron spectroscopy and density functional theory calculations we have been able to determine that the reactivity is dependent on (1) the oxidation states of the metal centers, (2) the availability of 5d orbitals to form metal oxide bonds, and (3) the presence of electrons in the 6s* orbital. The results of this study can be used to inform design of catalytic materials for the water gas shift reaction.

  7. Nickel aluminides and nickel-iron aluminides for use in oxidizing environments

    DOEpatents

    Liu, Chain T.

    1988-03-15

    Nickel aluminides and nickel-iron aluminides treated with hafnium or zirconium, boron and cerium to which have been added chromium to significantly improve high temperature ductility, creep resistance and oxidation properties in oxidizing environments.

  8. Panthenol-stabilized cerium dioxide nanoparticles for cosmeceutic formulations against ROS-induced and UV-induced damage.

    PubMed

    Zholobak, N M; Shcherbakov, A B; Bogorad-Kobelska, A S; Ivanova, O S; Baranchikov, A Ye; Spivak, N Ya; Ivanov, V K

    2014-01-01

    A method of panthenol-stabilized cerium dioxide nanoparticles synthesis was developed and their effect on the survival rate of human epidermoid cancer cells HEp-2 and diploid epithelial swine testicular cell line (ST-cells) under oxidative stress conditions induced by hydrogen peroxide introduction and UV irradiation was studied. The results obtained indicate that the use of panthenol as a stabilizer supposedly provides a substantial increase in the efficiency of protection. The degree of protection is determined by panthenol-to-ceria molar ratio. The combination of panthenol and nano-ceria protects biological objects under study from reactive oxygen species (ROS) and UV-irradiation more effectively than individual panthenol or ceria. The protective action of panthenol-stabilized cerium dioxide nanoparticles depends strongly on their composition and the means of their application.

  9. Panthenol-stabilized cerium dioxide nanoparticles for cosmeceutic formulations against ROS-induced and UV-induced damage.

    PubMed

    Zholobak, N M; Shcherbakov, A B; Bogorad-Kobelska, A S; Ivanova, O S; Baranchikov, A Ye; Spivak, N Ya; Ivanov, V K

    2014-01-01

    A method of panthenol-stabilized cerium dioxide nanoparticles synthesis was developed and their effect on the survival rate of human epidermoid cancer cells HEp-2 and diploid epithelial swine testicular cell line (ST-cells) under oxidative stress conditions induced by hydrogen peroxide introduction and UV irradiation was studied. The results obtained indicate that the use of panthenol as a stabilizer supposedly provides a substantial increase in the efficiency of protection. The degree of protection is determined by panthenol-to-ceria molar ratio. The combination of panthenol and nano-ceria protects biological objects under study from reactive oxygen species (ROS) and UV-irradiation more effectively than individual panthenol or ceria. The protective action of panthenol-stabilized cerium dioxide nanoparticles depends strongly on their composition and the means of their application. PMID:24300997

  10. A structural and thermodynamic basis for the catalytic behavior of single phase and multiphase bismuth cerium molybdate ammoxidation catalysts

    SciTech Connect

    Brazdil, J.F.; Glaeser, L.C.; Grasselli, R.K.; Teller, R.G.

    1983-09-01

    The vast majority of fundamental studies of metal oxide selective oxidation catalysts have been performed with single phase systems. These investigations established the basic tenents of the redox mechanism of selective oxidation and ammoxidation catalysis. By comparison, structural and kinetic investigations of multiphase oxide catalysts are less numerous because of the inherent difficulties in understanding the relative contributions of separate phases to the catalytic behavior of the composite catalyst. Some attempts have been made in the past to understand the complex chemistry of multiphase catalysts and additional important insights have been realized more recently. However, a clear understanding of the most significant catalytic interactions between individual phases of a multiphase multicomponent redox catalyst is still lacking. In an effort to provide an understanding and a physical basis for the observed synergism in multiphase oxide catalysts, the structural and chemical features which dictate the catalytic behavior of bismuth cerium molybdate catalysts were assessed. Bismuth cerium molybdates are known to be active catalysts for the selective oxidation and ammoxidation of olefins. Compositions with superior catalytic performance have been identified in both the single phase and two phase regions of the Bi/sub 2/(MoO/sub 4/)/sub 3/ - Ce/sub 2/(MoO/sub 4/)/sub 3/ phase diagram. Hence, this catalyst system serves as a useful model for determining key structural and thermodynamic aspects of the catalytic behavior of multicomponent single phase and multiphase redox catalysts.

  11. Mechanical and Thermophysical Properties of Cerium Monopnictides

    NASA Astrophysics Data System (ADS)

    Bhalla, Vyoma; Singh, Devraj; Jain, S. K.

    2016-03-01

    The ultrasonic attenuation due to phonon-phonon interaction, thermoelastic relaxation and dislocation damping mechanisms has been investigated in cerium monopnictides CeX (X: N, P, As, Sb and Bi) for longitudinal and shear waves along {< }100{rangle }, {< }110{rangle } and {< }111{rangle } directions. The second- and third-order elastic constants of CeX have also been computed in the temperature range 0 K to 500 K using Coulomb and Born-Mayer potential upto second nearest neighbours. The computed values of these elastic constants have been applied to find out Young's moduli, bulk moduli, Breazeale's non-linearity parameters, Zener anisotropy, ultrasonic velocity, ultrasonic Grüneisen parameter, thermal relaxation time, acoustic coupling constants and ultrasonic attenuation. The fracture/toughness ratio is less than 1.75, which shows that the chosen materials are brittle in nature as found for other monopnictides. The drag coefficient acting on the motion of screw and edge dislocations due to shear and compressional phonon viscosities of the lattice have also been evaluated for both the longitudinal and shear waves. The thermoelastic loss and dislocation damping loss are negligible in comparison to loss due to Akhieser damping (phonon-phonon interaction). The obtained results for CeX are in qualitative agreement with other semi-metallic monopnictides.

  12. Characterization of cerium fluoride nanocomposite scintillators

    SciTech Connect

    Stange, Sy; Esch, Ernst I; Brown, Leif O; Couture, Aaron J; Mckigney, Edward A; Muenchausen, Ross E; Del Sesto, Rico E; Gilbertson, Robert D; Mccleskey, T Mark; Reifarth, Rene

    2009-01-01

    Measurement of the neutron capture cross-sections of a number of short-lived isotopes would advance both pure and applied scientific research. These cross-sections are needed for calculation of criticality and waste production estimates for the Advanced Fuel Cycle Initiative, for analysis of data from nuclear weapons tests, and to improve understanding of nucleosynthesis. However, measurement of these cross-sections would require a detector with a faster signal decay time than those used in existing neutron capture experiments. Crystals of faster detector materials are not available in sufficient sizes and quantities to supply these large-scale experiments. Instead, we propose to use nanocomposite detectors, consisting of nanoscale particles of a scintillating material dispersed in a matrix material. We have successfully fabricated cerium fluoride (CeF{sub 3}) nanoparticles and dispersed them in a liquid matrix. We have characterized this scintillator and have measured its response to neutron capture. Results of the optical, structural, and radiation characterization will be presented.

  13. Dehydrogenation of isopropanol on a cerium-nickel catalyst

    NASA Astrophysics Data System (ADS)

    Platonov, E. A.; Naumkin, A. V.; Maslakov, K. I.; Yagodovskii, V. D.

    2012-12-01

    The effect of a cerium additive on the catalytic activity of a 2 wt % Ni/SiO2 catalyst is studied. It found that under both flow and static conditions the activity of (2 wt % Ni + 0.2 wt % Ce)/SiO2 catalyst is higher than that of the original sample; the increase in activity results from a sharp increase in the number of active sites. A change in the composition of the surface layer of the catalysts is analyzed by X-ray photoelectron spectroscopy. It was found that the fraction of nickel decreases and the fraction of carbon increases in cerium-containing catalyst. An explanation of the change in the elemental composition of the catalytic active sites of a nickel catalyst in the presence of cerium is proposed on the basis of XPS data and previous quantum chemical calculations.

  14. Gene-Expression Changes in Cerium Chloride-Induced Injury of Mouse Hippocampus

    PubMed Central

    Sheng, Lei; Zhu, Liyuan; Guan, Ning; Gui, Suxin; Sang, Xuezi; Zhao, Xiaoyang; Sun, Qingqing; Wang, Ling; Cheng, Jie; Hu, Renping; Hong, Fashui

    2013-01-01

    Cerium is widely used in many aspects of modern society, including agriculture, industry and medicine. It has been demonstrated to enter the ecological environment, is then transferred to humans through food chains, and causes toxic actions in several organs including the brain of animals. However, the neurotoxic molecular mechanisms are not clearly understood. In this study, mice were exposed to 0.5, 1, and 2 mg/kg BW cerium chloride (CeCl3) for 90 consecutive days, and their learning and memory ability as well as hippocampal gene expression profile were investigated. Our findings suggested that exposure to CeCl3 led to hippocampal lesions, apoptosis, oxidative stress and impairment of spatial recognition memory. Furthermore, microarray data showed marked alterations in the expression of 154 genes involved in learning and memory, immunity and inflammation, signal transduction, apoptosis and response to stress in the 2 mg/kg CeCl3 exposed hippocampi. Specifically, the significant up-regulation of Axud1, Cdc37, and Ube2v1 caused severe apoptosis, and great suppression of Adcy8, Fos, and Slc5a7 expression led to impairment of mouse cognitive ability. Therefore, Axud1, Cdc37, Ube2v1, Adcy8, Fos, and Slc5a7 may be potential biomarkers of hippocampal toxicity caused by CeCl3 exposure. PMID:23573234

  15. In situ growth of epitaxial cerium tungstate (100) thin films.

    PubMed

    Skála, Tomáš; Tsud, Nataliya; Orti, Miguel Ángel Niño; Menteş, Tevfik Onur; Locatelli, Andrea; Prince, Kevin Charles; Matolín, Vladimír

    2011-04-21

    The deposition of ceria on a preoxidized W(110) crystal at 870 K has been studied in situ by photoelectron spectroscopy and low-energy electron diffraction. Formation of an epitaxial layer of crystalline cerium tungstate Ce(6)WO(12)(100), with the metals in the Ce(3+) and W(6+) chemical states, has been observed. The interface between the tungsten substrate and the tungstate film consists of WO suboxide. At thicknesses above 0.89 nm, cerium dioxide grows on the surface of Ce(6)WO(12), favoured by the limited diffusion of tungsten from the substrate. PMID:21399780

  16. Activity and stability enhancement of copper-alumina catalysts using cerium and zinc promoters for the selective production of hydrogen via steam reforming of methanol

    NASA Astrophysics Data System (ADS)

    Patel, Sanjay; Pant, K. K.

    The catalytic activity and hydrogen selectivity of cerium and zinc promoted copper-alumina catalysts have been investigated for the selective production of hydrogen via steam reforming of methanol (SRM). The SRM was carried out in a fixed bed tubular reactor at atmospheric pressure over a temperature range 200-300 °C. The major reaction products were hydrogen and carbon dioxide with traces of carbon monoxide. Catalysts of varying compositions were prepared by the wet impregnation method and characterized by atomic absorption spectroscopy (AAS), BET surface area, pore volume, pore size, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and thermogravimetry analysis (TGA). Results revealed that the methanol conversion, hydrogen selectivity and carbon monoxide formation varied with the type of promoter and content of copper in the catalyst. Cerium promoted Cu-Zn-Ce-Al-oxide catalysts improved the activity and hydrogen selectivity greatly and also kept the CO formation very low. Using cerium the SRM could be carried out at lower temperature with high methanol conversion, results in suppression of methanol decomposition and reverse water gas shift reactions eventually end-up with the low carbon monoxide and hydrogen rich product stream. Cerium also stabilizes the copper-alumina catalysts effectively that was confirmed by deactivation studies in which cerium promoted Cu-Zn-Ce-Al-oxide catalysts gave the consistent performance for a long run-time compared to catalysts containing only zinc promoter. The optimum operating conditions for SRM have been investigated by detailed study of effects of reaction temperature, contact time and steam to methanol molar ratio on methanol conversion, hydrogen selectivity and CO formation. Reaction pathway has been proposed for the SRM based on results obtained.

  17. Cerium phosphate nanotubes: synthesis, characterization and biosensing

    NASA Astrophysics Data System (ADS)

    Meng, Ling; Yang, Lige; Zhou, Bo; Cai, Chenxin

    2009-01-01

    Cerium phosphate (CeP) nanotubes have been synthesized and confirmed by x-ray diffraction (XRD) and transmission electron microscopy (TEM). The 1D nanomaterial has a monoclinic crystal structure with a mean width of 15-20 nm and a length up to several micrometers. The nanotubes have been employed as electrode substrates for immobilization and direct electrochemistry of heme proteins/enzymes with myoglobin (Mb) as a model. The electrochemical characteristics of the Mb-CeP/GC electrode were studied by voltammetry. After being immobilized on the nanotubes, Mb can keep its natural structure and undergo effective direct electron transfer reaction with a pair of well-defined redox peaks at -(367 ± 3) mV (pH 7.5). The apparent electron transfer rate constant is (9.1 ± 1.4) s-1. The electrode displays good features in the electrocatalytic reduction of H2O2, and thus can be used as a biosensor for detecting the substrate with a low detection limit (0.5 ± 0.05 µM), a wide linear range (0.01-2 mM), high sensitivity (14.4 ± 1.2 µA mM-1), as well as good stability and reproducibility. CeP nanotubes can become a simple and effective biosensing platform for the integration of heme proteins/enzymes and electrodes, which can provide analytical access to a large group of enzymes for a wide range of bioelectrochemical applications.

  18. Aqueous medium induced optical transitions in cerium oxide nanoparticles

    SciTech Connect

    Inerbaev, Talgat M.; Karakoti, Ajay S.; Kuchibhatla, S. V. N. T.; Kumar, Amit; Masunov, Artem E.; Seal, Sudipta

    2015-03-07

    Experimental and theoretical investigations were performed to investigate the effect of water on optical properties of nanoceria as a function of Ce3+ concentration. Theoretical studies based on density functional plane-wave calculations reveal that the indirect optical transitions in bare ceria nanoparticles are red-shifted with an increase in the concentration of Ce3+. However, ceria nanoparticles model with adsorbed water molecules show a blue shift in the indirect optical spectra under identical conditions. Direct optical transitions are almost independent of Ce3+ concentration but show a pronounced blue shift in the aqueous environment relative to the bare nanoparticles. The theoretical study is consistent with our experimental observation in difference of shift behaviour in bare and aqueous suspended ceria nanoparticles. This change from red- to blue-shift in indirect optical transitions is associated with the polarization effect of water molecules on f-electron states.

  19. Aqueous medium induced optical transitions in cerium oxide nanoparticles.

    PubMed

    Inerbaev, Talgat M; Karakoti, Ajay S; Kuchibhatla, Satyanarayana V N T; Kumar, Amit; Masunov, Artëm E; Seal, Sudipta

    2015-03-01

    Experimental and theoretical investigations were performed to investigate the effect of water on optical properties of nanoceria as a function of Ce(3+) concentration. Theoretical studies based on density functional plane-wave calculations reveal that the indirect optical transitions in bare ceria nanoparticles are red-shifted with an increase in the concentration of Ce(3+). However, ceria nanoparticles model with adsorbed water molecules show a blue shift in the indirect optical spectra under identical conditions. Direct optical transitions are almost independent of Ce(3+) concentration but show a pronounced blue shift in the aqueous environment relative to the bare nanoparticles. The theoretical study is consistent with our experimental observation in difference of shift behaviour in bare and aqueous suspended ceria nanoparticles. This change from red- to blue-shift in indirect optical transitions is associated with the polarization effect of water molecules on f-electron states. PMID:25655842

  20. Impact of cerium oxide nanoparticles on cilantro ( Coriandrum sativum)

    NASA Astrophysics Data System (ADS)

    Morales, Maria Isabel

    Studies have shown that plants exposed to ENPs suffer different types of stress. Other studies have revealed that plants can take up and accumulate CeO2 NPs without modification. Thus, these NPs could enter the food chain through edible plants, posing a threat for human health. Cilantro (Coriandrum sativum) is a worldwide culinary and medicinal plant consumed either as a fresh herb or a spice. In this research, cilantro plants were germinated and cultivated for 30 days in organic soil treated with CeO2 NPs at concentrations varying from 0 to 500 mg kg -1. Subsequently, plant organs were analyzed by using spectroscopic techniques and biochemical assays. Results indicate that at 125 mg kg -1, the CeO2 NPs significantly increased the root size compared with the other treatments. The ICP-OES results showed that plants exposed to 500 mg kg-1 had significantly (p ≤ 0.05) more Ce in shoots and roots compared to the other treatments. Results from the biochemical assays showed that at 125 mg kg-1, catalese activity significantly increased in shoots and ascorbate peroxidase in roots (p ≤ 0.05). In addition, the FTIR analyses revealed that at 125 mg kg-1, the CeO2 NPs changed the chemical environment of the carbohydrates within the cilantro shoots, for which changes in the area of the stretching frequencies were observed. Moreover, analyses of antioxidant compounds showed a significant ( p ≤ 0.05) reduction on total phenolic content in shoots of cilantro plants treated with 500 mg CeO2 NPs kg-1 . This suggests that the CeO2 NPs have the potential to diminish the ability of cilantro plants to scavenge reactive oxygen species. The multi-elemental analysis showed that plants treated with CeO2 at the 500 mg kg-1 treatment had a significant ( p ≤ 0.05) reduction in shoots' sulfur, silicon, and zinc accumulation. The results of this research indicate that the CeO2 NPs at 500 mg CeO2 kg-1 concentration cause a reduction in the antioxidant ability and nutritional properties of cilantro plants.

  1. Study on the adsorptive stripping voltammetric determination of trace cerium at a carbon paste electrode modified in situ with cetyltrimethylammonium bromide

    NASA Astrophysics Data System (ADS)

    Liu, Shumei; Li, Junan; Zhang, Shijie; Zhao, Jianqing

    2005-12-01

    A procedure was developed for the determination of trace cerium based on the oxidation of the absorbed cerium (III)-alizarin complexon (ALC) complex at a carbon paste electrode (CPE) modified in situ with cetyltrimethylammonium bromide (CTAB). Optimum experiment conditions included 2.0 × 10 -6 mol l -1 ALC, 6.0 × 10 -5 mol l -1 CTAB , 0.1 mol l -1 acetic acid and sodium acetate (HAc-NaAc) and 0.2 mol l -1 potassium biphthalate (KHP), pH 5.0, an accumulation potential of -0.1 V, and a scan rate of 100 mV s -1. Linearity between peak currents and concentrations existed for 8.0 × 10 -10 to 8.0 × 10 -9 mol l -1 for 120 s accumulation and 8.0 × 10 -9 to 1.0 × 10 -7 mol l -1 for 60 s accumulation. The detection limit after a 120 s preconcentration was 6.0 × 10 -10 mol l -1 (S/N = 3). The relative standard deviation was 4.9% for eight successive determinations on the same electrode surface at 2.0 × 10 -8 mol l -1 level. The procedure was expected to determine trace cerium with elevated selectivity. The results were quite consistent with the certified values for the determination of cerium in rare earth nodular cast iron samples.

  2. Nanoparticulate cerium dioxide and cerium dioxide-titanium dioxide composite thin films on glass by aerosol assisted chemical vapour deposition

    NASA Astrophysics Data System (ADS)

    Qureshi, Uzma; Dunnill, Charles W.; Parkin, Ivan P.

    2009-11-01

    Two series of composite thin films were deposited on glass by aerosol assisted chemical vapour deposition (AACVD)—nanoparticulate cerium dioxide and nanoparticulate cerium dioxide embedded in a titanium dioxide matrix. The films were analysed by a range of techniques including UV-visible absorption spectroscopy, X-ray diffraction, scanning electron microscopy and energy dispersive analysis by X-rays. The AACVD prepared films showed the functional properties of photocatalysis and super-hydrophilicity. The CeO 2 nanoparticle thin films displaying photocatalysis and photo-induced hydrophilicity almost comparable to that of anatase titania.

  3. Cerium; crystal structure and position in the periodic table.

    PubMed

    Johansson, Börje; Luo, Wei; Li, Sa; Ahuja, Rajeev

    2014-09-17

    The properties of the cerium metal have intrigued physicists and chemists for many decades. In particular a lot of attention has been directed towards its high pressure behavior, where an isostructural volume collapse (γ phase → α phase) has been observed. Two main models of the electronic aspect of this transformation have been proposed; one where the 4f electron undergoes a change from being localized into an itinerant metallic state, and one where the focus is on the interaction between the 4f electron and the conduction electrons, often referred to as the Kondo volume collapse model. However, over the years it has been repeatedly questioned whether the cerium collapse really is isostructural. Most recently, detailed experiments have been able to remove this worrisome uncertainty. Therefore the isostructural aspect of the α-γ transition has now to be seriously addressed in the theoretical modeling, something which has been very much neglected. A study of this fundamental characteristic of the cerium volume collapse is made in present paper and we show that the localized [rlhar2 ] delocalized 4f electron picture provides an adequate description of this unique behavior. This agreement makes it possible to suggest that an appropriate crossroad position for cerium in The Periodic Table.

  4. Cerium; Crystal Structure and Position in The Periodic Table

    PubMed Central

    Johansson, Börje; Luo, Wei; Li, Sa; Ahuja, Rajeev

    2014-01-01

    The properties of the cerium metal have intrigued physicists and chemists for many decades. In particular a lot of attention has been directed towards its high pressure behavior, where an isostructural volume collapse (γ phase → α phase) has been observed. Two main models of the electronic aspect of this transformation have been proposed; one where the 4f electron undergoes a change from being localized into an itinerant metallic state, and one where the focus is on the interaction between the 4f electron and the conduction electrons, often referred to as the Kondo volume collapse model. However, over the years it has been repeatedly questioned whether the cerium collapse really is isostructural. Most recently, detailed experiments have been able to remove this worrisome uncertainty. Therefore the isostructural aspect of the α-γ transition has now to be seriously addressed in the theoretical modeling, something which has been very much neglected. A study of this fundamental characteristic of the cerium volume collapse is made in present paper and we show that the localized ⇌ delocalized 4f electron picture provides an adequate description of this unique behavior. This agreement makes it possible to suggest that an appropriate crossroad position for cerium in The Periodic Table. PMID:25227991

  5. 40 CFR 721.8657 - Cerium, hydroxy oleate propionate complexes.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... complexes. 721.8657 Section 721.8657 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED... Specific Chemical Substances § 721.8657 Cerium, hydroxy oleate propionate complexes. (a) Chemical substance..., hydroxy oleate propionate complexes (PMN P-99-0026) is subject to reporting under this section for...

  6. Steric and electronic effects of 1,3-disubstituted cyclopentadienyl ligands on metallocene derivatives of Cerium, Titanium, Manganese, and Iron

    SciTech Connect

    Sofield, C.D.

    2000-05-19

    Sterically demanding 1,3-disubstituted cyclopentadienyl ligands were used to modify the physical properties of the corresponding metallocenes. Sterically demanding ligands provided kinetic stabilization for trivalent cerium compounds. Tris(di-t-butylcyclopentadienyl)cerium was prepared and anion competition between halides and cyclopentadienyl groups which had complicated synthesis of the tris(cyclopentadienyl)compound was qualitatively examined. Bis(di-t-butylcyclopentadienyl)cerium methyl was prepared and its rate of decomposition, by ligand redistribution, to tris(di-t-butylcyclopentadienyl)cerium was shown to be slower than the corresponding rate for less sterically demanding ligands. Asymmetrically substituted ligands provided a symmetry label for examination of chemical exchange processes. Tris[trimethylsilyl(t-butyl)cyclopentadienyl]cerium was prepared and the rate of interconversion between the C1 and C3 isomers was examined. The enthalpy difference between the two distereomers is 7.0 kJ/mol. The sterically demanding cyclopentadienyl ligands ansa-di-t-butylcyclopentadiene (Me2Si[(Me3C)2C5H3]2), ansa-bis(trimethylsilyl)cyclopentadiene (Me2Si[(Me3Si)2C5H3]2) and tetra-t-butylfulvalene and metallocene derivatives of the ligands were prepared and their structures were examined by single crystal X-ray crystallography. The effect that substituents on the cyclopentadienyl ring have on the pi-electron system of the ligand was examined through interaction between ligand and metal orbitals. A series of 1,3-disubstituted manganocenes was prepared and their electronic states were determined by solid-state magnetic susceptibility, electron paramagnetic resonance, X-ray crystallography, and variable temperature UV-vis spectroscopy. Spin-equilibria in [(Me3C)2C5H3]2Mn and [(Me3C)(Me3Si)C5H3]2Mn were examined and indicate an enthalpy difference of 15 kJ/mol between the high-spin and low-spin forms. Cyclopentadienyl groups resistant to intramolecular oxidative addition

  7. [Determination of silver and cerium in the liver and the kidney from a severely burned infant treated with silver sulfadiazine and cerium nitrate].

    PubMed

    Hirakawa, K

    1983-02-01

    Silver and cerium in the liver and the kidney from severely burned infant were analyzed by neutron activation method. The patient was treated topically with cerium nitrate/silver sulfadiazine cream and cerium nitrate solution for 3 months. Then, the treatment with these drugs was stopped because of abdominal distention. The patient died 1 month after the cessation of the treatment with these drugs. The tissue specimens, blank liver sample and reference standards were irradiated with TRIGA MARK II Reactor of Rikkyo University. About 1 month after the irradiation, the activities were measured with a Ge(Li) detector coupled to a 4096 channel pulse height analyzer. A large amount of silver was detected both in the liver and in the kidney and a trace of cerium only in the liver. A considerable amount of silver was detected in the liver and its quantity was about 1600 times more than that of normal livers reported by Hamilton, Minski and Cleary (1972-73). Neither silver nor cerium were detected in the blank liver. These results suggest that prolonged topical chemotherapy of cerium nitrate/silver sulfadiazine cream and cerium nitrate solution for the extensive burn injuries causes considerable absorption of silver and cerium into the liver and the kidney. PMID:6867381

  8. Changes in Physiological and Agronomical Parameters of Barley (Hordeum vulgare) Exposed to Cerium and Titanium Dioxide Nanoparticles

    PubMed Central

    Marchiol, Luca; Mattiello, Alessandro; Pošćić, Filip; Fellet, Guido; Zavalloni, Costanza; Carlino, Elvio; Musetti, Rita

    2016-01-01

    The aims of our experiment were to evaluate the uptake and translocation of cerium and titanium oxide nanoparticles and to verify their effects on the growth cycle of barley (Hordeum vulgare L.). Barley plants were grown to physiological maturity in soil enriched with either 0, 500 or 1000 mg·kg−1 cerium oxide nanoparticles (nCeO2) or titanium oxide nanoparticles (nTiO2) and their combination. The growth cycle of nCeO2 and nTiO2 treated plants was about 10 days longer than the controls. In nCeO2 treated plants the number of tillers, leaf area and the number of spikes per plant were reduced respectively by 35.5%, 28.3% and 30% (p ≤ 0.05). nTiO2 stimulated plant growth and compensated for the adverse effects of nCeO2. Concentrations of Ce and Ti in aboveground plant fractions were minute. The fate of nanomaterials within the plant tissues was different. Crystalline nTiO2 aggregates were detected within the leaf tissues of barley, whereas nCeO2 was not present in the form of nanoclusters. PMID:26999181

  9. Changes in Physiological and Agronomical Parameters of Barley (Hordeum vulgare) Exposed to Cerium and Titanium Dioxide Nanoparticles.

    PubMed

    Marchiol, Luca; Mattiello, Alessandro; Pošćić, Filip; Fellet, Guido; Zavalloni, Costanza; Carlino, Elvio; Musetti, Rita

    2016-03-17

    The aims of our experiment were to evaluate the uptake and translocation of cerium and titanium oxide nanoparticles and to verify their effects on the growth cycle of barley (Hordeum vulgare L.). Barley plants were grown to physiological maturity in soil enriched with either 0, 500 or 1000 mg · kg(-1) cerium oxide nanoparticles (nCeO₂) or titanium oxide nanoparticles (nTiO₂) and their combination. The growth cycle of nCeO₂ and nTiO₂ treated plants was about 10 days longer than the controls. In nCeO₂ treated plants the number of tillers, leaf area and the number of spikes per plant were reduced respectively by 35.5%, 28.3% and 30% (p ≤ 0.05). nTiO₂ stimulated plant growth and compensated for the adverse effects of nCeO₂. Concentrations of Ce and Ti in aboveground plant fractions were minute. The fate of nanomaterials within the plant tissues was different. Crystalline nTiO₂ aggregates were detected within the leaf tissues of barley, whereas nCeO₂ was not present in the form of nanoclusters.

  10. Apparatus and method for oxidizing organic materials

    DOEpatents

    Surma, Jeffrey E.; Bryan, Garry H.; Geeting, John G. H.; Butner, R. Scott

    1998-01-01

    The invention is a method and apparatus using high cerium concentration in the anolyte of an electrochemical cell to oxidize organic materials. The method and apparatus further use an ultrasonic mixer to enhance the oxidation rate of the organic material in the electrochemical cell.

  11. Apparatus and method for oxidizing organic materials

    SciTech Connect

    Surma, J.E.; Bryan, G.H.; Geeting, J.G.H.; Butner, R.S.

    1998-01-13

    The invention is a method and apparatus using high cerium concentration in the anolyte of an electrochemical cell to oxidize organic materials. The method and apparatus further use an ultrasonic mixer to enhance the oxidation rate of the organic material in the electrochemical cell. 6 figs.

  12. Preparation of olefins from synthesis gas using ruthenium supported on ceric oxide

    DOEpatents

    Pierantozzi, R.

    1985-04-09

    A catalyst comprising a ruthenium carbonyl compound deposited on a cerium oxide-containing support material provides for the selective synthesis of low molecular weight olefinic hydrocarbons from mixtures of hydrogen and carbon monoxide.

  13. Ruthenium carbonyl catalyst supported on ceric oxide for preparation of olefins from synthesis gas

    DOEpatents

    Pierantozzi, R.

    1985-04-02

    A catalyst comprising a ruthenium carbonyl compound deposited on a cerium oxide-containing support material provides for the selective synthesis of low molecular weight olefinic hydrocarbons from mixtures of hydrogen and carbon monoxide.

  14. Ruthenium carbonyl catalyst supported on ceric oxide for preparation of olefins from synthesis gas

    DOEpatents

    Pierantozzi, Ronald

    1985-01-01

    A catalyst comprising a ruthenium carbonyl compound deposited on a cerium oxide-containing support material provides for the selective synthesis of low molecular weight olefinic hydrocarbons from mixtures of hydrogen and carbon monoxide.

  15. Preparation of olefins from synthesis gas using ruthenium supported on ceric oxide

    DOEpatents

    Pierantozzi, Ronald

    1985-01-01

    A catalyst comprising a ruthenium carbonyl compound deposited on a cerium oxide-containing support material provides for the selective synthesis of low molecular weight olefinic hydrocarbons from mixtures of hydrogen and carbon monoxide.

  16. Perovskite catalysts for oxidative coupling

    DOEpatents

    Campbell, K.D.

    1991-06-25

    Perovskites of the structure A[sub 2]B[sub 2]C[sub 3]O[sub 10] are useful as catalysts for the oxidative coupling of lower alkane to heavier hydrocarbons. A is alkali metal; B is lanthanide or lanthanum, cerium, neodymium, samarium, praseodymium, gadolinium or dysprosium; and C is titanium.

  17. Perovskite catalysts for oxidative coupling

    DOEpatents

    Campbell, Kenneth D.

    1991-01-01

    Perovskites of the structure A.sub.2 B.sub.2 C.sub.3 O.sub.10 are useful as catalysts for the oxidative coupling of lower alkane to heavier hydrocarbons. A is alkali metal; B is lanthanide or lanthanum, cerium, neodymium, samarium, praseodymium, gadolinium or dysprosium; and C is titanium.

  18. Study of cerium diffusion in undoped lithium-6 enriched glass with Rutherford backscattering spectrometry

    NASA Astrophysics Data System (ADS)

    Zhang, Xiaodong; Moore, Michael E.; Lee, Kyung-Min; Lukosi, Eric D.; Hayward, Jason P.

    2016-07-01

    Undoped lithium-6 enriched glasses coated with pure cerium (99.9%) with a gold protection layer on top were heated at three different temperatures (500, 550, and 600 °C) for varied durations (1, 2, and 4 h). Diffusion profiles of cerium in such glasses were obtained with the conventional Rutherford backscattering technique. Through fitting the diffusion profiles with the thin-film solution of Fick's second law, diffusion coefficients of cerium with different annealing temperatures and durations were solved. Then, the activation energy of cerium for the diffusion process in the studied glasses was found to be 114 kJ/mol with the Arrhenius equation.

  19. Oxide modified air electrode surface for high temperature electrochemical cells

    DOEpatents

    Singh, Prabhakar; Ruka, Roswell J.

    1992-01-01

    An electrochemical cell is made having a porous cermet electrode (16) and a porous lanthanum manganite electrode (14), with solid oxide electrolyte (15) between them, where the lanthanum manganite surface next to the electrolyte contains a thin discontinuous layer of high surface area cerium oxide and/or praseodymium oxide, preferably as discrete particles (30) in contact with the air electrode and electrolyte.

  20. Isomorphic phase transformation in shocked cerium using molecular dynamics

    SciTech Connect

    Dupont, Virginie; Germann, Timothy C; Chen, Shao - Ping

    2010-08-12

    Cerium (Ce) undergoes a significant ({approx}16%) volume collapse associated with an isomorphic fcc-fcc phase transformation when subject to compressive loading. We present here a new Embedded Atom Method (EAM) potential for Cerium that models two minima for the two fcc phases. We show results from its use in Molecular Dynamics (MD) simulations of Ce samples subjected to shocks with pressures ranging from 0.5 to 25 GPa. A split wave structure is observed, with an elastic precursor followed by a plastic wave. The plastic wave causes the expected fcc-fcc phase transformation. Comparisons to experiments and MD simulations on Cesium (Cs) indicate that three waves could be observed. The construction of the EAM potential may be the source of the difference.

  1. Formation of alumina-ceria mixed oxide in model systems

    NASA Astrophysics Data System (ADS)

    Skála, Tomáš; Tsud, Nataliya; Prince, Kevin C.; Matolín, Vladimír

    2011-02-01

    Interaction of aluminium with cerium oxide was studied by photoelectron spectroscopy of Al/CeO2(1 1 1) and CeO2/Al(1 1 1) model systems. It was found in both cases that metallic aluminium was immediately oxidized, CeO2 was partially reduced and a mixed oxide with cerium present as Ce3+ was formed. The compound is probably cerium aluminate CeAlO3 mixed with Al2O3 or Ce2O3. In both cases the intermixing was limited by the diffusion of aluminium into ceria. The excess of deposited material above this limit formed AlOx and CeO2 overlayers on the top of the mixed oxide + aluminate/CeO2 and mixed oxide + aluminate/Al films, respectively.

  2. Optical Response of Shocked Cerium-Doped Lutetium Oxyorthosilicate

    SciTech Connect

    G. D. Stevens

    2003-03-01

    Shock experiments were performed in order to characterize the triboluminescent signature of cerium-doped lutetium oxyorthosilicate (LSO:Ce). This material shows prompt, nano-second timescale light emission when driven by explosive detonation. When properly applied to a surface, it may be used as a shock arrival sensor, and also for imaging the propagation of a shock front. Triboluminescent rise times, spectral content, and spatial resolution measurements are presented.

  3. Jet formation in cerium metal to examine material strength

    SciTech Connect

    Jensen, B. J. Cherne, F. J.; Prime, M. B.; Yeager, J. D.; Ramos, K. J.; Hooks, D. E.; Cooley, J. C.; Dimonte, G.; Fezzaa, K.; Iverson, A. J.; Carlson, C. A.

    2015-11-21

    Examining the evolution of material properties at extreme conditions advances our understanding of numerous high-pressure phenomena from natural events like meteorite impacts to general solid mechanics and fluid flow behavior. Recent advances in synchrotron diagnostics coupled with dynamic compression platforms have introduced new possibilities for examining in-situ, spatially resolved material response with nanosecond time resolution. In this work, we examined jet formation from a Richtmyer-Meshkov instability in cerium initially shocked into a transient, high-pressure phase, and then released to a low-pressure, higher-temperature state. Cerium's rich phase diagram allows us to study the yield stress following a shock induced solid-solid phase transition. X-ray imaging was used to obtain images of jet formation and evolution with 2–3 μm spatial resolution. From these images, an analytic method was used to estimate the post-shock yield stress, and these results were compared to continuum calculations that incorporated an experimentally validated equation-of-state (EOS) for cerium coupled with a deviatoric strength model. Reasonable agreement was observed between the calculations and the data illustrating the sensitivity of jet formation on the yield stress values. The data and analysis shown here provide insight into material strength during dynamic loading which is expected to aid in the development of strength aware multi-phase EOS required to predict the response of matter at extreme conditions.

  4. Cerium stable isotope ratios in ferromanganese deposits and their potential as a paleo-redox proxy

    NASA Astrophysics Data System (ADS)

    Nakada, Ryoichi; Takahashi, Yoshio; Tanimizu, Masaharu

    2016-05-01

    The cerium (Ce) anomaly observed in rare earth element (REE) patterns has been used to estimate the redox state of paleo-marine environments. Cerium is unique because it forms tetravalent cations under oxic conditions, in contrast to the other REEs that occur in a trivalent state. This characteristic leads to anomalously high or low Ce concentrations relative to neighboring REEs. However, the use of Ce anomaly as a paleo-redox proxy is not well calibrated. This study shows that coupling of the Ce anomaly and Ce stable isotope ratio (δ142Ce) is more quantitative redox proxy to distinguish suboxic and oxic redox conditions. Our results revealed a progressive enrichment in heavy Ce isotopes in consecutive formations of iron (Fe) and manganese (Mn) precipitate from hot spring water without any associated change in REE patterns. The δ142Ce values of Mn precipitates were approximately 0.35‰ heavier than those of the Fe precipitates, which was consistent with experiment-based predictions. The δ142Ce values of marine ferromanganese deposits with three different formation processes were hydrogenetic (+0.25‰) > diagenetic (+0.10‰) ⩾ hydrothermal (+0.05‰), which also reflects redox conditions of their formation environment. These observations suggest that the Ce stable isotope ratios yield more quantitative information regarding redox state than REE patterns alone. We thus suggest that this novel proxy can be successfully utilized to reconstruct marine redox states, particularly from slightly oxic to highly oxic conditions such as the Great Oxidation Event (GOE).

  5. Cerium Substitution in Yttrium Iron Garnet: Valence State, Structure, and Energetics

    SciTech Connect

    Guo, Xiaofeng; Tavakoli, Amir H.; Sutton, Steve; Kukkadapu, Ravi K.; Qi, Liang; Lanzirotti, Anthony; Newville, Mathew; Asta, Mark D.; Navrotsky, Alexandra

    2014-01-28

    The garnet structure is a promising nuclear waste form because it can accommodate various actinide elements. Y3Fe5O12 (YIG) is a model composition for such substitutions. Since cerium (Ce) can be considered an analogue of actinide elements such as thorium (Th), plutonium (Pu), and uranium (U), studying the local structure and thermodynamic stability of Ce-substituted YIG (Ce:YIG) can provide insights into the structural and energetic aspects of large ion substitution in garnets. Single phases of yttrium iron garnet with Ce substitution up to 20 mol % (Y3-xCexFe5O12 with 0 ≤ x ≤ 0.2) were synthesized through a citrate-nitrate combustion method. The oxidation state of cerium was examined by X-ray absorption near edge structure spectroscopy (XANES); the oxidation state and site occupancy of Fe as a function of Ce loading also was monitored by 57Fe-Mössbauer spectroscopy. These measurements establish that Ce is predominantly in the trivalent state at low substitution levels, while a mixture of trivalent and tetravalent states are observed at higher concentrations. Fe was predominately trivalent and exists in multiple environments. High temperature oxide melt solution calorimetry was used to determine the enthalpy of formation of these Ce-substituted YIG garnets. The thermodynamic analysis demonstrated that, although there is an entropic driving force for the substitution of Ce for Y, the substitution reaction is enthalpically unfavorable. The experimental results are complemented by electronic structure calculations performed within the framework of density functional theory (DFT) with Hubbard-U corrections, which reproduce the observed increase in the tendency for tetravalent Ce to be present with higher loading of Ce. The DFT+U results suggest that the energetics underlying the formation of tetravalent Ce involves a competition between an unfavorable energy to oxidize Ce and reduce Fe, and a favorable contribution due to strain-energy reduction. The structural

  6. Potential of a Hydrometallurgical Recycling Process for Catalysts to Cover the Demand for Critical Metals, Like PGMs and Cerium

    NASA Astrophysics Data System (ADS)

    Steinlechner, Stefan; Antrekowitsch, Jürgen

    2015-02-01

    The metals from the platinum group are used in many different industries, for example dental, jewelry, and chemicals. Nevertheless, the most important use is based on their catalytic properties. Approximately 50% of platinum and palladium are used as automotive and industrial catalysts. In case of rhodium, an even higher percentage (around 80-90%) is used as an alloying element in the active layer of different catalysts. The high required amount of 300-900 kg of treated ore to obtain approximately 1 g of PGM is responsible for the high prices. On average, the contents in the ore of Pt and Pd are 5-10 times higher than Rh and Ru and around 50 times higher than Ir and Os. Additionally, the regional limitation of ore bodies leads to a strong dependence on mainly South Africa and Russia as PGM suppliers. Based on the strong discrepancy in supply and demand of PGM's around the world, recycling of catalysts is mandatory and meaningful from the ecological and economical point of view. Based on the high prices of PGM, the industry is forced to improve the efficiency of catalysts, which is done by improving the wash coat technology. By using rare-earth elements, like cerium oxide, the surface can be increased and the ability to supply oxygen is secured. As a side effect, cerium as an additional critical element is introduced into the recycling circuit of catalytic converters, forming a further valuable component and forming a major challenge for common pyrometallurgical converter recycling. Therefore, this article introduces a hydrometallurgical process, developed together with Railly&Hill Inc., for PGM as well as cerium recovery from catalytic converters.

  7. Equation of state of quartz glass and cerium in their abnormal compressibility range

    NASA Astrophysics Data System (ADS)

    Molodets, A. M.

    2016-09-01

    In this work, the semiempirical equation of state of quartz glass and polycrystalline γ-cerium are plotted and verified at the compressive pressures to 3 GPa. The proposed equations are shown to uniformly describe the thermophysical and physicomechanical properties of quartz glass and polycrystalline γ-cerium at their abnormal compressibility in compression. The room isotherms of these materials are discussed, as well.

  8. Reactions of carbonyl compounds with Grignard reagents in the presence of cerium chloride

    SciTech Connect

    Imamoto, Tsuneo; Takiyama, Nobuyuki; Nakamura, Kimikazu; Hatajima, Toshihiko; Kamiya, Yasuo )

    1989-06-07

    The addition of Grignard reagents to ketones is significantly enhanced by cerium chloride with remarkable suppression of side reactions, particularly enolization. Some esters, which are prone to side reactions, also react readily with Grignard reagents in the presence of cerium chloride to give normal reaction products in reasonable to high yields.

  9. Modified cermet fuel electrodes for solid oxide electrochemical cells

    DOEpatents

    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.

  10. Effect of ultrasound treatment on the morpho-structural and luminescent characteristics of cerium doped yttrium silicate phosphors

    SciTech Connect

    Muresan, L.E.; Cadis, A.I.; Perhaita, I.; Silipas, D.T.; Tudoran, L. Barbu

    2015-08-15

    Highlights: • Y{sub 2}SiO{sub 5}:Ce is prepared by gel combustion in ultrasound conditions (US). • Morpho-structural characteristics are revealed based on FTIR, SEM, XRD, BET. • Incorporation of Ce{sup 3+} in X1/X2 type centers depends on preparative conditions. • US treatment increases the luminescent performances up to 151%. - Abstract: Cerium activated yttrium silicate (Y{sub 2}SiO{sub 5}:Ce) phosphors were prepared by gel-combustion, using yttrium–cerium nitrate as oxidizer, aspartic acid as fuel and TEOS as source of silicon. Two modalities for samples preparation were approached namely: the classical gel-combustion and sonication gel-combustion. The ultrasound treatment during the gelling stage has a positive effect on the structural and luminescent characteristics of the final product. Therefore, a well crystallized single X2–Y{sub 2}SiO{sub 5} phase phosphor was obtained at 1200 °C. Based on FT-IR and XRD investigations, conversion of X1 to X2–Y{sub 2}SiO{sub 5} phases is observed as the firing temperature is varied (1100 °C, 1200 °C, 1300 °C 1400 °C). The ultrasound treatment leads to smaller particle size and enhances the luminescent performances up to 151% in comparison with samples prepared by classical way.

  11. Molecular mechanisms of silk gland damage caused by phoxim exposure and protection of phoxim-induced damage by cerium chloride in Bombyx mori.

    PubMed

    Li, Bing; Sun, Qingqing; Yu, Xiaohong; Xie, Yi; Hong, Jie; Zhao, Xiaoyang; Sang, Xuezi; Shen, Weide; Hong, Fashui

    2015-09-01

    It is known that exposure to organophosphorus pesticides (OP) including phoxim can produce oxidative stress, neurotoxicity, and greatly attenuate cocooning rate in the silkworm, Bombyx mori. Cerium treatment has been demonstrated to relieve phoxim-induced toxicity in B. mori; however, very little is known about the molecular mechanisms of silk gland injury due to OP exposure and protection of gland damage due to cerium pretreatment. The aim of this study was to evaluate silk gland damage and its molecular mechanisms in phoxim-induced silkworm toxicity and the protective mechanisms of cerium following exposure to phoxim. The results showed that phoxim exposure resulted in severe gland damage, reductions in protein synthesis and the cocooning rate of silkworms. Cerium (Ce) attenuated gland damage caused by phoxim, promoted protein synthesis, increased the antioxidant capacity of the gland and increased the cocooning rate of B. mori. Furthermore, digital gene expression data suggested that phoxim exposure led to significant up-regulation of 714 genes and down-regulation of 120 genes. Of these genes, 122 were related to protein metabolism, specifically, the down-regulated Ser2, Ser3, Fib-L, P25, and CYP450. Ce pretreatment resulted in up-regulation of 162 genes, and down-regulation of 141 genes, importantly, Ser2, Ser3, Fib-L, P25, and CYP333B8 were up-regulated. Treatment with CeCl3 + phoxim resulted in higher levels of Fib-L, P25, Ser2, Ser3, CAT, TPx, and CYP333B8 expression in the silk gland of silkworms. These findings indicated that Ce increased cocooning rate via the promotion of silk protein synthesis-related gene expression in the gland under phoxim-induced toxicity. These findings may expand the application of rare earths in sericulture.

  12. Cerium redox cycles and rare earth elements in the Sargasso Sea

    SciTech Connect

    Sholkovitz, E.R.; Schneider, D.L. )

    1991-10-01

    Two profiles of the rare earth elements (REEs) are reported for the upper water column of the Sargasso Sea. The trivalent-only REEs have remarkably constant concentrations in the upper 500m of an April 1989 profile and in the upper 200m of a May 1989 profile. In contrast, Ce concentrations decrease smoothly with increasing depth. In April 1989 Ce decreases from 15.7 pmol/kg at 20 m to 5.1 pmol/kg at 750 m. Cerium, which has Redox transformations in seawater, behaves anomalously with respect to its REE(III) neighbors. While both dissolved Ce and Mn have elevated concentrations in the upper 200m, their vertical gradients are distinctly different. In contrast to Mn, which reaches a minimum dissolved concentration near the zone (150-250 m) of a particulate Mn maximum, Ce is being removed both near this zone and to depths of at least 750m. These new profiles indicate that Ce is involved in an upper ocean redox cycle. This interpretation is consistent with the MOFFETT (1990) incubation tracer experiments on the same May 1989 seawater. He showed that Ce(III) oxidation is biologically mediated, probably light inhibited, increases with depth, and 3-4 times slower than Mn(II) oxidation in the 100-200 m zone. CERoclines provide new information into the fine scale zonation of redox process operating in the upper columns of oligotrophic oceans.

  13. Cerium(III) Complex Modified Gold Electrode: An Efficient Electrocatalyst for the Oxygen Evolution Reaction.

    PubMed

    Garain, Samiran; Barman, Koushik; Sinha, Tridib Kumar; Jasimuddin, Sk; Haeberle, Jörg; Henkel, Karsten; Schmeisser, Dieter; Mandal, Dipankar

    2016-08-24

    Exploring efficient and inexpensive electrocatalysts for the oxidation of water is of great importance for various electrochemical energy storage and conversion technologies. In the present study, a new water-soluble [Ce(III)(DMF) (HSO4)3] complex was synthesized and characterized by UV-vis, photoluminescence, and high-resolution X-ray photoelectron spectroscopy techniques. Owing to classic 5d → 4f transitions, an intense photoluminescence in the UV region was observed from the water-soluble [Ce(III)(DMF) (HSO4)3] complex. A stacking electrode was designed where self-assembled l-cysteine monolayer modified gold was immobilized with the synthesized cerium complex and was characterized by scanning electron microscopy, electrochemical impedance spectroscopy, and cyclic voltammetry. The resulting electrode, i.e., [Ce(III)(DMF) (HSO4)3]-l-cysteine-Au stacks shows high electrocatalytic water oxidation behavior at an overpotential of η ≈ 0.34 V under neutral pH conditions. We also demonstrated a way where the overpotential is possible to decrease upon irradiation of UV light. PMID:27490440

  14. Thermal Signatures of The Kondo Volume Collapse in Cerium

    SciTech Connect

    Lipp, M; Jackson, D; Cynn, H; Aracne, C; Evans, W; McMahan, A

    2008-05-23

    X-ray diffraction measurements of cerium in the vicinity of the isostructural {gamma}-{alpha} transition have been performed with high precision and accuracy from room temperature to almost 800 K. The disputed location of the critical point has been found to occur at 1.5 {+-} 0.1 GPa and 480 {+-} 10 K. The data is well fit by the Kondo volume collapse model plus a quasiharmonic representation of the phonons. The resultant free energy is validated against data for the thermodynamic Grueneisen parameter, and beyond the dominant spin fluctuation contribution, indicates a dramatic change in the lattice Grueneisen parameter across the transition.

  15. Identification of the Charge Carriers in Cerium Phosphate Ceramics

    SciTech Connect

    Ray, Hannah L.; Jonghe, Lutgard C. De

    2010-06-02

    The total conductivity of Sr-doped cerium orthophosphate changes by nearly two orders of magnitude depending on the oxygen and hydrogen content of the atmosphere. The defect model for the system suggests that this is because the identity of the dominant charge carrier can change from electron holes to protons when the sample is in equilibrium with air vs. humidified hydrogen. In this work are presented some preliminary measurements that can help to clarify this exchange between carriers. The conduction behavior of a 2percent Sr-doped CePO4 sample under symmetric atmospheric conditions is investigated using several techniques, including AC impedance, H/D isotope effects, and chronoamperometry.

  16. Properties of hot liquid cerium by LDA + U molecular dynamics.

    PubMed

    Siberchicot, Bruno; Clérouin, Jean

    2012-11-14

    We present ab initio simulations of liquid cerium in the framework of the LDA + U formulation. The liquid density has been determined self-consistently by searching for the zero pressure equilibrium state at 1320 K with the same set of parameters (U and J) and occupation matrices as those optimized for the γ phase. We have computed static and transport properties. The liquid produced by the simulations appears more structured than the available measurements. This raises questions regarding the ability of the theory to describe such a complex liquid. Conductivity calculations and temperature dependences are nevertheless in reasonable agreement with data.

  17. Water oxidation by manganese oxides, a new step towards a complete picture: simplicity is the ultimate sophistication.

    PubMed

    Najafpour, Mohammad Mahdi; Sedigh, Davood Jafarian

    2013-09-14

    We, for the first time, report that many Mn oxides (Mn3O4, α-Mn2O3, β-MnO2, CaMnO3, Ca2Mn3O8, CaMn3O6 and CaMn4O8) in the presence of cerium(IV) ammonium nitrate, in the water oxidation, convert to layered Mn oxide. This layered Mn oxide is an efficient water oxidizing catalyst.

  18. Hydrothermal synthesis of cerium titanate nanorods and its application in visible light photocatalysis

    SciTech Connect

    Pei, L.Z. Liu, H.D.; Lin, N.; Yu, H.Y.

    2015-01-15

    Highlights: • Cerium titanate nanorods have been synthesized by a simple hydrothermal process. • The size of the cerium titanate nanorods can be controlled by growth conditions. • Cerium titanate nanorods exhibit good photocatalytic activities for methyl blue. - Abstract: Cerium titanate nanorods have been prepared via a hydrothermal process using sodium dodecyl sulfate (SDS) as the surfactant. The cerium titanate nanorods have been analyzed by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), high-resolution TEM (HRTEM), and ultraviolet–visible (UV–vis) diffuse reflectance spectrum. XRD shows that the nanorods are composed of CeTi{sub 21}O{sub 38} phase. Electron microscopy observations indicate that the nanorods have good single crystalline nature. The diameter and length of the nanorods are about 50–200 nm and 1–2 μm, respectively. Cerium titanate nanorods have a band gap of 2.65 eV. The photocatalytic activities of the nanorods have been investigated by degrading methylene blue (MB) under visible light irradiation. MB solution with the concentration of 10 mg L{sup −1} can be degraded totally with the irradiation time increasing to 240 min. Cerium titanate nanorods exhibit great potential in photocatalytic degradation of MB under visible light irradiation.

  19. Dissolution of Neptunium and Plutonium Oxides Using a Catalyzed Electrolytic Process

    SciTech Connect

    Hylton, TD

    2004-10-25

    This report discusses the scoping study performed to evaluate the use of a catalyzed electrolytic process for dissolving {sup 237}Np oxide targets that had been irradiated to produce {sup 238}Pu oxide. Historically, these compounds have been difficult to dissolve, and complete dissolution was obtained only by adding hydrofluoric acid to the nitric acid solvent. The presence of fluoride in the mixture is undesired because the fluoride ions are corrosive to tank and piping systems and the fluoride ions cause interferences in the spectrophotometric analyses. The goal is to find a dissolution method that will eliminate these issues and that can be incorporated into a processing system to support the domestic production and purification of {sup 238}Pu. This study evaluated the potential of cerium(IV) ions, a strong oxidant, to attack and dissolve the oxide compounds. In the dissolution process, the cerium(IV) ions are reduced to cerium(III) ions, which are not oxidants. Therefore, an electrolytic process was incorporated to continuously convert cerium(III) ions back to cerium(IV) ions so that they can dissolve more of the oxide compounds. This study showed that the neptunium and plutonium oxides were successfully dissolved and that more development work should be performed to optimize the procedure.

  20. Catalyst for reduction of nitrogen oxides

    DOEpatents

    Ott, Kevin C.

    2010-04-06

    A Selective Catalytic Reduction (SCR) catalyst was prepared by slurry coating ZSM-5 zeolite onto a cordierite monolith, then subliming an iron salt onto the zeolite, calcining the monolith, and then dipping the monolith either into an aqueous solution of manganese nitrate and cerium nitrate and then calcining, or by similar treatment with separate solutions of manganese nitrate and cerium nitrate. The supported catalyst containing iron, manganese, and cerium showed 80 percent conversion at 113 degrees Celsius of a feed gas containing nitrogen oxides having 4 parts NO to one part NO.sub.2, about one equivalent ammonia, and excess oxygen; conversion improved to 94 percent at 147 degrees Celsius. N.sub.2O was not detected (detection limit: 0.6 percent N.sub.2O).

  1. Serum ornithine carbamoyltransferase (OCT) in rats poisoned with lanthanum, cerium and praseodymium.

    PubMed

    Marciniak, M; Bałtrukiewicz, Z

    1977-01-01

    Serum ornithine carbamoyltransferase (OCT) in rats poisoned with lanthanum, cerium and praseodymium. Acta Physiol. Pol., 1977, 28 (6): 589-594. The serum ornithine carbamoyltransferase in relation to doses of lanthanum, cerium and praseodymium, administered intravenously as chlorides, was investigated. A directly proportional relationship was found between the doses of these compounds and the serum enzyme level in rats. The lowest doses at which a rise in the serum OCT level occured were determined. They were: lanthanum - 0.75 mg/kg of body weight, cerium - 1.5 mg/kg, and praseodymium - 3 mh/kg. A decreasing toxicity of these elements with increasing value of atomic number was observed.

  2. Cerium-Based Magnets: Novel High Energy Permanent Magnet Without Critical Elements

    SciTech Connect

    2012-01-01

    REACT Project: Ames Laboratory will develop a new class of permanent magnets based on the more commonly available element cerium for use in both EVs and renewable power generators. Cerium is 4 times more abundant and significantly less expensive than the rare earth element neodymium, which is frequently used in today’s most powerful magnets. Ames Laboratory will combine other metal elements with cerium to create a new magnet that can remain stable at the high temperatures typically found in electric motors. This new magnetic material will ultimately be demonstrated in a prototype electric motor, representing a cost-effective and efficient alternative to neodymium-based motors.

  3. Fabrication of cerium active terbium aluminum garnet (TAG:Ce) phosphor powder via the solid-state reaction method

    SciTech Connect

    Tsai, M.-S. Liu, G.-M.; Chung, S.-L.

    2008-05-06

    A modified solid-state reaction method for the formation of terbium aluminum garnet (TAG:Ce) powder was studied. The starting materials, which included terbium oxide (Tb{sub 4}O{sub 7}), boehmite and cerium chloride (CeCl{sub 3}.7H{sub 2}O), were pre-aged at pH 3. This pre-aging process helps to form the core-shell structure, which leads to the formation of TAG:Ce phosphor powder via a solid-state reaction more easily. The emission intensity at 551 nm of the product pre-aged at pH 3 is higher than that formed without pre-aging.

  4. Press or pulse exposures determine the environmental fate of cerium nanoparticles in stream mesocosms.

    PubMed

    Baker, Leanne F; King, Ryan S; Unrine, Jason M; Castellon, Benjamin T; Lowry, Gregory V; Matson, Cole W

    2016-05-01

    Risk-assessment models indicate that stream ecosystems receiving municipal wastewater effluent may have the greatest potential for exposure to manufactured nanoparticles. The authors determined the fate of cerium oxide (CeO2 ) nanoparticles in outdoor stream mesocosms using 1) 1-time pulse addition of CeO2 nanoparticles, representative of accidental release, and 2) continuous, low-level press addition of CeO2 nanoparticles, representative of exposure via wastewater effluent. The pulse addition led to rapid nanoparticle floc formation, which appeared to preferentially deposit on periphyton in low-energy areas downstream from the location of the input, likely as a result of gravitational sedimentation. Floc formation limited the concentration of suspended nanoparticles in stream water to <5% of target and subsequent downstream movement. In contrast, press addition of nanoparticles led to higher suspended nanoparticle concentrations (77% of target) in stream water, possibly as a result of stabilization of suspended nanoparticles through interaction with dissolved organic carbon. Smaller nanoparticle aggregates appeared to preferentially adsorb to stream surfaces in turbulent sections, where Ce concentrations were highest in the press, likely a result of stochastic encounter with the surface. Streams receiving wastewater effluent containing nanoparticles may lead to exposure of aquatic organisms over a greater spatial extent than a similar amount of nanoparticles from an accidental release. Exposure models must take into account these mechanisms controlling transport and depositional processes. PMID:26576038

  5. Novel cerium doped glass-reinforced hydroxyapatite with antibacterial and osteoconductive properties for bone tissue regeneration.

    PubMed

    Morais, D S; Fernandes, S; Gomes, P S; Fernandes, M H; Sampaio, P; Ferraz, M P; Santos, J D; Lopes, M A; Sooraj Hussain, N

    2015-09-01

    The aim of this work was to develop a bioactive bone substitute with an effective antibacterial ability based on a cerium (Ce) doped glass-reinforced hydroxyapatite (GR-HA) composite. Developed composites were physicochemically characterized, using x-ray diffraction (XRD) analysis, SEM, energy dispersive x-ray spectroscopy (EDS), and flexural bending strength (FBS) tests. X-ray photoelectron spectroscopy (XPS) analysis was performed to analyze the oxidation state of Ce in the prepared doped glass. The antimicrobial activity of the composites was evaluated against Staphylococcus aureus, Staphylococcus epidermidis and Pseudomonas aeruginosa; whether the cytocompatibility profile was assayed with human osteoblastic-like cells (Mg-63 cell line). The results revealed that the Ce inclusion in the GR-HA matrix induced the antimicrobial ability of the composite. In addition, Ce-doped materials reported an adequate biological behavior following seeding of osteoblastic populations, by inducing cell adhesion and proliferation. Developed materials were also found to enhance the expression of osteoblastic-related genes. Overall, the developed GR-HA_Ce composite is a prospective candidate to be used within the clinical scenario with a successful performance due to the effective antibacterial properties and capability of enhancing the osteoblastic cell response. PMID:26391473

  6. Determination of thorium and of rare earth elements in cerium earth minerals and ores

    USGS Publications Warehouse

    Carron, M.K.; Skinner, D.L.; Stevens, R.E.

    1955-01-01

    The conventional oxalate method for precipitating thorium and the rare earth elements in acid solution exhibits definite solubilities of these elements. The present work was undertaken to establish conditions overcoming these solubilities and to find optimum conditions for precipitating thorium and the rare earth elements as hydroxides and sebacates. The investigations resulted in a reliable procedure applicable to samples in which the cerium group elements predominate. The oxalate precipitations are made from homogeneous solution at pH 2 by adding a prepared solution of anhydrous oxalic acid in methanol instead of the more expensive crystalline methyl oxalate. Calcium is added as a carrier. Quantitative precipitation of thorium and the rare earth elements is ascertained by further small additions of calcium to the supernatant liquid, until the added calcium precipitates as oxalate within 2 minutes. Calcium is removed by precipitating the hydroxides of thorium and rare earths at room temperature by adding ammonium hydroxide to pH > 10. Thorium is separated as the sebacate at pH 2.5, and the rare earths are precipitated with ammonium sebacate at pH 9. Maximum errors for combined weights of thorium and rare earth oxides on synthetic mixtures are ??0.6 mg. Maximum error for separated thoria is ??0.5 mg.

  7. Stabilized tin-oxide-based oxidation/reduction catalysts

    NASA Technical Reports Server (NTRS)

    Jordan, Jeffrey D. (Inventor); Schryer, David R. (Inventor); Davis, Patricia P. (Inventor); Leighty, Bradley D. (Inventor); Watkins, Anthony Neal (Inventor); Schryer, Jacqueline L. (Inventor); Oglesby, Donald M. (Inventor); Gulati, Suresh T. (Inventor); Summers, Jerry C. (Inventor)

    2008-01-01

    The invention described herein involves a novel approach to the production of oxidation/reduction catalytic systems. The present invention serves to stabilize the tin oxide reducible metal-oxide coating by co-incorporating at least another metal-oxide species, such as zirconium. In one embodiment, a third metal-oxide species is incorporated, selected from the group consisting of cerium, lanthanum, hafnium, and ruthenium. The incorporation of the additional metal oxide components serves to stabilize the active tin-oxide layer in the catalytic process during high-temperature operation in a reducing environment (e.g., automobile exhaust). Moreover, the additional metal oxides are active components due to their oxygen-retention capabilities. Together, these features provide a mechanism to extend the range of operation of the tin-oxide-based catalyst system for automotive applications, while maintaining the existing advantages.

  8. Correction: Single-molecule magnet behaviour in polynuclear assembly of trivalent cerium ions with polyoxomolybdates.

    PubMed

    Khélifa, A Ben; Belkhiria, M Salah; Huang, G; Freslon, S; Guillou, O; Bernot, K

    2016-06-01

    Correction for 'Single-molecule magnet behaviour in polynuclear assembly of trivalent cerium ions with polyoxomolybdates' by A. Ben Khélifa, et al., Dalton Trans., 2015, 44, 16458-16464. PMID:27161299

  9. Calculation of a volume effect accompanying an electronic topological transition in pure cerium

    NASA Astrophysics Data System (ADS)

    Ponomaryova, S. O.; Koval', Yu. M.; Ponomaryov, O. P.

    2012-10-01

    An analytic expression for estimating the volume effect accompanying an electronic topological transition (ETT) in pure cerium is derived on the basis of the microscopic Falikov-Ramirez-Kimball model.

  10. Static and dynamic high pressure experiments on cerium

    SciTech Connect

    Jensen, Brian J; Velisavljevic, Nenad; Cherne, Frank J; Stevens, Gerald; Tschauner, Oliver

    2011-01-25

    There is a scientific need to obtain dynamic data to develop and validate multi phase equation-of-state (EOS) models for metals. Experiments are needed to examine the relevant pure phases, to locate phase boundaries and the associated transition kinetics, and other material properties such as strength. Cerium is an ideal material for such work because it exhibits a complex multiphase diagram at relatively moderate pressures readily accessible using standard shock wave methods. In the current work, shock wave (dynamic) and diamond anvil cell (static) experiments were performed to examine the high pressure, low temperature region of the phase diagram to obtain EOS data and to search for the {alpha}-{var_epsilon} boundary. Past work examining the shock-melt transition and the low-pressure {gamma}-{alpha} transition will be presented in brief followed by details of recent results obtained from DAC and double-shock experiments.

  11. The Spin Glass-Kondo Competition in Disordered Cerium Systems

    NASA Astrophysics Data System (ADS)

    Magalhaes, S. G.; Zimmer, F.; Coqblin, B.

    2013-10-01

    We discuss the competition between the Kondo effect, the spin glass state and a magnetic order observed in disordered Cerium systems. We present firstly the experimental situation of disordered alloys such as CeNi1 - xCux and then the different theoretical approaches based on the Kondo lattice model, with different descriptions of the intersite exchange interaction for the spin glass. After the gaussian approach of the Sherrington-Kirkpatrick model, we discuss the Mattis and the van Hemmen models. Then, we present simple cluster calculations in order to describe the percolative evolution of the clusters from the cluster spin glass to the inhomogeneous ferromagnetic order recently observed in CeNi1 - xCux disordered alloys and finally we discuss the effect of random and transverse magnetic field.

  12. Characterization of a zinc-cerium flow battery

    NASA Astrophysics Data System (ADS)

    Leung, P. K.; Ponce-de-León, C.; Low, C. T. J.; Shah, A. A.; Walsh, F. C.

    The performance of a divided, parallel-plate zinc-cerium redox flow battery using methanesulfonic acid electrolytes was studied. Eight two and three-dimensional electrodes were tested under both constant current density and constant cell voltage discharge. Carbon felt and the three-dimensional platinised titanium mesh electrodes exhibited superior performance over the 2-dimensional electrodes. The charge and discharge characteristics of the redox flow battery were studied under different operating conditions and Zn/Ce reactant, as well as methansulfonic acid concentration. The cell performance improved at higher operating temperatures and faster electrolyte flow velocities. The number of possible cycles increased at reduced states of charge. During 15 min charge/discharge per cycle experiment, 57 cycles were obtained and the zinc reaction was found to be the limiting process during long term operation.

  13. An Alkali Metal-Capped Cerium(IV) Imido Complex.

    PubMed

    Solola, Lukman A; Zabula, Alexander V; Dorfner, Walter L; Manor, Brian C; Carroll, Patrick J; Schelter, Eric J

    2016-06-01

    Structurally authenticated, terminal lanthanide-ligand multiple bonds are rare and expected to be highly reactive. Even capped with an alkali metal cation, poor orbital energy matching and overlap of metal and ligand valence orbitals should result in strong charge polarization within such bonds. We expand on a new strategy for isolating terminal lanthanide-ligand multiple bonds using cerium(IV) complexes. In the current case, our tailored tris(hydroxylaminato) ligand framework, TriNOx(3-), provides steric protection against ligand scrambling and metal complex oligomerization and electronic protection against reduction. This strategy culminates in isolation of the first formal Ce═N bonded moiety in the complex [K(DME)2][Ce═N(3,5-(CF3)2C6H3)(TriNOx)], whose Ce═N bond is the shortest known at 2.119(3) Å. PMID:27163651

  14. Microstructure, texture evolution and magnetic properties of strip-casting non-oriented 6.5 wt.% Si electrical steel doped with cerium

    SciTech Connect

    Li, Hao-Ze Liu, Hai-Tao; Liu, Zhen-Yu Wang, Guo-Dong

    2015-05-15

    A 0.3 mm thick non-oriented 6.5 wt.% Si electrical steel sheet doped with cerium is produced by twin-roll strip casting, hot rolling, warm rolling and annealing. A detailed study of the cerium precipitates in the as-cast strip, microstructure and texture evolution at different processing stages is carried out by electron probe micro-analysis, optical microscopy, X-ray diffraction and electron backscattered diffraction analysis. Grain interior distributing precipitates identified as Ce-oxides, Ce-oxysulfides and Ce-phosphides, and boundary distributing Ce-oxides and Ce-phosphides are observed in the as-cast strip. The initial as-cast strip is characterized by a much finer solidification microstructure and dominated by obvious < 001 >//ND texture through the strip thickness. After hot and warm rolling, inhomogeneous microstructure containing large amounts of in-grain shear bands is characterized by mixed < 110 >//RD and < 111 >//ND textures. The texture of the annealed sheet with a relatively large average grain size is far more optimized by the domination of the beneficial cube, rotated cube, (001)< 120 > to (001)< 130 > and Goss texture components, and the elimination of the detrimental γ-fiber texture, leading to a superior magnetic induction and improved iron loss. - Highlights: • An Fe–6.5 wt.% Si as-cast strip doped with cerium was produced. • A thin warm rolled sheet with limited edge cracks was obtained. • Microstructure and texture evolution at each stage were investigated. • Strong λ-fiber and Goss recrystallization textures were formed. • The magnetic properties of the annealed sheet were significantly improved.

  15. Impact of Rh-CeOx interaction on CO oxidation mechanisms

    NASA Astrophysics Data System (ADS)

    Ševčíková, Klára; Kolářová, Tatiana; Skála, Tomáš; Tsud, Nataliya; Václavů, Michal; Lykhach, Yaroslava; Matolín, Vladimír; Nehasil, Václav

    2015-03-01

    We have investigated the impact of electronic metal-support interaction on catalytic properties of Rh/CeOx system, i.e. its capacity for the reverse and direct oxygen spillover, in the context of CO oxidation. The studies were carried out on two types of samples consisting of Rh particles supported on polycrystalline nearly stoichiometric and partially reduced cerium oxide films using temperature programmed reaction, temperature programmed desorption, and conventional X-ray and resonant photoelectron spectroscopies. We have found that the electronic Rh-CeOx interaction leads to a buildup of a net positive charge on Rh particles supported on stoichiometric cerium oxide, and a net negative charge on Rh particles on reduced cerium oxide. The effect of the Rh-CeOx interaction is manifested in suppression of the reverse and direct oxygen spillover on Rh particles supported on partially reduced ceria.

  16. Magmatic oxygen fugacity estimated using zircon-melt partitioning of cerium

    NASA Astrophysics Data System (ADS)

    Smythe, Duane J.; Brenan, James M.

    2016-11-01

    Using a newly-calibrated relation for cerium redox equilibria in silicate melts (Smythe and Brenan, 2015), and an internally-consistent model for zircon-melt partitioning of Ce, we provide a method to estimate the prevailing redox conditions during crystallization of zircon-saturated magmas. With this approach, oxygen fugacities were calculated for samples from the Bishop tuff (USA), Toba tuff (Indonesia) and the Nain plutonic suite (Canada), which typically agree with independent estimates within one log unit or better. With the success of reproducing the fO2 of well-constrained igneous systems, we have applied our Ce-in-zircon oxygen barometer to estimating the redox state of Earth's earliest magmas. Using the composition of the Jack Hills Hadean zircons, combined with estimates of their parental magma composition, we determined the fO2 during zircon crystallization to be between FMQ -1.0 to +2.5 (where FMQ is the fayalite-magnetite-quartz buffer). Of the parental magmas considered, Archean tonalite-trondhjemite-granodiorite (TTG) compositions yield zircon-melt partitioning most similar to well-constrained modern suites (e.g., Sano et al., 2002). Although broadly consistent with previous redox estimates from the Jack Hills zircons, our results provide a more precise determination of fO2, narrowing the range for Hadean parental magmas by more than 8 orders of magnitude. Results suggest that relatively oxidized magmatic source regions, similar in oxidation state to that of 3.5 Ga komatiite suites, existed by ∼4.4 Ga.

  17. Adsorption properties of aluminium oxide modified with palladium, gold, and cerium oxide nanoparticles

    NASA Astrophysics Data System (ADS)

    Lanin, S. N.; Bannykh, A. A.; Vinogradov, A. E.; Kovaleva, N. V.; Lanina, K. S.; Nikolaev, S. A.

    2016-07-01

    The adsorption properties of nanocomposites based on γ-Al2O3 modified with CeO x , Au/CeO x , and Pd/CeO x nanoparticles with contents of deposited metals ranging from 0.07 to 1.71 wt % are investigated by means of dynamic sorption method. n-Alkanes (C6-C8), acetonitrile, diethyl ether, tetrahydrofuran, and dioxane are used as test adsorbates. Adsorption isotherms are measured, and the isosteric heats of adsorption of a number of test adsorbates are calculated. Electron-donor and electron-acceptor characteristics of the surfaces of γ-Al2O3-based nanocomposites are estimated. It is shown that Au(0.1%)/CeO x (0.07%)/γ-Al2O3 nanocomposite, which has the lowest content of nanoparticles of the deposited metals, has the highest adsorption activity.

  18. Copper, Boron, and Cerium Additions in Type 347 Austenitic Steel to Improve Creep Rupture Strength

    NASA Astrophysics Data System (ADS)

    Laha, Kinkar; Kyono, J.; Shinya, Norio

    2012-04-01

    Type 347 austenitic stainless steel (18Cr-12Ni-Nb) was alloyed with copper (3 wt pct), boron (0.01 to 0.06 wt pct), and cerium (0.01 wt pct) with an aim to increase the creep rupture strength of the steel through the improved deformation and cavitation resistance. Short-term creep rupture strength was found to increase with the addition of copper in the 347 steel, but the long-term strength was inferior. Extensive creep cavitation deprived the steel of the beneficial effect of creep deformation resistance induced by nano-size copper particles. Boron and cerium additions in the copper-containing steel increased its creep rupture strength and ductility, which were more for higher boron content. Creep deformation, grain boundary sliding, and creep cavity nucleation and growth in the steel were found to be suppressed by microalloying the copper-containing steel with boron and cerium, and the suppression was more for higher boron content. An auger electron spectroscopic study revealed the segregation of boron instead of sulfur on the cavity surface of the boron- and cerium-microalloyed steel. Cerium acted as a scavenger for soluble sulfur in the steels through the precipitation of cerium sulfide (CeS). This inhibited the segregation of sulfur and facilitated the segregation of boron on cavity surface. Boron segregation on the nucleated cavity surface reduced its growth rate. Microalloying the copper-containing 347 steel with boron and cerium thus enabled to use the full extent of creep deformation resistance rendered by copper nano-size particle by increase in creep rupture strength and ductility.

  19. Apparatus and method for constant flow oxidizing of organic materials

    DOEpatents

    Surma, Jeffrey E.; Nelson, Norvell; Steward, G. Anthony; Bryan, Garry H.

    1999-01-01

    The invention is a method and apparatus using high cerium concentration in the anolyte of an electrochemical cell to oxidize organic materials. The method and apparatus further use an ultrasonic mixer to enhance the oxidation rate of the organic material in the electrochemical cell. A reaction vessel provides an advantage of independent reaction temperature control and electrochemical cell temperature control. A separate or independent reaction vessel may be used without an ultrasonic mixer to oxidize gaseous phase organic materials.

  20. Deposition and investigation of lanthanum-cerium hexaboride thin films

    SciTech Connect

    Kuzanyan, A.S. . E-mail: akuzan@ipr.sci.am; Harutyunyan, S.R.; Vardanyan, V.O.; Badalyan, G.R.; Petrosyan, V.A.; Kuzanyan, V.S.; Petrosyan, S.I.; Karapetyan, V.E.; Wood, K.S.; Wu, H.-D.

    2006-09-15

    Thin films of lanthanum-cerium hexaboride, the promising thermoelectric material for low-temperature applications, are deposited on various substrates by the electron-beam evaporation, pulsed laser deposition and magnetron sputtering. The influence of the deposition conditions on the films X-ray characteristics, composition, microstructure and physical properties, such as the resistivity and Seebeck coefficient, is studied. The preferred (100) orientation of all films is obtained from XRD traces. In the range of 780-800 deg. C deposition temperature the highest intensity of diffractions peaks and the highest degree of the preferred orientation are observed. The temperature dependence of the resistivity and the Seebeck coefficient of films are investigated in the temperature range of 4-300 K. The features appropriate to Kondo effect in the dependences {rho}(T) and S(T) are detected at temperatures below 20 K. Interplay between the value of the Seebeck coefficient, metallic parameters and Kondo scattering of investigated films is discussed. - Graphical abstract: Kondo scattering in (La,Ce)B{sub 6} films: temperature dependence of the resistivity of (La,Ce)B{sub 6} films on various substrates and the ceramics La{sub 0.99}Ce{sub 0.01}B{sub 6}.

  1. Intravenous and Gastric Cerium Dioxide Nanoparticle Exposure Disrupts Microvascular Smooth Muscle Signaling

    PubMed Central

    Minarchick, Valerie C.; Stapleton, Phoebe A.; Fix, Natalie R.; Leonard, Stephen S.; Sabolsky, Edward M.; Nurkiewicz, Timothy R.

    2015-01-01

    Cerium dioxide nanoparticles (CeO2 NP) hold great therapeutic potential, but the in vivo effects of non-pulmonary exposure routes are unclear. The first aim was to determine whether microvascular function is impaired after intravenous and gastric CeO2 NP exposure. The second aim was to investigate the mechanism(s) of action underlying microvascular dysfunction following CeO2 NP exposure. Rats were exposed to CeO2 NP (primary diameter: 4 ± 1 nm, surface area: 81.36 m2/g) by intratracheal instillation, intravenous injection, or gastric gavage. Mesenteric arterioles were harvested 24 h post-exposure and vascular function was assessed using an isolated arteriole preparation. Endothelium-dependent and independent function and vascular smooth muscle (VSM) signaling (soluble guanylyl cyclase [sGC] and cyclic guanosine monophosphate [cGMP]) were assessed. Reactive oxygen species (ROS) generation and nitric oxide (NO) production were analyzed. Compared with controls, endothelium-dependent and independent dilation were impaired following intravenous injection (by 61% and 45%) and gastric gavage (by 63% and 49%). However, intravenous injection resulted in greater microvascular impairment (16% and 35%) compared with gastric gavage at an identical dose (100 µg). Furthermore, sGC activation and cGMP responsiveness were impaired following pulmonary, intravenous, and gastric CeO2 NP treatment. Finally, nanoparticle exposure resulted in route-dependent, increased ROS generation and decreased NO production. These results indicate that CeO2 NP exposure route differentially impairs microvascular function, which may be mechanistically linked to decreased NO production and subsequent VSM signaling. Fully understanding the mechanisms behind CeO2 NP in vivo effects is a critical step in the continued therapeutic development of this nanoparticle. PMID:25481005

  2. Thorium and cerium chemical behaviour in ion-irradiated alkali-borosilicate glasses

    NASA Astrophysics Data System (ADS)

    Trocellier, P.; Haddi, A.; Poissonnet, S.; Bonnaillie, P.; Serruys, Y.

    2006-08-01

    Simple alkali-borosilicate glasses containing SiO2-B2O3-Li2O-Na2O and only one or two transition metal oxides (CeO2 and/or ThO2) have been synthesized by melting the stoichiometric powder mixture at 1100 °C in a platinum crucible. Thorium and cerium were used as chemical analogs of minor actinides (Pu and Am). Th is a purely tetravalent element, although Ce can be tetravalent or trivalent. Glass samples were submitted to aqueous leaching tests at 90 °C in deionised water for one week, with or without having previously been ion-irradiated. The irradiation experiments were conducted in the nuclear energy loss regime. Kr ions supplied by a 1 MV electrostatic Van de Graaff accelerator, were used to produce displacement cascades in the first hundreds of nanometers beneath the sample's surfaces. The leached samples were then characterized by scanning electron microscopy (SEM), electron microprobe analysis (EMA) and ion beam analytical (IBA) methods: Rutherford backscattering spectrometry and elastic recoil detection analysis (RBS and ERDA), proton-induced X-ray or gamma ray emission (PIXE and PIGE). Th and Ce are shown to be enriched in the near surface region of leached glasses due to the extremely low solubility of their hydroxides. The effect of surface damage on the chemical behaviour of Th and Ce is then detailed. The possibility for Ce(IV) to be reduced as Ce(III) during ion-irradiation just before leaching and its consequences on the relative solubility of corresponding chemical species is discussed in terms of hydroxide solubility thermodynamical equilibria.

  3. Catalyst and method for reduction of nitrogen oxides

    DOEpatents

    Ott, Kevin C.

    2008-05-27

    A Selective Catalytic Reduction (SCR) catalyst was prepared by slurry coating ZSM-5 zeolite onto a cordierite monolith, then subliming an iron salt onto the zeolite, calcining the monolith, and then dipping the monolith either into an aqueous solution of manganese nitrate and cerium nitrate and then calcining, or by similar treatment with separate solutions of manganese nitrate and cerium nitrate. The supported catalyst containing iron, manganese, and cerium showed 80 percent conversion at 113 degrees Celsius of a feed gas containing nitrogen oxides having 4 parts NO to one part NO.sub.2, about one equivalent ammonia, and excess oxygen; conversion improved to 94 percent at 147 degrees Celsius. N.sub.2O was not detected (detection limit: 0.6 percent N.sub.2O).

  4. Catalyst and method for reduction of nitrogen oxides

    DOEpatents

    Ott, Kevin C.

    2008-08-19

    A Selective Catalytic Reduction (SCR) catalyst was prepared by slurry coating ZSM-5 zeolite onto a cordierite monolith, then subliming an iron salt onto the zeolite, calcining the monolith, and then dipping the monolith either into an aqueous solution of manganese nitrate and cerium nitrate and then calcining, or by similar treatment with separate solutions of manganese nitrate and cerium nitrate. The supported catalyst containing iron, manganese, and cerium showed 80 percent conversion at 113 degrees Celsius of a feed gas containing nitrogen oxides having 4 parts NO to one part NO.sub.2, about one equivalent ammonia, and excess oxygen; conversion improved to 94 percent at 147 degrees Celsius. N.sub.2O was not detected (detection limit: 0.6 percent N.sub.2O).

  5. Excitation induced spectroscopic study and quenching effect in cerium samarium codoped lithium aluminoborate glasses

    NASA Astrophysics Data System (ADS)

    Kaur, Parvinder; Kaur, Simranpreet; Singh, Gurinder Pal; Arora, Deepawali; Kumar, Sunil; Singh, D. P.

    2016-08-01

    Lithium aluminium borate host has been codoped with cerium and samarium to prepare glass by conventional melt quench technique. Their structural and spectroscopic investigation has been carried out using XRD, FTIR and density measurements. The UV-Vis absorption spectra and fluorescence spectra (λexc.=380 nm and 400 nm) have been studied for spectroscopic analysis. The amorphous nature of the prepared samples is shown by XRD. The density is increasing with addition of cerium at the expense of aluminium, keeping other components constant. FTIR study also shows the presence of compact and stable tetrahedral BO4 units thus supporting the density results. The UV- Vis absorption spectra show a shift of optical absorption edge towards longer wavelength along with an increase in intensity of peaks with rising samarium concentration. The fluorescence spectra show a blue shift and subsequent suppression of cerium peaks with addition of samarium.

  6. Eucalyptus tolerance mechanisms to lanthanum and cerium: subcellular distribution, antioxidant system and thiol pools.

    PubMed

    Shen, Yichang; Zhang, Shirong; Li, Sen; Xu, Xiaoxun; Jia, Yongxia; Gong, Guoshu

    2014-12-01

    Guanglin 9 (Eucalyptus grandis × Eucalyptus urophlla) and Eucalyptus grandis 5 are two eucalyptus species which have been found to grow normally in soils contaminated with lanthanum and cerium, but the tolerance mechanisms are not clear yet. In this study, a pot experiment was conducted to investigate the tolerance mechanisms of the eucalyptus to lanthanum and cerium. Cell walls stored 45.40-63.44% of the metals under lanthanum or cerium stress. Peroxidase and catalase activities enhanced with increasing soil La or Ce concentrations up to 200 mg kg(-1), while there were no obvious changes in glutathione and ascorbate concentrations. Non-protein thiols concentrations increased with increasing treatment levels up to 200 mg kg(-1), and then decreased. Phytochelatins concentrations continued to increase under La or Ce stress. Therefore, the two eucalyptus species are La and Ce tolerant plants, and the tolerance mechanisms include cell wall deposition, antioxidant system response, and thiol compound synthesis. PMID:25303462

  7. Synthesis and photocatalytic activity of mesoporous cerium doped TiO{sub 2} as visible light sensitive photocatalyst

    SciTech Connect

    Aman, Noor; Satapathy, P.K.; Mishra, T.; Mahato, M.; Das, N.N.

    2012-02-15

    Graphical abstract: Cerium doped titania having optimum 5 wt% of cerium can decompose methylene blue and reduce selenium (IV) efficiently under visible light. Highlights: Black-Right-Pointing-Pointer Effect of cerium doping on the surface properties and visible light mediated photocatalytic reaction is studied. Black-Right-Pointing-Pointer Cerium doping increases the anatase phase stability, surface area (up to 137 m{sup 2}/g) and visible light absorption. Black-Right-Pointing-Pointer Importance of Ce{sup 3+}/Ce{sup 4+}, oxygen vacancy, surface area and crystallinity is correlated with improved catalytic activity. Black-Right-Pointing-Pointer Material with 5 wt% Ce is found to be most active photocatalyst for methylene blue decomposition and Se (IV) reduction. -- Abstract: Cerium doped titania materials were synthesized varying the cerium concentration from 0 to 10 wt%. Materials are characterised by XRD, TEM, XPS and N{sub 2} adsorption desorption method. Surface area and visible light absorption substantially increases and crystallite size decreases with the increasing cerium content. Cerium doping stabilizes the anatase phase and surface area even at 600 Degree-Sign C calcination. Photocatalytic activity towards methylene blue decomposition and selenium (IV) reduction is found to increase with the cerium content up to 5 wt% and then decreases. Materials calcined at 600 Degree-Sign C shows better activity than that calcined at 400 Degree-Sign C, even though surface area decreases. Anatase crystallinity mostly decides the photocatalytic activity rather than only surface area. It can be concluded that the optimum visible light absorption and oxygen vacancy with 5% cerium doping enhances the photocatalytic activity. In addition photocatalytic performance is found to depend on the presence of Ce{sup 4+}/Ce{sup 3+} rather than only visible light absorption.

  8. Ab initio studies of anisotropic magnetism in uranium and cerium monopnictides and monochalcogenides

    NASA Astrophysics Data System (ADS)

    Collins, Eric Mason

    We have applied two ab initio based methods to investigate the origin in the electronic structure of the unusual magnetic behavior of the cerium and uranium monopnictides and monochalcogenides. First, we have carried out spin-polarized electronic structure calculations, based on the full potential linear muffin tin (FPLMTO) method, with spin polarization (orbital polarization only via spin-orbit coupling) and also with orbital polarization correction. Second, we have carried out ab initio based calculations synthesizing (1) a phenomenological theory of orbitally driven magnetism based on the Anderson and Kondo, lattice model which incorporates explicitly the hybridization induced and the Coulomb exchange interactions on an equal footing, and (2) FPLMTO electronic structure calculations allowing a first principles evaluation of all the parameters entering the model Hamiltonian. For the cerium compounds, we also include the crystal field interactions on an equal footing with the hybridization and Coulomb exchange interactions with a scaling determined by experiment. The results for the uranium compound calculations show that both methods are limited to the extremes to which they are best suited. The pure band structure calculations provide the best agreement for the lighter uranium compounds, while the model hamiltonian approach provides better agreement for the heavier uranium compounds. In the case of the cerium compounds, while the pure FPLMTO calculations yield values for the magnetic moment in agreement with experiment for the lighter cerium chalcogenides, they fail to give, even qualitatively, the magnetic properties for all other systems. On the other hand, the ab initio based model Hamiltonian calculations reveal for the first time the interplay of hybridization, Coulomb exchange, and crystal field interactions across the cerium series, and give results for the low-temperature moment and ordering temperature in excellent agreement with experiment, for the

  9. Protection by Thermal and Chemical Activation with Cerium Salts of the Alloy AA2017 in Aqueous Solutions of NaCl

    NASA Astrophysics Data System (ADS)

    Bethencourt, Manuel; Botana, Francisco Javier; Cano, María José; González-Rovira, Leandro; Marcos, Mariano; Sánchez-Amaya, José María

    2012-01-01

    A wide variety of anticorrosive treatments for aluminum alloys that can be employed as "green" alternatives to those based on Cr(VI) are currently under development. This article reports a study of the morphological and anticorrosive characteristics of surface layers formed on the Al-Cu alloy AA2017 by immersion treatment in baths of cerium salt, accelerated by increased temperature and the employment of hydrogen peroxide. Scanning electron microscopy (SEM)/X-ray energy dispersive spectroscopy (XEDS) studies of the samples treated have demonstrated the existence of a heterogeneous layer formed by a film of aluminum oxide/hydroxide on the matrix, and a series of dispersed islands of cerium over the cathodic intermetallics. The protective efficacy has been evaluated using electrochemical techniques, linear polarizations (LP) and electrochemical impedance spectroscopy (EIS), and salt spray tests. The results obtained indicate that the layer provided good resistance to corrosion in media with chlorides, and the method gives a considerable reduction of the time required for the immersion treatments.

  10. The investigation of cerium as a cathodic inhibitor for aluminum-copper alloys

    SciTech Connect

    Aldykewicz, A.J. Jr.; Isaacs, H.S.; Davenport, A.J.

    1995-10-01

    In situ current density mapping, scanning electron microscopy , and energy dispersive spectroscopy were used to study the effects of cerium as a corrosion inhibitor for an aluminum copper alloy (Al 2024-T4) in chloride containing solutions. It was found that cerium inhibits corrosion of this alloy by reducing the rate of the cathodic reaction. This was due to the carried out on an aluminum/copper galvanic couple, which was used to simulate the electrochemical behavior of the copper containing intermetallics, showed that corrosion inhibition was associated with the formation of a Ce-rich film over the copper in agreement with that observed for the alloy.

  11. Synthesis and characterization of two dimensional metal organic framework of cerium with tetraaza macrocyclic

    SciTech Connect

    Bt Safiin, Nurul Atikah; Yarmo, Ambar; Yamin, Bohari M.

    2013-11-27

    A two dimensional metal organic framework containing cerium sufate layers and ethylenediaminium between layers was obtained by refluxing the mixture of cerium sulphate and 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradeca-7, 14-diene bromide. The complex was characterized by infrared spectroscopy and microelemental analysis. X-ray study showed that the complex adopts eleven coordination environments about the central atom. Thermogravimetric study showed the removal of water molecules at about 70°C followed by a gradual mass loss until the whole structure collapsed at about 400°C.

  12. METHOD OF SEPARATING TETRAVALENT PLUTONIUM VALUES FROM CERIUM SUB-GROUP RARE EARTH VALUES

    DOEpatents

    Duffield, R.B.; Stoughton, R.W.

    1959-02-01

    A method is presented for separating plutonium from the cerium sub-group of rare earths when both are present in an aqueous solution. The method consists in adding an excess of alkali metal carbonate to the solution, which causes the formation of a soluble plutonium carbonate precipitate and at the same time forms an insoluble cerium-group rare earth carbonate. The pH value must be adjusted to bctween 5.5 and 7.5, and prior to the precipitation step the plutonium must be reduced to the tetravalent state since only tetravalent plutonium will form the soluble carbonate complex.

  13. Systematic variation of rare-earth elements in cerium-earth minerals

    USGS Publications Warehouse

    Murata, K.J.; Rose, H.J.; Carron, M.K.; Glass, J.J.

    1957-01-01

    In a continuation of a study reported previously, rare-earth elements and thorium have been determined in monazite, allanite, cerite, bastnaesite, and a number of miscellaneous cerium-earth minerals. A quantity called sigma (???), which is the sum of the atomic percentages of La, Ce, and Pr, is proposed as an index of composition of all cerium-earth minerals with respect to the rare-earth elements. The value of ??? for all of the minerals analysed falls between 58 and 92 atomic per cent. Monazites, allanites, and cerites cover the entire observed range, whereas bastnaesites are sharply restricted to the range between 80 and 92 atomic per cent. The minimum value of ??? for a cerium-earth mineral corresponds to the smallest possible unit-cell size of the mineral. In monazite, this structurally controlled minimum value of ??? is estimated to be around 30 atomic per cent. Neodymium, because of its abundance, and yttrium, because of its small size, have dominant roles in contraction of the structure. In the other direction, the limit of variation in composition will be reached when lanthanum becomes the sole rare-earth element in a cerium-earth mineral. Cerium-earth minerals from alkalic rocks are all characterized by values of ??? greater than 80 atomic per cent, indicating that the processes that formed these rocks were unusually efficient in fractionating the rare-earth elements-efficient in the sense that a highly selected assemblage is produced without eliminating the bulk of these elements. Analyses of inner and outer parts of two large crystals of monazite from different deposits show no difference in ??? in one crystal and a slightly smaller value of ??? in the outer part of the other crystal compared to the inner part. The ??? of monazites from pegmatites that intrude genetically related granitic rocks in North Carolina is found to be either higher or lower than the ??? of monazites in the intruded host rock. These results indicate that the fractionation of the

  14. Cytoprotective effects of cerium and selenium nanoparticles on heat-shocked human dermal fibroblasts: an in vitro evaluation.

    PubMed

    Yuan, Bo; Webster, Thomas J; Roy, Amit K

    2016-01-01

    It is a widely accepted fact that environmental factors affect cells by modulating the components of subcellular compartments and altering metabolic enzymes. Factors (such as oxidative stress and heat-shock-induced proteins and heat shock factors, which upregulate stress-response related genes to protect affected cells) are commonly altered during changes in environmental conditions. Studies by our group and others have shown that nanoparticles (NPs) are able to efficiently attenuate oxidative stress by penetrating into specific tissues or organs. Such findings warrant further investigation on the effects of NPs on heat-shock-induced stress, specifically in cells in the presence or absence (pretreated) of NPs. Here, we examined the cytoprotective effects of two different NPs (cerium and selenium) on heat-induced cell death for a model cell using dermal fibroblasts. We report for the first time that both ceria and selenium NPs (at 500 µg/mL) possess stress-relieving behavior on fibroblasts undergoing heat shock. Such results indicate the need to further develop these NPs as a novel treatment for heat shock. PMID:27103800

  15. Cytoprotective effects of cerium and selenium nanoparticles on heat-shocked human dermal fibroblasts: an in vitro evaluation

    PubMed Central

    Yuan, Bo; Webster, Thomas J; Roy, Amit K

    2016-01-01

    It is a widely accepted fact that environmental factors affect cells by modulating the components of subcellular compartments and altering metabolic enzymes. Factors (such as oxidative stress and heat-shock-induced proteins and heat shock factors, which upregulate stress-response related genes to protect affected cells) are commonly altered during changes in environmental conditions. Studies by our group and others have shown that nanoparticles (NPs) are able to efficiently attenuate oxidative stress by penetrating into specific tissues or organs. Such findings warrant further investigation on the effects of NPs on heat-shock-induced stress, specifically in cells in the presence or absence (pretreated) of NPs. Here, we examined the cytoprotective effects of two different NPs (cerium and selenium) on heat-induced cell death for a model cell using dermal fibroblasts. We report for the first time that both ceria and selenium NPs (at 500 µg/mL) possess stress-relieving behavior on fibroblasts undergoing heat shock. Such results indicate the need to further develop these NPs as a novel treatment for heat shock. PMID:27103800

  16. Particulate Emissions from the Combustion of Diesel Fuel with a Fuel-Borne Nanoparticulate Cerium Catalyst

    NASA Astrophysics Data System (ADS)

    Conny, J. M.; Willis, R. D.; Weinstein, J. P.; Krantz, T.; King, C.

    2013-12-01

    To address the adverse impacts on health and climate from the use of diesel-fueled vehicles, a number of technological solutions have been developed for reducing diesel soot emissions and to improve fuel economy. One such solution is the use fuel-borne metal oxide catalysts. Of current interest are commercially-available fuel additives consisting of nanoparticulate cerium oxide (CeO2). In response to the possible use of CeO2-containing fuels in on-road vehicles in the U.S., the Environmental Protection Agency is conducting research to address the potential toxicity and environmental effects of particulate CeO2 emitted with diesel soot. In this study, emissions from a diesel-fueled electric generator were size-segregated on polished silicon wafers in a nanoparticle cascade impactor. The diesel fuel contained 10 ppm Ce by weight in the form of crystalline CeO2 nanoparticles 4 nm to 7.5 nm in size. Primary CeO2 nanoparticles were observed in the diesel emissions as well as CeO2 aggregates encompassing a broad range of sizes up to at least 200 nm. We report the characterization of individual particles from the size-resolved samples with focused ion-beam scanning electron microscopy and energy-dispersive x-ray spectroscopy. Results show a dependency between the impactor size range and CeO2 agglomeration state: in the larger size fractions of the impactor (e.g., 560 nm to 1000 nm) CeO2 nanoparticles were predominantly attached to soot particles. In the smaller size fractions of the impactor (e.g., 100 nm to 320 nm), CeO2 aggregates tended to be larger and unattached to soot. The result is important because the deposition of CeO2 nanoparticles attached to soot particles in the lung or on environmental surfaces such as plant tissue will likely present different consequences than the deposition of unagglomerated CeO2 particles. Disclaimer The U.S. Environmental Protection Agency through its Office of Research and Development funded and collaborated in the research described

  17. Treatment of Radioactive Organic Wastes by an Electrochemical Oxidation

    SciTech Connect

    Kim, K.H.; Ryue, Y.G.; Kwak, K.K.; Hong, K.P.; Kim, D.H.

    2007-07-01

    A waste treatment system by using an electrochemical oxidation (MEO, Mediated Electrochemical Oxidation) was installed at KAERI (Korea Atomic Energy Research Institute) for the treatment of radioactive organic wastes, especially EDTA (Ethylene Diamine Tetraacetic Acid) generated during the decontamination activity of nuclear installations. A cerium and silver mediated electrochemical oxidation technique method has been developed as an alternative for an incineration process. An experiment to evaluate the applicability of the above two processes and to establish the conditions to operate the pilot-scale system has been carried out by changing the concentration of the catalyst and EDTA, the operational current density, the operating temperature, and the electrolyte concentration. As for the results, silver mediated oxidation was more effective in destructing the EDTA wastes than the cerium mediated oxidation process. For a constant volume of the EDTA wastes, the treatment time for the cerium-mediated oxidation was 9 hours and its conversion ratio of EDTA to water and CO{sub 2} was 90.2 % at 80 deg. C, 10 A, but the treatment time for the silver-mediated oxidation was 3 hours and its conversion ratio was 89.2 % at 30 deg. C, 10 A. (authors)

  18. Synthesis and characterization of linear cerium(IV) Schiff-base coordination polymers

    SciTech Connect

    Chen, H.; Cronin, J.A.; Archer, R.D. . Dept. of Chemistry)

    1994-04-11

    The first soluble linear Schiff-base rare earth coordination polymer, catena-poly[cerium-(4)-[mu]-N,N[prime],N[double prime],N[prime][double prime]-tetrasalicylidene (3,3[prime]-diaminobenzidinato)-O,N,N[prime],O[prime],O[double prime],N[double prime],N[prime][double prime],O[prime][double prime

  19. Fabrication and characterization of cerium-doped barium titanate inverse opal by sol-gel method

    SciTech Connect

    Jin Yi; Zhu Yihua Yang Xiaoling; Li Chunzhong; Zhou Jinghong

    2007-01-15

    Cerium-doped barium titanate inverted opal was synthesized from barium acetate contained cerous acetate and tetrabutyl titanate in the interstitial spaces of a polystyrene (PS) opal. This procedure involves infiltration of precursors into the interstices of the PS opal template followed by hydrolytic polycondensation of the precursors to amorphous barium titanate and removal of the PS opal by calcination. The morphologies of opal and inverse opal were characterized by scanning electron microscope (SEM). The pores were characterized by mercury intrusion porosimetry (MIP). X-ray photoelectron spectroscopy (XPS) investigation showed the doping structure of cerium, barium and titanium. And powder X-ray diffraction allows one to observe the influence of doping degree on the grain size. The lattice parameters, crystal size and lattice strain were calculated by the Rietveld refinement method. The synthesis of cerium-doped barium titanate inverted opals provides an opportunity to electrically and optically engineer the photonic band structure and the possibility of developing tunable three-dimensional photonic crystal devices. - Graphical abstract: Cerium-doped barium titanate inverted opal was synthesized from barium acetate acid contained cerous acetate and tetrabutyl titanate in the interstitial spaces of a PS opal, which involves infiltration of precursors into the interstices of the PS opal template and removal of the PS opal by calcination.

  20. Calculation of the volume effect at an electron phase transition in pure cerium and praseodymium

    NASA Astrophysics Data System (ADS)

    Ponomareva, S. A.; Koval', Yu. N.; Ponomarev, A. P.

    2014-03-01

    The experimental values of the volume effect at an electronic phase transition in several rare-earth metals are discussed. Specifically, volume changes at phase transitions in cerium and praseodymium are calculated using a semiphenomenological relationship derived in terms of the Falikov-Ramirez-Kimball model. A number of factors influencing the amount of the volume effect at electronic phase transitions are analyzed.

  1. Synthesis, electrical and dielectric characterization of cerium doped nano copper ferrites

    SciTech Connect

    Malana, Muhammad Aslam Qureshi, Raheela Beenish; Ashiq, Muhammad Naeem; Zafar, Zafar Iqbal

    2013-11-15

    Graphical abstract: Lattice constant (a) and activation energy (Ea) as a function of Ce (cerium) content. - Highlights: • The simple and economic method has been adopted for the synthesis of nanoferrites. • The electrical resistivity increases with cerium concentration. • DC electrical resistivity of these materials favours their use in microwave devices. • Dielectric measurements show semiconductor nature of the synthesized ferrites. - Abstract: The nanosized CuFe{sub 2−x}Ce{sub x}O{sub 4} (x = 0.0, 0.2, 0.4, 0.6, 0.8) ferrites doped with cerium are synthesized by chemical co-precipitation method. The synthesized materials are characterized by XRD, FTIR, TGA and SEM. XRD analysis of cerium substituted copper ferrites confirms the cubic spinel structure. The average crystallite size calculated by using Scherrer's formula ranges from 37 to 53 nm. The values of cell constant and cell volume vary with the dopant concentration. These variations can be explained in terms of their ionic radii. The DC electrical resistivity, measured by two point probe method, increases with increase in dopant concentration while it decreases with rise in temperature exhibiting semiconductor behaviour. Energy of activation of these ferrites is calculated by using Arrhenius type resistivity plots. Dielectric measurements of the synthesized compounds show exponential decrease in dielectric constant and dielectric loss factor with increase in frequency. This indicates the normal dielectric behaviour of ferrites.

  2. Demonstration of enhanced K-edge angiography using a cerium target x-ray generator

    SciTech Connect

    Sato, Eiichi; Tanaka, Etsuro; Mori, Hidezo; Kawai, Toshiaki; Ichimaru, Toshio; Sato, Shigehiro; Takayama, Kazuyoshi; Ido, Hideaki

    2004-11-01

    The cerium target x-ray generator is useful in order to perform enhanced K-edge angiography using a cone beam because K-series characteristic x rays from the cerium target are absorbed effectively by iodine-based contrast mediums. The x-ray generator consists of a main controller, a unit with a Cockcroft-Walton circuit and a fixed anode x-ray tube, and a personal computer. The tube is a glass-enclosed diode with a cerium target and a 0.5-mm-thick beryllium window. The maximum tube voltage and current were 65 kV and 0.4 mA, respectively, and the focal-spot sizes were 1.0x1.3 mm. Cerium K{alpha} lines were left using a barium sulfate filter, and the x-ray intensity was 0.48 {mu}C/kg at 1.0 m from the source with a tube voltage of 60 kV, a current of 0.40 mA, and an exposure time of 1.0 s. Angiography was performed with a computed radiography system using iodine-based microspheres. In coronary angiography of nonliving animals, we observed fine blood vessels of approximately 100 {mu}m with high contrasts.

  3. Long range ordered alloys modified by addition of niobium and cerium

    DOEpatents

    Liu, C.T.

    1984-08-22

    Long range ordered alloys are described having the nominal composition (Fe,Ni,Co)/sub 3/ (V,M) where M is a ductility enhancing metal selected from the group Ti, Zr, Hf with additions of small amounts of cerium and niobium to dramatically enhance the creep properties of the resulting alloys.

  4. Long range ordered alloys modified by addition of niobium and cerium

    DOEpatents

    Liu, Chain T.

    1987-01-01

    Long range ordered alloys are described having the nominal composition (Fe,Ni,Co).sub.3 (V,M) where M is a ductility enhancing metal selected from the group Ti, Zr, Hf with additions of small amounts of cerium and niobium to drammatically enhance the creep properties of the resulting alloys.

  5. Resonant photoemission study of the 4f spectral function of cerium in Ce/Fe(100) interfaces

    SciTech Connect

    Witkowski, N.; Bertran, F.; Gourieux, T.; Kierren, B.; Malterre, D.; Panaccione, G. |

    1997-11-01

    In this paper, we present a resonant photoemission study of the cerium 4f spectral function in Ce/Fe(100) interfaces. By covering cerium ultrathin films with lanthanum, we completely suppress the surface contribution of the spectra. Then we show that the cerium atoms at the interface are in an intermediate valent state, whereas the f{sup 1} configuration is stabilized in the top layer. This method allows us to obtain the genuine 4f spectral function of the interface, and could be extended to a study of Ce-based compounds. {copyright} {ital 1997} {ital The American Physical Society}

  6. 4d → 4f resonance in photoabsorption of cerium ion Ce3+ and endohedral cerium in fullerene complex {\\rm{Ce}}@{{{\\rm{C}}}_{82}}^{+}

    NASA Astrophysics Data System (ADS)

    Schrange-Kashenock, G.

    2016-09-01

    The theoretical investigation of the single-photoionization spectra in the 4d-resonance region (120-150 eV) for the ionic cerium Ce3+ and cerium in the endohedral complex {{Ce}}@{{{{C}}}82}+ (in practice, {{{Ce}}}3+@{{{{C}}}82}2-) is presented. The fullerene cage is modeled by ab initio spherical jellium shell with an accurate account for the real distribution of carbon electron density. The oscillator strengths are calculated within the multiconfiguration Dirac-Fock (MCDF) approach for phototransitions from the outermost shells of the ion Ce3+ with and without the influence of the potential generated by a fullerene cage. It is shown that the integrated oscillator strengths have the main contribution from the Ce3+ 4d → 4f (ten possible from the phototransitions {}2F{7/2,5/2}\\to {}2D{3/2,5/2},{}2F{5/2,7/2},{}2G{5/2,7/2}) resonance photoexcitations. The corresponding precise MCDF values for the oscillator strengths and the transition energies are presented for the first time. It is demonstrated that the resonance {f}4d\\to 4f oscillator strengths are slightly affected by the presence of the cage potential, despite the fact that the spectral levels structure is changed when the effect of this potential is included. The Auger 4d -1 decay from the cerium free ion Ce3+ and the encapsulated endohedral ion Ce3+@ are considered within the two-step model and the corresponding Lorentzian profiles are presented. This model clearly reveals the correspondence of the complex resonance profile in the Ce3+ photoabsorption to the fine structure of ion energy levels. The smoothing of the resonance profile in the photoabsorption of the endohedral system {{Ce}}@{{{{C}}}82}+ compared with the free ion Ce3+ is attributed to increasing the linewidths of the Auger transitions. This increase is estimated from the relevant experiment (Müller et al 2008 Phys. Rev. Lett. 101 133001) to be strong; as at least three times the value for an isolated ion. The presence of the confining fullerene

  7. 4d → 4f resonance in photoabsorption of cerium ion Ce3+ and endohedral cerium in fullerene complex {\\rm{Ce}}@{{{\\rm{C}}}_{82}}^{+}

    NASA Astrophysics Data System (ADS)

    Schrange-Kashenock, G.

    2016-09-01

    The theoretical investigation of the single-photoionization spectra in the 4d-resonance region (120–150 eV) for the ionic cerium Ce3+ and cerium in the endohedral complex {{Ce}}@{{{{C}}}82}+ (in practice, {{{Ce}}}3+@{{{{C}}}82}2-) is presented. The fullerene cage is modeled by ab initio spherical jellium shell with an accurate account for the real distribution of carbon electron density. The oscillator strengths are calculated within the multiconfiguration Dirac–Fock (MCDF) approach for phototransitions from the outermost shells of the ion Ce3+ with and without the influence of the potential generated by a fullerene cage. It is shown that the integrated oscillator strengths have the main contribution from the Ce3+ 4d → 4f (ten possible from the phototransitions {}2F{7/2,5/2}\\to {}2D{3/2,5/2},{}2F{5/2,7/2},{}2G{5/2,7/2}) resonance photoexcitations. The corresponding precise MCDF values for the oscillator strengths and the transition energies are presented for the first time. It is demonstrated that the resonance {f}4d\\to 4f oscillator strengths are slightly affected by the presence of the cage potential, despite the fact that the spectral levels structure is changed when the effect of this potential is included. The Auger 4d ‑1 decay from the cerium free ion Ce3+ and the encapsulated endohedral ion Ce3+@ are considered within the two-step model and the corresponding Lorentzian profiles are presented. This model clearly reveals the correspondence of the complex resonance profile in the Ce3+ photoabsorption to the fine structure of ion energy levels. The smoothing of the resonance profile in the photoabsorption of the endohedral system {{Ce}}@{{{{C}}}82}+ compared with the free ion Ce3+ is attributed to increasing the linewidths of the Auger transitions. This increase is estimated from the relevant experiment (Müller et al 2008 Phys. Rev. Lett. 101 133001) to be strong; as at least three times the value for an isolated ion. The presence of the confining

  8. Cerium, uranium, and plutonium behavior in glass-bonded sodalite, a ceramic nuclear waste form.

    SciTech Connect

    Lewis, M. A.; Lexa, D.; Morss, L. R.; Richmann, M. K.

    1999-09-03

    Glass-bonded sodalite is being developed as a ceramic waste form (CWF) to immobilize radioactive fission products, actinides, and salt residues from electrometallurgical treatment of spent nuclear reactor fuel. The CWF consists of about 75 mass % sodalite, 25 mass % glass, and small amounts of other phases. This paper presents some results and interpretation of physical measurements to characterize the CWF structure, and dissolution tests to measure the release of matrix components and radionuclides from the waste form. Tests have been carried out with specimens of the CWF that contain rare earths at concentrations similar to those expected in the waste form. Parallel tests have been carried out on specimens that have uranium or plutonium as well as the rare earths at concentrations similar to those expected in the waste forms; in these specimens UCl{sub 3} forms UO{sub 2} and PuCl{sub 3} forms PuO{sub 2}. The normalized releases of rare earths in dissolution tests were found to be much lower than those of matrix elements (B, Si, Al, Na). When there is no uranium in the CWF, the release of cerium is two to ten times lower than the release of the other rare earths. The low release of cerium may be due to its tetravalent state in uranium-free CWF. However, when there is uranium in the CWF, the release of cerium is similar to that of the other rare earths. This trivalent behavior of cerium is attributed to charge transfer or covalent interactions among cerium, uranium, and oxygen in (U,Ce)O{sub 2}.

  9. Methodology for the effective stabilization of tin-oxide-based oxidation/reduction catalysts

    NASA Technical Reports Server (NTRS)

    Jordan, Jeffrey D. (Inventor); Schryer, David R. (Inventor); Davis, Patricia P. (Inventor); Leighty, Bradley D. (Inventor); Watkins, Anthony N. (Inventor); Schryer, Jacqueline L. (Inventor); Oglesby, Donald M. (Inventor); Gulati, Suresh T. (Inventor); Summers, Jerry C. (Inventor)

    2011-01-01

    The invention described herein involves a novel approach to the production of oxidation/reduction catalytic systems. The present invention serves to stabilize the tin oxide reducible metal-oxide coating by co-incorporating at least another metal-oxide species, such as zirconium. In one embodiment, a third metal-oxide species is incorporated, selected from the group consisting of cerium, lanthanum, hafnium, and ruthenium. The incorporation of the additional metal oxide components serves to stabilize the active tin-oxide layer in the catalytic process during high-temperature operation in a reducing environment (e.g., automobile exhaust). Moreover, the additional metal oxides are active components due to their oxygen-retention capabilities. Together, these features provide a mechanism to extend the range of operation of the tin-oxide-based catalyst system for automotive applications, while maintaining the existing advantages.

  10. Radioactive waste forms stabilized by ChemChar gasification: characterization and leaching behavior of cerium, thorium, protactinium, uranium, and neptunium.

    PubMed

    Marrero, T W; Morris, J S; Manahan, S E

    2004-02-01

    The uses of a thermally reductive gasification process in conjunction with vitrification and cementation for the long-term disposal of low level radioactive materials have been investigated. gamma-ray spectroscopy was used for analysis of carrier-free protactinium-233 and neptunium-239 and a stoichiometric amount of cerium (observed cerium-141) subsequent to gasification and leaching, up to 48 days. High resolution ICP-MS was used to analyze the cerium, thorium, and uranium from 46 to 438 days of leaching. Leaching procedures followed the guidance of ASTM Procedure C 1220-92, Standard Test Method for Static Leaching of Monolithic Waste Forms for Disposal of Radioactive Waste. The combination of the thermally reductive pretreatment, vitrification and cementation produced a highly non-leachable form suitable for long-term disposal of cerium, thorium, protactinium, uranium, and neptunium.

  11. Radioactive waste forms stabilized by ChemChar gasification: characterization and leaching behavior of cerium, thorium, protactinium, uranium, and neptunium.

    PubMed

    Marrero, T W; Morris, J S; Manahan, S E

    2004-02-01

    The uses of a thermally reductive gasification process in conjunction with vitrification and cementation for the long-term disposal of low level radioactive materials have been investigated. gamma-ray spectroscopy was used for analysis of carrier-free protactinium-233 and neptunium-239 and a stoichiometric amount of cerium (observed cerium-141) subsequent to gasification and leaching, up to 48 days. High resolution ICP-MS was used to analyze the cerium, thorium, and uranium from 46 to 438 days of leaching. Leaching procedures followed the guidance of ASTM Procedure C 1220-92, Standard Test Method for Static Leaching of Monolithic Waste Forms for Disposal of Radioactive Waste. The combination of the thermally reductive pretreatment, vitrification and cementation produced a highly non-leachable form suitable for long-term disposal of cerium, thorium, protactinium, uranium, and neptunium. PMID:14637345

  12. A chemical-spectrochemical method for the determination of rare earth elements and thorium in cerium minerals

    USGS Publications Warehouse

    Rose, H.J.; Murata, K.J.; Carron, M.K.

    1954-01-01

    In a combined chemical-spectrochemical procedure for quantitatively determining rare earth elements in cerium minerals, cerium is determined volumetrically, a total rare earths plus thoria precipitate is separated chemically, the ceria content of the precipitate is raised to 80??0 percent by adding pure ceria, and the resulting mixture is analyzed for lanthanum, praseodymium, neodymium, samarium, gadolinium, yttrium, and thorium spectrochemically by means of the d.c. carbon arc. Spectral lines of singly ionized cerium are used as internal standard lines in the spectrochemical determination which is patterned after Fassel's procedure [1]. Results of testing the method with synthetic mixtures of rare earths and with samples of chemically analyzed cerium minerals show that the coefficient of variation for a quadruplicate determination of any element does not exceed 5??0 (excepting yttrium at concentrations less than 1 percent) and that the method is free of serious systematic error. ?? 1954.

  13. Composite catalyst for carbon monoxide and hydrocarbon oxidation

    DOEpatents

    Liu, W.; Flytzani-Stephanopoulos, M.

    1996-03-19

    A method and composition are disclosed for the complete oxidation of carbon monoxide and/or hydrocarbon compounds. The method involves reacting the carbon monoxide and/or hydrocarbons with an oxidizing agent in the presence of a metal oxide composite catalyst. The catalyst is prepared by combining fluorite-type oxygen ion conductors with active transition metals. The fluorite oxide, selected from the group consisting of cerium oxide, zirconium oxide, thorium oxide, hafnium oxide, and uranium oxide, and may be doped by alkaline earth and rare earth oxides. The transition metals, selected from the group consisting of molybdenum, copper, cobalt, manganese, nickel, and silver, are used as additives. The atomic ratio of transition metal to fluorite oxide is less than one.

  14. Composite catalyst for carbon monoxide and hydrocarbon oxidation

    DOEpatents

    Liu, Wei; Flytzani-Stephanopoulos, Maria

    1996-01-01

    A method and composition for the complete oxidation of carbon monoxide and/or hydrocarbon compounds. The method involves reacting the carbon monoxide and/or hydrocarbons with an oxidizing agent in the presence of a metal oxide composite catalyst. The catalyst is prepared by combining fluorite-type oxygen ion conductors with active transition metals. The fluorite oxide, selected from the group consisting of cerium oxide, zirconium oxide, thorium oxide, hafnium oxide, and uranium oxide, and may be doped by alkaline earth and rare earth oxides. The transition metals, selected from the group consisting of molybdnum, copper, cobalt, maganese, nickel, and silver, are used as additives. The atomic ratio of transition metal to fluorite oxide is less than one.

  15. Composite solid oxide fuel cell anode based on ceria and strontium titanate

    DOEpatents

    Marina, Olga A.; Pederson, Larry R.

    2008-12-23

    An anode and method of making the same wherein the anode consists of two separate phases, one consisting of a doped strontium titanate phase and one consisting of a doped cerium oxide phase. The strontium titanate phase consists of Sr.sub.1-xM.sub.xTiO.sub.3-.delta., where M is either yttrium (Y), scandium (Sc), or lanthanum (La), where "x" may vary typically from about 0.01 to about 0.5, and where .delta. is indicative of some degree of oxygen non-stoichiometry. A small quantity of cerium may also substitute for titanium in the strontium titanate lattice. The cerium oxide consists of N.sub.yCe.sub.1-yO.sub.2-.delta., where N is either niobium (Nb), vanadium (V), antimony (Sb) or tantalum (Ta) and where "y" may vary typically from about 0.001 to about 0.1 and wherein the ratio of Ti in said first phase to the sum of Ce and N in the second phase is between about 0.2 to about 0.75. Small quantities of strontium, yttrium, and/or lanthanum may additionally substitute into the cerium oxide lattice. The combination of these two phases results in better performance than either phase used separately as an anode for solid oxide fuel cell or other electrochemical device.

  16. Bimetallic bonding and mixed oxide formation in the Ga-Pd-CeO2 system

    NASA Astrophysics Data System (ADS)

    Skála, Tomáš; Tsud, Nataliya; Prince, Kevin C.; Matolín, Vladimír

    2011-08-01

    The interaction of gallium and palladium with 2 nm CeO2(111) layers grown on Cu(111) was studied by core level photoelectron spectroscopy and resonant valence band spectroscopy. Palladium alone interacted weakly with ceria layers. Gallium deposited on cerium dioxide formed a mixed Ga2O3-Ce2O3 oxide of 1:1 stoichiometry (cerium gallate CeGaO3), with both metals in the M3+ oxidation state. Increasing Ga coverages led to the formation of lower oxidation states, i.e., Ga1+ in Ga2O oxide and metallic Ga0. Palladium deposited onto this complex system interacted with gallium leading to a breakage of Ga-ceria bonds, a decrease of the oxidation state of gallium, and formation of a Ga-Pd intermetallic alloy in which all components (CeO2, CeGaO3, Ga2O, Ga-Pd, and Pd) are in equilibrium.

  17. A DFT + U study of cerium solubility in La₂Zr₂O₇

    SciTech Connect

    Wang, X. J.; Xiao, Haiyan Y.; Zu, Xiaotao; Weber, William J.

    2012-02-17

    Density functional theory plus Hubbard U correction is employed to study the solubility of cerium in La₂Zr₂O₇. The results show that La₂Zr₂O₇ and Ce₂Zr₂O₇ form a solid solution over the whole range of cerium content. The solubility of Ce in La₂Zr₂O₇ can be partially attributed to the similar ionic radii of La³+ and Ce³+. Electronic structures of the La₂₋yCeyZr₂O₇ solid solution have been analyzed. The Ce 4ƒ states are found to be partially occupied, and Ce in the La₂₋yCeyZr₂O₇ solid solution exhibits a reduced charge state.

  18. Cerium Binding Activity of Pectins Isolated from the Seagrasses Zostera marina and Phyllospadix iwatensis

    PubMed Central

    Khotimchenko, Yuri; Khozhaenko, Elena; Kovalev, Valeri; Khotimchenko, Maxim

    2012-01-01

    Cerium binding activity of three different water soluble pectin compounds of different origin was studied in a batch sorption system. The Langmuir, Freundlich and BET sorption models were adopted to describe the binding reactions between metal ions and pectin molecules. The Langmuir model provided the best fit. Within the pH range from 4.0 to 6.0, the largest amount of the cerium ions was bound by pectin isolated from the seagrass Phylospadix iwatensis in comparison to pectin extracted from the seagrass Zostera marina and pectin obtained from citrus peel (commercial grade). The Langmuir constants were also highest for the pectin samples isolated from the seagrass P. iwatensis. The results obtained from this study suggest that pectin is a prospective source for the development of radioisotope-removing pharmaceuticals. PMID:22690146

  19. Measurement of the magnetic behaviour of 147Eu and 149Eu in cerium and platinum

    NASA Astrophysics Data System (ADS)

    Dietrich, M.; Zeitz, W.-D.; Weber, A.; Potzger, K.; Unterricker, S.; Schneider, F.; Samokhvalov, V.; Isolde Collaboration

    2005-07-01

    The local magnetism at europium in platinum and in cerium was studied using perturbed angular correlation (PAC) spectroscopy. In platinum, europium shows the electronic properties of the trivalent status, which has a non-magnetic ground state ( J=0). As a consequence, the Van Vleck contributions from the complete multiplet-level system predominantly determine the magnetic behaviour. In cerium, the measured data are close to the predictions for divalent europium. Here, only the electronic ground state, the pure spin state ( J=5/2), has to be taken into account. The measurements were done utilising the isomeric 11/2 - nuclear levels in 147Eu and 149Eu at 625 and 496 keV, respectively, after the precursors had been produced at the ion beam laboratory ISL Berlin or the on-line mass separator ISOLDE in Geneva.

  20. Luminescent Properties of Cerium Doped Potassium Iodide Single Crystals in Response to γ-irradiation.

    PubMed

    Bangaru, S; Saradha, K; Muralidharan, G

    2015-05-01

    Potassium iodide doped with cerium ions were prepared by Bridgemann Stockbarger technique and investigated by optical absorption, Photoluminescence(PL), Thermoluminescence(TL), Photostimulated Luminescence(PSL) and TL emission. The optical absorption measurement indicates that F and V centers are formed in the crystals during the γ-ray irradiation process. Optical absorption and Photoluminescence studies confirm the presence of cerium ions in the trivalent state. Spectral distribution under the Thermoluminescence Emission(TLE) and Optically Stimulated Luminescence(OSL) support the idea that the defect annihilation process to be due to thermal release of F-electron in KI:Ce(3+) crystals. Both Ce(3+) and Ce(2+) emissions were observed in the Thermoluminescence emission of the crystals. Thermoluminescence(TL) has been identified to be due to thermal release of electron produced during colouration process. PMID:25744528

  1. Thermodynamics of the α -γ transition in cerium studied by an LDA + Gutzwiller method

    NASA Astrophysics Data System (ADS)

    Tian, Ming-Feng; Song, Hai-Feng; Liu, Hai-Feng; Wang, Cong; Fang, Zhong; Dai, Xi

    2015-03-01

    Utilizing the local-density approximation (LDA) + Gutzwiller method, we have studied the α -γ transition in cerium. Our results indicate that the volume collapse transition between α and γ phases is present at zero temperature with negative pressure. By further providing a newly finite temperature generalization of the LDA + Gutzwiller method (using the mean-field potential approach), the entropy contributed by both electronic quasiparticles and lattice vibration included, we obtain the Gibbs free energy at a given volume and temperature, from which we get the α -γ transition at finite temperature and pressure. Our results indicate that the electronic entropy and lattice vibrational entropy both play important roles in the α -γ transition. We also calculated the equation of state and phase diagram of cerium, finding good agreement with the experiments.

  2. A cerium-lead redox flow battery system employing supporting electrolyte of methanesulfonic acid

    NASA Astrophysics Data System (ADS)

    Na, Zhaolin; Xu, Shengnan; Yin, Dongming; Wang, Limin

    2015-11-01

    A novel cerium-lead redox flow battery (RFB) employing Ce(IV)/Ce(III) and Pb(II)/Pb redox couples in the supporting electrolyte of methanesulfonic acid (MSA) is developed and preliminarily investigated. The RFB requires no additional catalyst and uses kinetically favorable reactions between low-cost reactants, and provides a desirable discharge voltage of approximately 1.7 V, with high average coulombic efficiency (CE) of 92% and energy efficiency (EE) of 86% over 800 cycles at 298 K. Stable cycling with an acceptable performance is achieved for a board operating temperature range of 253 K-313 K. The excellent performance obtained from the preliminary study suggests that the cerium-lead RFB promises to be applicable to large-scale energy storage for electricity grids.

  3. Improvement and analysis of the hydrogen-cerium redox flow cell

    NASA Astrophysics Data System (ADS)

    Tucker, Michael C.; Weiss, Alexandra; Weber, Adam Z.

    2016-09-01

    The H2-Ce redox flow cell is optimized using commercially-available cell materials. Cell performance is found to be sensitive to the upper charge cutoff voltage, membrane boiling pretreatment, methanesulfonic-acid concentration, (+) electrode surface area and flow pattern, and operating temperature. Performance is relatively insensitive to membrane thickness, Cerium concentration, and all features of the (-) electrode including hydrogen flow. Cell performance appears to be limited by mass transport and kinetics in the cerium (+) electrode. Maximum discharge power of 895 mW cm-2 was observed at 60 °C; an energy efficiency of 90% was achieved at 50 °C. The H2-Ce cell is promising for energy storage assuming one can optimize Ce reaction kinetics and electrolyte.

  4. PURIFICATION OF PLUTONIUM USING A CERIUM PRECIPITATE AS A CARRIER FOR FISSION PRODUCTS

    DOEpatents

    Faris, B.F.; Olson, C.M.

    1961-07-01

    Bismuth phosphate carrier precipitation processes are described for the separation of plutonium from fission products wherein in at least one step bismuth phosphate is precipitated in the presence of hexavalent plutonium thereby carrying a portion of the fission products from soluble plu tonium values. In this step, a cerium phosphate precipitate is formed in conjunction with the bismuth phosphate precipitate, thereby increasing the amount of fission products removed from solution.

  5. Application of cerium nitrate-silver sulphadiazine allows for postponement of excision and grafting.

    PubMed

    Vehmeyer-Heeman, M; Tondu, T; Van den Kerckhove, E; Boeckx, W

    2006-02-01

    Early excision and grafting cannot always be performed due to patient's medical status, and the lack of adequate donor sites. The use of cerium nitrate-silver sulphadiazine cream, which causes the formation of a leather-like eschar with excellent resistance to infection, is an alternative method. In order to postpone operations by using cerium nitrate-silver sulphadiazine, we compared the differences in contamination of the grafted areas between early and delayed excision. Eighteen patients underwent excision and grafting within 5 days post burn and nineteen patients were surgically treated after 5 days. Twelve months later the grafted areas were evaluated. Contamination of the grafted area occurred in 17 patients. No differences in contamination occurred between the early and delayed excision group, 8 versus 9. Also no differences in type of organism cultured and follow-up results were found between the early and delayed excision group. Cerium nitrate-silver sulphadiazine allows surgical treatment to be delayed without an increase of contamination of the grafted area and does not adversely affect the long-term outcome.

  6. Cerium, gallium and zinc containing mesoporous bioactive glass coating deposited on titanium alloy

    NASA Astrophysics Data System (ADS)

    Shruti, S.; Andreatta, F.; Furlani, E.; Marin, E.; Maschio, S.; Fedrizzi, L.

    2016-08-01

    Surface modification is one of the methods for improving the performance of medical implants in biological environment. In this study, cerium, gallium and zinc substituted 80%SiO2-15%CaO-5%P2O5 mesoporous bioactive glass (MBG) in combination with polycaprolactone (PCL) were coated over Ti6Al4 V substrates by dip-coating method in order to obtain an inorganic-organic hybrid coating (MBG-PCL). Structural characterization was performed using XRD, nitrogen adsorption, SEM-EDXS, FTIR. The MBG-PCL coating uniformly covered the substrate with the thickness found to be more than 1 μm. Glass and polymer phases were detected in the coating along with the presence of biologically potent elements cerium, gallium and zinc. In addition, in vitro bioactivity was investigated by soaking the coated samples in simulated body fluid (SBF) for up to 30 days at 37 °C. The apatite-like layer was monitored by FTIR, SEM-EDXS and ICP measurements and it formed in all the samples within 15 days except zinc samples. In this way, an attempt was made to develop a new biomaterial with improved in vitro bioactive response due to bioactive glass coating and good mechanical strength of Ti6Al4 V alloy along with inherent biological properties of cerium, gallium and zinc.

  7. Controlled Redox Chemistry at Cerium within a Tripodal Nitroxide Ligand Framework.

    PubMed

    Bogart, Justin A; Lippincott, Connor A; Carroll, Patrick J; Booth, Corwin H; Schelter, Eric J

    2015-12-01

    Ligand reorganization has been shown to have a profound effect on the outcome of cerium redox chemistry. Through the use of a tethered, tripodal, trianionic nitroxide ligand, [((2-tBuNOH)C6 H4 CH2 )3 N](3-) (TriNOx (3-) ), controlled redox chemistry at cerium was accomplished, and typically reactive complexes of tetravalent cerium were isolated. These included rare cationic complexes [Ce(TriNOx )thf][BAr(F) 4 ], in which Ar(F) =3,5-(CF3 )2 -C6 H3 , and [Ce(TriNOx )py][OTf]. A rare complete Ce-halide series, Ce(TriNOx )X, in which X=F(-) , Cl(-) , Br(-) , I(-) , was also synthesized. The solution chemistry of these complexes was explored through detailed solution-phase electrochemistry and (1) H NMR experiments and showed a unique shift in the ratio of species with inner- and outer-sphere anions with size of the anionic X(-) group. DFT calculations on the series of calculations corroborated the experimental findings.

  8. Microstructure and electrochemical behavior of cerium conversion coating modified with silane agent on magnesium substrates

    NASA Astrophysics Data System (ADS)

    Lei, Li; Shi, Jing; Wang, Xin; Liu, Dan; Xu, Haigang

    2016-07-01

    The cerium conversion coating with and without different concentrations of silane agent bis-(γ-triethoxysilylpropyl)-tetrasulfide (BTESPT) modification is obtained on magnesium alloys. Detailed properties of the coatings and the role of BTESPT as an additive are studied and followed with careful discussion. The coating morphology, wettability, chemical composition and corrosion resistance are characterized by scanning electronic microscope (SEM), water contact-angle, X-ray photoelectron spectroscopy (XPS), potentiodynamic measurements and electrochemical impedance spectroscopy (EIS). The electrochemical behavior of the coatings is investigated using EIS. The results indicate that the coating morphology and composition can be controlled by changing silane concentration. The combination of cerium ions and silane molecules could promote the formation of more homogenous and higher hydrophobic coating. The coating turns to be more compact and the adhesive strength between the coating and the magnesium substrate are strongly improved with the formation of Sisbnd Osbnd Si and Sisbnd Osbnd M chemical bonds. The optimum corrosion resistance of the coating in the corrosive media is obtained by 25 ml L-1 BTESPT modification. This whole study implies that the cerium conversion coating modified with certain silane agent deserves cautiousness before its application for corrosion resistance.

  9. Treated Nanolayered Mn Oxide by Oxidizable Compounds: A Strategy To Improve the Catalytic Activity toward Water Oxidation.

    PubMed

    Mahdi Najafpour, Mohammad; Jafarian Sedigh, Davood; Maedeh Hosseini, Seyedeh; Zaharieva, Ivelina

    2016-09-01

    Herein, we investigate the effect of post-treatment of nanolayered manganese oxide by different inorganic and organic compounds. We use the fact that nanolayered manganese oxides are among the strongest naturally occurring oxidants, capable of oxidizing a wide range of organic molecules. Post-treatment of the synthetic Mn oxides with oxidizable compounds increases the cerium(IV)-driven water oxidation catalyzed by treated layered manganese oxides more than 25 times. On the basis of X-ray absorption investigations, we attribute this effect to the increased amount of manganese(III) ions. This finding can explain some puzzles in water oxidation by manganese oxides and may help to advance toward an efficient design strategy of water-oxidizing catalyst in artificial photosynthetic systems. PMID:27537432

  10. Catalytic Degradation of Benzene over Nanocatalysts containing Cerium and Manganese

    PubMed Central

    Wang, Zhen; Deng, Yuzhou; Shen, Genli; Akram, Sadia; Han, Ning

    2016-01-01

    Abstract A Ce–Mn composite oxide possessing a rod‐like morphology (with a fixed molar ratio of Ce/Mn=3:7) was synthesized through a hydrothermal method. Mn ions were doped into a CeO2 framework to replace Ce ions, thereby increasing the concentration of oxygen vacancies. The formation energies of O vacancies for the Ce–Mn composite oxide were calculated by applying density functional theory (DFT). The data showed that it was easier to form an O vacancy in the composite. The catalytic behavior of the Ce–Mn composite oxide for benzene degradation was researched in detail, which exhibited a higher activity than the pure phases. Based on this, the Ce–Mn composite oxide was chosen as a supporter to load PdO nanoparticles. The activity was enhanced further compared with that of the supporter alone (for the supporter, the reaction rate R 214 °C=0.68×10−4 mol gcat −1 s−1 and apparent activation energy E a=12.75 kJ mol−1; for the supporting catalyst, R 214 °C=1.46×10−4 mol gcat −1 s−1, E a=10.91 kJ mol−1). The corresponding catalytic mechanism was studied through in situ Raman and FTIR spectroscopy, which indicated that the process of benzene oxidation was related to different types of oxygen species existing at the surface of the catalysts. PMID:27777843

  11. Integrated Heat Switch/Oxide Sorption Compressor

    NASA Technical Reports Server (NTRS)

    Bard, Steven

    1989-01-01

    Thermally-driven, nonmechanical compressor uses container filled with compressed praseodymium cerium oxide powder (PrCeOx) to provide high-pressure flow of oxygen gas for driving closed-cycle Joule-Thomson-expansion refrigeration unit. Integrated heat switch/oxide sorption compressor has no moving parts except check valves, which control flow of oxygen gas between compressor and closed-cycle Joule-Thomson refrigeration system. Oxygen expelled from sorbent at high pressure by evacuating heat-switch gap and turning on heater.

  12. Preparation of Thin Melanin-Type Films by Surface-Controlled Oxidation.

    PubMed

    Salomäki, Mikko; Tupala, Matti; Parviainen, Timo; Leiro, Jarkko; Karonen, Maarit; Lukkari, Jukka

    2016-04-26

    The preparation of thin melanin films suitable for applications is challenging. In this work, we present a new alternative approach to thin melanin-type films using oxidative multilayers prepared by the sequential layer-by-layer deposition of cerium(IV) and inorganic polyphosphate. The interfacial reaction between cerium(IV) in the multilayer and 5,6-dihydroxyindole (DHI) in the adjacent aqueous solution leads to the formation of a thin uniform film. The oxidation of DHI by cerium(IV) proceeds via known melanin intermediates. We have characterized the formed DHI-melanin films using scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), UV-vis spectroscopy, and spectroelectrochemistry. When a five-bilayer oxidative multilayer is used, the film is uniform with a thickness of ca. 10 nm. Its chemical composition, as determined using XPS, is typical for melanin. It is also redox active, and its oxidation occurs in two steps, which can be assigned to semiquinone and quinone formation within the indole structural motif. Oxidative multilayers can also oxidize dopamine, but the reaction stops at the dopamine quinone stage because of the limited amount of the multilayer-based oxidizing agent. However, dopamine oxidation by Ce(IV) was studied also in solution by UV-vis spectroscopy and mass spectrometry in order to verify the reaction mechanism and the final product. In solution, the oxidation of dopamine by cerium shows that the indole ring formation takes place already at low pH and that the mass spectrum of the final product is practically identical with that of commercial melanin. Therefore, layer-by-layer formed oxidative multilayers can be used to deposit functional melanin-type thin films on arbitrary substrates by a surface-controlled reaction.

  13. Grain Growth Behavior, Tensile Impact Ductility, and Weldability of Cerium-Doped Iridium Alloys

    SciTech Connect

    McKamey, C.G.

    2002-05-28

    An iridium alloy doped with small amounts of cerium and thorium is being developed as a potential replacement for the iridium-based DOP-26 alloy (doped with thorium only) that is currently used by the National Aeronautics and Space Administration (NASA) for cladding and post-impact containment of the radioactive fuel in radioisotope thermoelectric generator (RTG) heat sources which provide electric power for interplanetary spacecraft. This report summarizes results of studies conducted to date under the Iridium Alloy Characterization and Development subtask of the Radioisotope Power System Materials Production and Technology Program to characterize the properties of the iridium-based alloy (designated as DOP-40) containing both cerium and thorium. Included within this report are data on grain growth of sheet material in vacuum and low-pressure oxygen environments, grain growth in vacuum of the clad vent set cup material, weldability, and the effect of grain size and test temperature on tensile properties. Where applicable, data for the DOP-26 alloy are included for comparison. Both grain size and grain-boundary cohesion affect the ductility of iridium alloys. In this study it was found that cerium and thorium, when added together, refine grain size more effectively than when thorium is added by itself (especially at high temperatures). In addition, the effect of cerium additions on grain-boundary cohesion is similar to that of thorium. Mechanical testing at both low ({approx} 10{sup -3}s{sup -1}) and high ({approx} 10{sup -3}s{sup -1}) strain rates showed that the Ce/Th-doped alloys have tensile ductilities that are as good or better than the DOP-26 alloy. The general conclusion from these studies is that cerium can be used to replace some of the radioactive thorium currently used in DOP-26 while maintaining or improving its metallurgical properties. The current DOP-26 alloy meets all requirements for cladding the radioactive fuel in the RTG heat source, but the

  14. Formation of δ-Lactones by Cerium-Catalyzed, Baeyer-Villiger-Type Coupling of β-Oxoesters, Enol Acetates, and Dioxygen.

    PubMed

    Geibel, Irina; Dierks, Anna; Schmidtmann, Marc; Christoffers, Jens

    2016-09-01

    Formation of δ-lactones is observed when cyclopentanone-2-carboxylates are converted in a cerium-catalyzed reaction with α-aryl vinyl acetates under oxidative conditions. The products of this transformation possess a 1,4-dicarbonyl constitution together with a quaternary carbon center. Atmospheric oxygen is the oxidant in this process, which can be regarded as ideal from economic and ecological points of view. Further advantages of this new C-C coupling and oxidation reaction are its operational simplicity and the application of nontoxic and inexpensive CeCl3·7 H2O as precatalyst. This so far unprecedented reaction is proposed to proceed via 1,2-dioxane derivatives, which decompose under formation of an oxycarbenium cation in a Baeyer-Villiger-type pathway. This mechanistic picture is supported by the observation that electron-rich (donor substituted or heteroaromatic) enol esters give higher yields than electron deficient congeners. Apart from 1,4-diketones and α-hydroxylated β-oxoesters formed as byproducts, the yields of δ-lactones range from moderate to good (up to 74%). PMID:27494288

  15. Synthesis, Characterization, and Application of 1-D Cerium Oxide Nanomaterials: A Review

    PubMed Central

    Lin, Kuen-Song; Chowdhury, Sujan

    2010-01-01

    The present work provides a comprehensive overview of the recent progress of research work toward developing new one dimensional (1-D) ceria (CeO2) nanomaterials. The review has been classified into three parts: the preparation procedures with identification of the existing different dimensional ceria nanomaterials, the formation mechanisms, and an analysis of their applications. From literature survey, it is inaugurated that the fundamental structures of the ceria nanomaterials constructively dominate their properties and applications. In addition, this work will also provide a perspective on the future technical trends for the development of different dimensional CeO2 nanomaterials. PMID:20957090

  16. Metallic phases of cobalt-based catalysts in ethanol steam reforming: The effect of cerium oxide

    SciTech Connect

    Lin, Sean S.-Y.; Kim, Do Heui; Ha, Su Y.

    2009-02-28

    The catalytic activity of cobalt in the production of hydrogen via ethanol steam reforming has been investigated in its relation to the crystalline structure of metallic cobalt. At a reaction temperature of 350 8C, the specific hydrogen production rates show that hexagonal close-packed (hcp) cobalt possesses higher activity than face-centered cubic (fcc) cobalt. However, at typical reaction temperatures (400– 500 8C) for ethanol steam reforming, hcp cobalt is transformed to less active fcc cobalt, as confirmed by in situ X-ray diffractometry (XRD). The addition of CeO2 promoter (10 wt.%) stabilizes the hcp cobalt structure at reforming temperatures up to 600 8C. Moreover, during the pre-reduction process, CeO2 promoter prevents sintering during the transformation of Co3O4 to hcp cobalt. Both reforming experiments and in situ diffuse-reflectance infrared Fourier transform spectroscopy (DRIFTS) showed that the surface reactions were modified by CeO2 promoter on 10% Ce–Co (hcp) to give a lower CO selectivity and a higher H2 yield as compared with the unpromoted hcp Co.

  17. Cerium dioxide and zinc oxide nanoparticles alter the nutritional value of soil cultivated soybean plants.

    PubMed

    Peralta-Videa, Jose R; Hernandez-Viezcas, Jose A; Zhao, Lijuan; Diaz, Baltazar Corral; Ge, Yuan; Priester, John H; Holden, Patricia Ann; Gardea-Torresdey, Jorge L

    2014-07-01

    The aim of this study was to determine nutrient elements in soybean (Glycine max) plants cultivated in farm soil amended with nCeO2 at 0-1000 mg kg(-1) and nZnO at 0-500 mg kg(-1). Digested samples were analyzed by ICP-OES/MS. Compared to control, pods from nCeO2 at 1000 mg kg(-1) had significantly less Ca but more P and Cu, while pods from 100 mg kg(-1)nZnO had more Zn, Mn, and Cu. Plants treated with nZnO showed significant correlations among Zn, P, and S in pods with Zn in roots. Correlations among pod Zn/root Zn was r = 0.808 (p ≤ 0.01) and pod P/root P was r = 0.541 (p ≤ 0.05). The correlation among pod S/root S was r = -0.65 (p ≤ 0.01). While nCeO2 treatments exhibited significant correlations between pod Ca/root Ca (r = 0.645, p ≤ 0.05). The data suggest that nCeO2 and nZnO alter the nutritional value of soybean, which could affect the health of plants, humans, and animals.

  18. The Effect of Cerium Oxide Addition on the Properties and Behavior of Y-TZP

    PubMed Central

    Ragurajan, D.; Satgunam, M.; Golieskardi, M.

    2014-01-01

    The effects of CeO2 addition on the sintering behavior and mechanical properties of Y-TZP have been investigated over a wide sintering regime by pressureless sintering. It has been revealed that small additions of CeO2 (0.3–1.0 wt%) to Y-TZP were beneficial in enhancing the mechanical properties and hydrothermal ageing resistance of Y-TZP. Sintered samples were used to evaluate the bulk density, Vickers's hardness, Young's modulus, and fracture toughness of the material. CeO2 doped Y-TZPs were sintered at relatively low temperatures (1250°C and 1350°C) retaining high bulk density (>97% of theoretical density) and high Young's modulus (>200 GPa) without sacrificing tetragonal phase stability. The optimum level of dopant was found to be at 0.5 wt% for sintering between 1250°C and 1450°C using the standard 2 h holding time cycle, with sintered body exhibiting excellent combination of properties when compared to the undoped ceramics. In this experiment, the addition of 0.5 wt% recorded a bulk density reading of 5.9 g/cm3, Vickers hardness value of 13.2 GPa, Young's modulus value of 211 GPa, and fracture toughness of 6.4 MPam1/2, respectively, in a temperature range of 1400–1450°C. PMID:27437471

  19. Dissolution of cerium(IV)-lanthanide(III) oxides: comparative effect of chemical composition, temperature, and acidity.

    PubMed

    Horlait, D; Clavier, N; Szenknect, S; Dacheux, N; Dubois, V

    2012-03-19

    The dissolution of Ce(1-x)Ln(x)O(2-x/2) solid solutions was undertaken in various acid media in order to evaluate the effects of several physicochemical parameters such as chemical composition, temperature, and acidity on the reaction kinetics. The normalized dissolution rates (R(L,0)) were found to be strongly modified by the trivalent lanthanide incorporation rate, due to the presence of oxygen vacancies decreasing the samples cohesion. Conversely, the nature of the trivalent cation considered only weakly impacted the R(L,0) values. The dependence of the normalized dissolution rates on the temperature then appeared to be of the same order of magnitude than that of chemical composition. Moreover, it allowed determining the corresponding activation energy (E(A) ≈ 60-85 kJ·mol(-1)) which accounts for a dissolution driven by surface-controlled reactions. A similar conclusion was made regarding the acidity of the solution: the partial order related to (H(3)O(+)) reaching about 0.7. Finally, the prevailing effect of the incorporation of aliovalent cations in the fluorite-type CeO(2) matrix on the dissolution kinetics precluded the observation of slight effects such as those linked to the complexing agents or to the crystal structure of the samples.

  20. Toxicity assessment of Titanium Dioxide and Cerium Oxide nanoparticles in Arabidopsis thaliana L.

    EPA Science Inventory

    The production and applications of nanoparticles (NP) in diverse fields has steadily increased in recent decades; however, knowledge about risks of NP to human health and ecosystems is still scarce. In this study, we assessed potential toxicity of two commercially used engineere...

  1. Oxygen exchange reaction kinetics for cerium(IV) oxide at 1000 °C

    SciTech Connect

    Whiting, Christofer E. Douglas, John M.; Cremeans, Bethany M.; Barklay, Chadwick D.; Kramer, Daniel P.

    2014-10-15

    Bulk oxygen exchange rate kinetics on CeO{sub 2} at 1000 °C were observed to have a first order dependence on the fraction of reaction remaining and to be independent of oxygen partial pressure, total pressure, particle size, and specific surface area. This suggests that the exchange reaction is dominated by an internal chemical reaction that is occurring throughout the bulk of the material, and not at the material surface. Oxygen exchange rates were limited by this internal chemical reaction for all CeO{sub 2} powders studied (15 nm to −325 mesh), and had a rate constant of 1.19×10{sup −2} s{sup −1} with a time to completion of 617 s. These results are similar to the exchange rates observed previously on PuO{sub 2}, suggesting that oxygen exchange on PuO{sub 2} may also be dominated by an internal chemical reaction under similar conditions. This work will help guide future experiments on {sup 238}PuO{sub 2} oxygen exchange reactions. - Graphical abstract: Oxygen exchange kinetics on CeO{sub 2} at 1000 °C are independent of a wide range of experimental conditions and exhibit first-order chemical reaction kinetics. - Highlights: • Stable oxygen exchange rates obtained on a variety of CeO{sub 2} powders at 1000 °C. • Exchange rates are independent of atmospheric composition and specific surface area. • Exchange rates are limited by an internal chemical reaction, not a surface reaction. • CeO{sub 2} exchange rates appear similar to the rates observed on PuO{sub 2} at 1000 °C.

  2. Toxicity assessment of cerium oxide nanoparticles in cilantro (Coriandrum sativum L.) plants grown in organic soil.

    PubMed

    Morales, Maria Isabel; Rico, Cyren M; Hernandez-Viezcas, Jose Angel; Nunez, Jose E; Barrios, Ana Cecilia; Tafoya, Alejandro; Flores-Marges, Juan Pedro; Peralta-Videa, Jose R; Gardea-Torresdey, Jorge L

    2013-07-01

    Studies have shown that CeO₂ nanoparticles (NPs) can be accumulated in plants without modification, which could pose a threat for human health. In this research, cilantro (Coriandrum sativum L.) plants were germinated and grown for 30 days in soil amended with 0 to 500 mg kg⁻¹ CeO₂ NPs and analyzed by spectroscopic techniques and biochemical assays. At 125 mg kg⁻¹, plants produced longer roots (p ≤ 0.05), and at 500 mg kg⁻¹, there was higher Ce accumulation in tissues (p ≤ 0.05). At 125 mg, catalase activity significantly increased in shoots and ascorbate peroxidase in roots (p ≤ 0.05). The FTIR analyses revealed that at 125 mg kg⁻¹ the CeO₂ NPs changed the chemical environment of carbohydrates in cilantro shoots, for which changes in the area of the stretching frequencies were observed. This suggests that the CeO₂ NPs could change the nutritional properties of cilantro.

  3. Particle-size dependent accumulation and trophic transfer of cerium oxide through a terrestrial food chain.

    PubMed

    Hawthorne, Joseph; De la Torre Roche, Roberto; Xing, Baoshan; Newman, Lee A; Ma, Xingmao; Majumdar, Sanghamitra; Gardea-Torresdey, Jorge; White, Jason C

    2014-11-18

    The accumulation and trophic transfer of nanoparticle (NP) or bulk CeO2 through a terrestrial food chain was evaluated. Zucchini (Cucurbita pepo L.) was planted in soil with 0 or 1228 μg/g bulk or NP CeO2. After 28 d, zucchini tissue Ce content was determined by ICP-MS. Leaf tissue from each treatment was used to feed crickets (Acheta domesticus). After 14 d, crickets were analyzed for Ce content or were fed to wolf spiders (family Lycosidae). NP CeO2 significantly suppressed flower mass relative to control and bulk treatments. The Ce content of zucchini was significantly greater when exposure was in the NP form. The flowers, leaves, stems, and roots of zucchini exposed to bulk CeO2 contained 93.3, 707, 331, and 119,000 ng/g, respectively; NP-exposed plants contained 153, 1510, 479, and 567 000 ng/g, respectively. Crickets fed NP CeO2-exposed zucchini leaves contained significantly more Ce (33.6 ng/g) than did control or bulk-exposed insects (15.0-15.2 ng/g). Feces from control, bulk, and NP-exposed crickets contained Ce at 248, 393, and 1010 ng/g, respectively. Spiders that consumed crickets from control or bulk treatments contained nonquantifiable Ce; NP-exposed spiders contained Ce at 5.49 ng/g. These findings show that NP CeO2 accumulates in zucchini at greater levels than equivalent bulk materials and that this greater NP intake results in trophic transfer and possible food chain contamination. PMID:25340623

  4. Effect of cobalt doping on structural, optical and redox properties cerium oxide nanoparticles

    NASA Astrophysics Data System (ADS)

    Ansari, Anees A.; Labis, J.; Alam, M.; Ramay, Shahid M.; Ahmad, N.; Mahmood, Asif

    2016-03-01

    Cobalt-doped ceria nanoparticles were synthesized using the polyol method under co-precipitation hydrolysis. The structural, morphological, optical and redox properties were observed to investigate the influence of different concentration of cobalt ion doping on the prepared CeO2 nanomaterials in terms of X-ray diffraction, field-emission transmission electron microscopy, thermogravimetric analysis, Fourier-transform infrared spectroscopy, UV/vis absorption spectroscopy and temperature program reduction techniques. The optical band gap energy was calculated from the optical absorption spectra for doped ceria nanoparticles, which have been found to be 2.68, 2.77, and 2.82 eV for the 2, 4, and 7 mol% Co ion-doped CeO2 nanoparticles, respectively. As observed, the band gap energies increases as the doping Co ion concentrations increased, which could be due to significant increased oxygen vacancies with Co doping. The synergistic interaction between Co and CeO2 was the main factor responsible for high catalytic activity of cobalt-doped CeO2 model catalysts.

  5. Cerium dioxide and zinc oxide nanoparticles alter the nutritional value of soil cultivated soybean plants.

    PubMed

    Peralta-Videa, Jose R; Hernandez-Viezcas, Jose A; Zhao, Lijuan; Diaz, Baltazar Corral; Ge, Yuan; Priester, John H; Holden, Patricia Ann; Gardea-Torresdey, Jorge L

    2014-07-01

    The aim of this study was to determine nutrient elements in soybean (Glycine max) plants cultivated in farm soil amended with nCeO2 at 0-1000 mg kg(-1) and nZnO at 0-500 mg kg(-1). Digested samples were analyzed by ICP-OES/MS. Compared to control, pods from nCeO2 at 1000 mg kg(-1) had significantly less Ca but more P and Cu, while pods from 100 mg kg(-1)nZnO had more Zn, Mn, and Cu. Plants treated with nZnO showed significant correlations among Zn, P, and S in pods with Zn in roots. Correlations among pod Zn/root Zn was r = 0.808 (p ≤ 0.01) and pod P/root P was r = 0.541 (p ≤ 0.05). The correlation among pod S/root S was r = -0.65 (p ≤ 0.01). While nCeO2 treatments exhibited significant correlations between pod Ca/root Ca (r = 0.645, p ≤ 0.05). The data suggest that nCeO2 and nZnO alter the nutritional value of soybean, which could affect the health of plants, humans, and animals. PMID:24751400

  6. Photoluminescence properties of cerium oxide nanoparticles as a function of lanthanum content

    SciTech Connect

    Deus, R.C.; Cortés, J.A.; Ramirez, M.A.; Ponce, M.A.; Andres, J.; Rocha, L.S.R.; and others

    2015-10-15

    Highlights: • CeO{sub 2} nanoparticles were obtained by microwave-hydrothermal method. • Rietveld refinement reveals a cubic structure. • KOH mineralizer agent exhibit weak agglomeration at low temperature and shorter time. - Abstract: The structural and photoluminescent properties at room temperature of CeO{sub 2} and La-doped CeO{sub 2} particles were undertaken. The obtained particles were synthesized by a microwave-assisted hydrothermal method (MAH) under different lanthanum contents. X-ray diffraction (XRD), Fourier transform infrared (FT-IR), Fourier transform Raman (FT-Raman), Ultra-violet spectroscopy (UV–vis) and photoluminescence (PL) measurements were carried out. XRD revealed that the powders are free of secondary phases and crystallize in the cubic structure. Raman data show that increasing La doping content increase oxygen vacancies due to lattice expansion. The UV/vis absorption spectroscopy suggested the presence of intermediate energy levels in the band gap of structurally ordered powders. Lanthanum addition creates oxygen vacancies and shifts the photoluminescence in the low energy range leading to intense PL emission.

  7. Dissolution of cerium(IV)-lanthanide(III) oxides: Comparative effect of chemical composition, temperature, and acidity

    SciTech Connect

    Horlait, D.; Clavier, N.; Szenknect, S.; Dacheux, N.; Dubois, V.

    2012-03-15

    The dissolution of Ce{sub 1-x}Ln{sub x}O{sub 2-x/2} solid solutions was undertaken in various acid media in order to evaluate the effects of several physicochemical parameters such as chemical composition, temperature, and acidity on the reaction kinetics. The normalized dissolution rates (R{sub L,0}) were found to be strongly modified by the trivalent lanthanide incorporation rate, due to the presence of oxygen vacancies decreasing the samples cohesion. Conversely, the nature of the trivalent cation considered only weakly impacted the R{sub L,0} values. The dependence of the normalized dissolution rates on the temperature then appeared to be of the same order of magnitude than that of chemical composition. Moreover, it allowed determining the corresponding activation energy (E{sub A} ≅ 60-85 kJ.mol{sup -1}) which accounts for a dissolution driven by surface-controlled reactions. A similar conclusion was made regarding the acidity of the solution: the partial order related to (H{sub 3}O{sup +}) reaching about 0.7. Finally, the prevailing effect of the incorporation of aliovalent cations in the fluorite-type CeO{sub 2} matrix on the dissolution kinetics precluded the observation of slight effects such as those linked to the complexing agents or to the crystal structure of the samples. (authors)

  8. The genotoxicity of titanium dioxide and cerium oxide nanoparticles in vitro

    EPA Science Inventory

    The use ofengineered nanoparticles in both current and future consumer products is steadily increasing. However, the health effects of exposure to these nanoparticles are not thoroughly understood. Recently, particular emphasis has been placed on particle characterization and the...

  9. Intergenerational studies on the effects of cerium oxide nanoparticles in wheat

    EPA Science Inventory

    The intergenerational impacts of engineered nanomaterials in plants are not yet well understood. A soil microcosm study was performed to assess the physiology, phenology, yield and nutrient uptake in wheat (Triticum aestivum) exposed to nanoceria (nCeO2). Seeds from parental plan...

  10. Self-poled transparent and flexible UV light-emitting cerium complex-PVDF composite: a high-performance nanogenerator.

    PubMed

    Garain, Samiran; Sinha, Tridib Kumar; Adhikary, Prakriti; Henkel, Karsten; Sen, Shrabanee; Ram, Shanker; Sinha, Chittaranjan; Schmeißer, Dieter; Mandal, Dipankar

    2015-01-21

    Cerium(III)-N,N-dimethylformamide-bisulfate [Ce(DMF)(HSO4)3] complex is doped into poly(vinylidene fluoride) (PVDF) to induce a higher yield (99%) of the electroactive phases (β- and γ-phases) of PVDF. A remarkable enhancement of the output voltage (∼32 V) of a nanogenerator (NG) based on a nonelectrically poled cerium(III) complex containing PVDF composite film is achieved by simple repeated human finger imparting, whereas neat PVDF does not show this kind of behavior. This high electrical output resembles the generation of self-poled electroactive β-phase in PVDF due to the electrostatic interactions between the fluoride of PVDF and the surface-active positive charge cloud of the cerium complex via H-bonding and/or bipolar interaction among the opposite poles of cerium complex and PVDF, respectively. The capacitor charging capability of the flexible NG promises its applicability as piezoelectric-based energy harvester. The cerium(III) complex doped PVDF composite film exhibit an intense photoluminescence in the UV region, which might be due to a participation of electron cloud from negative pole of bipolarized PVDF. This fact may open a new area for prospective development of high-performance energy-saving flexible solid-state UV light emitters. PMID:25523039

  11. Cerium and Neodymium Isotope Fractionation in Geochemical Samples

    NASA Astrophysics Data System (ADS)

    Ohno, T.; Ishibashi, T.

    2014-12-01

    The study of naturally occurring isotopic variations of rare earth elements (REE) has a potentially significant influence in geochemical research fields with other traditional studies of REE. One of the key features of REE are their chemical similarities and gradual changes of ionic radius, which may make the isotopic variation of REE a potential tool to understand the mechanisms of isotopic fractionation in nature. Among the REE, geochemical and physicochemical features of Ce could be anomalous, because Ce could be present as the tetravalent (+IV) state as well as the common trivalent (+III) state of other REE. Since the oxidation state of Ce can change by reflecting the redox conditions of the environment, the measured differences in the degree of isotopic fractionation between Ce and other REE can provide unique information about the redox conditions. In this study, we developed a new analytical method to determine the mass-dependent isotopic fractionations of Ce and Nd in geochemical samples. The reproducibility of the isotopic ratio measurements on 142Ce/140Ce, 146Nd/144Nd and 148Nd/144Nd were 0.08‰ (2SD, n=25), 0.06‰ (2SD, n=39) and 0.12‰ (2SD, n=39), respectively. The present technique was applied to determine the variations of the Ce and Nd isotopic ratios for five geochemical reference materials (igneous rocks, JB-1a and JA-2; sedimentary rocks, JMn-1, JCh-1 and JDo-1). The resulting ratios for two igneous rocks (JB-1a and JA-2) and two sedimentary rocks (JMn-1 and JCh-1) did not vary significantly among the samples, whereas the Ce and Nd isotope ratios for the carbonate samples (JDo-1) were significantly higher than those for igneous and sedimentary rock samples. The 1:1 simple correlation between δ142Ce and δ146Nd indicates that there were no significant difference in the degree of isotopic fractionation between the Ce and Nd. This suggests that the isotopic fractionation for Ce found in the JDo-1 could be induced by physicochemical processes

  12. Implementation of a complex multi-phase equation of state for cerium and its correlation with experiment

    SciTech Connect

    Cherne, Frank J; Jensen, Brian J; Elkin, Vyacheslav M

    2009-01-01

    The complexity of cerium combined with its interesting material properties makes it a desirable material to examine dynamically. Characteristics such as the softening of the material before the phase change, low pressure solid-solid phase change, predicted low pressure melt boundary, and the solid-solid critical point add complexity to the construction of its equation of state. Currently, we are incorporating a feedback loop between a theoretical understanding of the material and an experimental understanding. Using a model equation of state for cerium we compare calculated wave profiles with experimental wave profiles for a number of front surface impact (cerium impacting a plated window) experiments. Using the calculated release isentrope we predict the temperature of the observed rarefaction shock. These experiments showed that the release state occurs at different magnitudes, thus allowing us to infer where dynamic {gamma} - {alpha} phase boundary is.

  13. Ab initio molecular dynamics study of the properties of cerium in liquid sodium at 1000 K temperature

    SciTech Connect

    Samin, Adib; Li, Xiang; Zhang, Jinsuo; Mariani, R. D.; Unal, Cetin

    2015-12-21

    For liquid-sodium-cooled fast nuclear reactor systems, it is crucial to understand the behavior of lanthanides and other potential fission products in liquid sodium or other liquid metal solutions such as liquid cesium-sodium. In this study, we focus on lanthanide behavior in liquid sodium. Using ab initio molecular dynamics, we found that the solubility of cerium in liquid sodium at 1000 K was less than 0.78 at. %, and the diffusion coefficient of cerium in liquid sodium was calculated to be 5.57 × 10{sup −9} m{sup 2}/s. Furthermore, it was found that cerium in small amounts may significantly alter the heat capacity of the liquid sodium system. Our results are consistent with the experimental results for similar materials under similar conditions.

  14. Ab initio molecular dynamics study of the properties of cerium in liquid sodium at 1000 K temperature

    NASA Astrophysics Data System (ADS)

    Samin, Adib; Li, Xiang; Zhang, Jinsuo; Mariani, R. D.; Unal, Cetin

    2015-12-01

    For liquid-sodium-cooled fast nuclear reactor systems, it is crucial to understand the behavior of lanthanides and other potential fission products in liquid sodium or other liquid metal solutions such as liquid cesium-sodium. In this study, we focus on lanthanide behavior in liquid sodium. Using ab initio molecular dynamics, we found that the solubility of cerium in liquid sodium at 1000 K was less than 0.78 at. %, and the diffusion coefficient of cerium in liquid sodium was calculated to be 5.57 × 10-9 m2/s. Furthermore, it was found that cerium in small amounts may significantly alter the heat capacity of the liquid sodium system. Our results are consistent with the experimental results for similar materials under similar conditions.

  15. Recovery of plutonium from HEPA filters by Ce(IV)-promoted dissolution of PuO/sub 2/ and recycle of the cerium promoter

    SciTech Connect

    Leuze, R. E.; Bond, W. D.; Scheitlin, F. M.

    1980-01-01

    The experimental studies carried out included (1) the electrolytic production of Ce(IV) from Ce(III), (2) the leaching of refractory PuO/sub 2/ from HEPA filter materials with maintenance of Ce(IV) concentrations by anodic oxidation during leaching, and (3) evaluation of methods for contacting the HEPA solids with the leaching solution and for separating the solid residue from the leaching liquor. Anodic oxidation of Ce(III) was accomplished with an electric current efficiency of about 85% at current densities of 0.04 to 0.4 A/dm/sup 2/ at a platinum anode. Refractory PuO/sub 2/ was dissolved by a 4.0 M HNO/sub 3/ - 0.1 M Ce(IV) solution in 1.5 h at 100/sup 0/C using stirred-contact leaching of the solids or by recirculating the leachant through a packed column of the solids. Cerium (IV) concentrations were maintained continuously by anodic oxidation throughout leaching. Dissolution times up to 10 h were required unless the HEPA media were oxidized initially in air at 300/sup 0/C to destroy carbonaceous species which consumed Ce(IV) more rapidly than it could be regenerated by anodic oxidation. Leaching solids in packed columns avoided the relatively difficult liquid-solids separation by centrifugation which was required after stirred-contact leaching; however, the solids handling difficulties associated with charging and discharging of the packed columns in a remote environment remain a significant design obstacle. A chemical flowsheet is proposed for the recovery of actinides from HEPA filters. A 4 M HNO/sub 3/ - 0.1 M Ce(IV) nitrate solution is used as the leachant and the Ce(III) is recycled to the leaching operation using bidentate solvent extraction.

  16. Change of the cerium valence with temperature - Structure and chemical bonding of HT-CeRhGe

    NASA Astrophysics Data System (ADS)

    Svitlyk, Volodymyr; Hermes, Wilfried; Chevalier, Bernard; Matar, Samir F.; Gaudin, Etienne; Voßwinkel, Daniel; Chernyshov, Dmitry; Hoffmann, Rolf-Dieter; Pöttgen, Rainer

    2013-07-01

    Polycrystalline CeRhGe was prepared via arc-melting of the elements. Its TiNiSi-related structures (space groups Pnma) were studied by powder diffraction using synchrotron radiation over the temperature range of 315-770 K. CeRhGe shows a first-order structural phase transition at 520 K upon heating. Ab initio elelectronic structure calculations give evidence for the depletion of the cerium 4f band in HT-CeRhGe and in consequence a redistribution of the electron density from the cerium to the rhodium atoms. Purely trivalent cerium atoms in the low-temperature modification (LT) change to intermediate-valent cerium in the high-temperature modification (HT). The integrated crystal orbital Hamilton populations show an enhancement of the Ce-Rh bonding in HT-CeRhGe. The three-dimensional [RhGe] polyanionic network shows drastic puckering of the [Rh3Ge3] hexagons in LT-CeRhGe and a flattening in HT-CeRhGe. The cerium valence change is accompanied by a drastic jump in the lattice parameters: a = 7.42249(8), b = 4.46699(5) and c = 7.1276(1) Å at 315 K vs. a = 7.24579(6), b = 4.47506(4) and c = 7.43579(6) Å at 570 K. Large shifts occur for the x parameter of the rhodium and the z parameter of the cerium atomic positions (Wyckoff sites 4c (x 1/4 z)).

  17. Effect of ultrasound on the structural and textural properties of copper-impregnated cerium-modified zirconium-pillared bentonite

    NASA Astrophysics Data System (ADS)

    Tomul, Fatma

    2011-12-01

    In this study, the synthesis of zirconium-pillared bentonite modified with cerium was performed via two different methods by the application of conventional and ultrasonic treatments during the intercalation stage. To synthesise copper-impregnated pillared clays by wet impregnation, cerium-modified zirconium-pillared clays were used as supportive materials after being calcined at 300 °C. Ultrasonic treatment significantly decreased the required processing time compared with the conventional treatment of the synthesised pillared bentonites. Chemical analysis confirmed the incorporation of Zr 4+, Ce 4+ and Cu 2+ species into the pillared bentonites. X-ray diffraction (XRD) patterns of zirconium- and cerium/zirconium-pillared bentonites prepared by conventional treatment show that one large d-spacing above 3.5 nm corresponds to the mesoporous delaminated part, and another small d-spacing above 1.7 nm is indicative of the microporous pillared part. Zirconium- and cerium/zirconium-pillared bentonites prepared via ultrasonic treatment exhibited similar results, with the same high d-spacing but with a second low-intensity d-spacing above 1.9 nm. The delaminated structures of the pillared bentonites synthesised by both methods were conserved after copper impregnation. Nitrogen-adsorption isotherm analysis showed that the textural characteristics of products synthesised by ultrasonic treatment were comparable to those of products synthesised by conventional treatment. Fourier-transform infrared spectroscopy (FTIR) analyses showed the presence of Brønsted- and Lewis-acid sites, and zirconium-pillared clays synthesised by conventional treatment exhibited increased numbers of Brønsted- and Lewis-acid sites after cerium addition and copper impregnation. However, the products synthesised by ultrasonic treatment exhibited an increased number of Brønsted- and Lewis-acid sites after cerium addition, but a decreased number of acid sites after copper impregnation.

  18. Reactions of a cerium(iii) amide with heteroallenes: insertion, silyl-migration and de-insertion.

    PubMed

    Yin, Haolin; Carroll, Patrick J; Schelter, Eric J

    2016-07-28

    Reactions of Ce[N(SiMe3)Ph(F)]3 (-Ph(F) = pentafluorophenyl) toward small molecules of the type E1[double bond, length as m-dash]C[double bond, length as m-dash]E2 (E1, E2 = O, S, NR), including carbon disulfide, carbodiimide, carbon dioxide, isocyanate and isothiocyanate are reported, resulting in distinct products, including cerium(iii) dithiocarbamate, cerium(iii) guanidinate, isocyanates and unsymmetric carbodiimides. These reactions were rationalized as three consecutive stages of the same reaction pathway: insertion, silyl-migration and de-insertion. PMID:27416923

  19. Investigation of the elemental composition of lanthanum-cerium hexaboride crystals

    NASA Astrophysics Data System (ADS)

    Badalyan, Georgi; Kuzanyan, Armen; Petrosyan, Vahagn; Kuzanyan, Vazgen; Gulian, Armen

    2010-10-01

    Crystals of solid solutions of lanthanum-cerium hexaborides (La1-xCex)B6 possess unique thermoelectric properties in the temperature range of 0.3-9 K and they can be used in thermoelectric single-photon detectors as a sensor. One can observe a wide spread in thermoelectric measurement values reported in the literature, which is because of different qualities of studied crystals. The greatest influence on both the Seebeck coefficient and electrical resistivity of samples is exercised by the presence of uncontrolled impurities in crystals and the deviation from stoichiometry. In this work we have studied just the aforementioned parameters of the crystals obtained by three different methods.

  20. β Coronae Bolealis: Lithium and Cerium Contribution to the Blend at 6708 Å

    NASA Astrophysics Data System (ADS)

    Drake, N. A.; Hubrig, S.; Polosukhina, N. S.; de La Reza, R.

    2006-06-01

    We analyze the Li I 6708 Å spectral region of the chemically peculiar Ap star βCrB using high resolution, high signal-to-noise spectra obtained at different rotation phases. Our study shows that the Ce II line at 6708.099 Å is a main contributor to the spectral feature at 6708 Å. This fact explains the observed red shift of the Li I doublet of about 0.2 Å found by Hack et al. (1997). We derive the values of lithium and cerium abundances for different rotation phases and show that βCrB has ``cosmic'' Li abundance.

  1. Reduced graphene oxide/CeO2 nanocomposite with enhanced photocatalytic performance

    NASA Astrophysics Data System (ADS)

    Kaur, Jasmeet; Anand, Kanika; Anand, Kanica; Singh, Gurpreet; Hastir, Anita; Virpal, Singh, Ravi Chand

    2015-05-01

    In this work, reduced graphene oxide /cerium oxide (RGO/CeO2) nanocomposite was synthesized by in situ reduction of cerium nitrate Ce(NO3)3.6H2O in the presence of graphene oxide by hydrazine hydrate (N2H4.H2O). The intrinsic characteristics of as-prepared nanocomposite were studied using powder x-ray diffraction (XRD), Raman spectroscopy and field-emission scanning electron microscopy (FESEM). The photocatalytic degradation of methylene blue (MB) was employed as a model reaction to evaluate the photocatalytic activity of the RGO/CeO2 nanocomposite. The as-obtained RGO/CeO2 nanocomposite displays a significantly enhanced photocatalytic degradation of MB dye in comparison with bare CeO2 nanoparticles under sunlight irradiation, which can be attributed to the improved separation of electron-hole pairs and enhanced adsorption performance due to presence of RGO.

  2. Method of electrode fabrication for solid oxide electrochemical cells

    DOEpatents

    Jensen, Russell R.

    1990-01-01

    A process for fabricating cermet electrodes for solid oxide electrochemical cells by sintering is disclosed. First, a porous metal electrode is fabricated on a solid oxide cell, such as a fuel cell by, for example, sintering, and is then infiltrated with a high volume fraction stabilized zirconia suspension. A second sintering step is used to sinter the infiltrated zirconia to a high density in order to more securely attach the electrode to the solid oxide electrolyte of the cell. High performance fuel electrodes can be obtained with this process. Further electrode performance enhancement may be achieved if stabilized zirconia doped with cerium oxide, chromium oxide, titanium oxide, and/or praseodymium oxide for electronic conduction is used.

  3. Method of electrode fabrication for solid oxide electrochemical cells

    DOEpatents

    Jensen, R.R.

    1990-11-20

    A process for fabricating cermet electrodes for solid oxide electrochemical cells by sintering is disclosed. First, a porous metal electrode is fabricated on a solid oxide cell, such as a fuel cell by, for example, sintering, and is then infiltrated with a high volume fraction stabilized zirconia suspension. A second sintering step is used to sinter the infiltrated zirconia to a high density in order to more securely attach the electrode to the solid oxide electrolyte of the cell. High performance fuel electrodes can be obtained with this process. Further electrode performance enhancement may be achieved if stabilized zirconia doped with cerium oxide, chromium oxide, titanium oxide, and/or praseodymium oxide for electronic conduction is used. 5 figs.

  4. Studies on luminescence from a cerium-doped strontium stannate phosphor.

    PubMed

    Karabulut, Yüksel; Ayvacikli, Mehmet; Canimoglu, Adil; Garcia Guinea, Javier; Can, Nurdogan

    2015-06-01

    The crystal structure and morphology of Ce(3+) -doped SrSnO3 materials prepared using the solid-state reaction method were extensively characterized using experimental techniques. X-Ray diffraction results show that the cerium substitution of strontium does not change the structure of the strontium stannate. Raman spectroscopy was used to investigate the microstructures and lattice vibrations. Environmental scanning electron microscopy images showed that phosphors aggregate and their particles form irregular shapes. SrSnO3 exhibits an intense green emission with a broad band originating from the 5d(1)  → 4f(1) transition of cerium. It was observed that, after exposure to beta-irradiation, the glow curve of this material has two broad thermoluminescence peaks, one centered at ~ 127°C and the other at ~ 245°C for a heating rate of 5 K/s. The kinetic parameters, which include the frequency factor and the activation energy of the material, were calculated using Chen's method, after beta-irradiation. The fading and reusability of the phosphor were also studied and it was found that the phosphor is suitable for radiation dosimetry.

  5. [XPS study on the influence of calcination conditions to cerium ion valence].

    PubMed

    Mei, Yan; Yan, Jian-ping; Nie, Zuo-ren

    2010-01-01

    For the system of Ce(NO3)2.6H2O and urea solution during homogeneous precipitation method, X-ray diffraction (XRD), infrared spectrum (IR) and especially X-ray photoelectron spectroscopy (XPS) were used to study and characterize the product structure, variety of cerium ion valence, compound surface character and kernel electronic configurations. The results of XRD and IR showed that calcination temperature had a great effect on the cerium ion valence. The products are orthorhombic Ce2 O(CO3)2.H2O with valence III by using homogeneous precipitation method directly. When heated from the temperature 200 degrees C to 250 degrees C, the product of CeO(CO3)2.H2O with valence VI was finally changed into stable CeO2 with valence IV. XPS was used to study the surface character and kernel electronic configurations of the three different compounds through fine scanning of O(1s), Ce(3d) and Ce(4d) apices, and the results approved that the compounds with different valences are caused by the different valence electronic configurations of the products.

  6. Mixed mode and sequential oscillations in the cerium-bromate-4-aminophenol photoreaction

    SciTech Connect

    Bell, Jeffrey G.; Wang Jichang

    2013-09-15

    Cerium was introduced to the bromate-aminophenol photochemical oscillator to implement coupled autocatalytic feedbacks. Mixed mode and sequential oscillations emerged in the studied system, making it one of the few chemical oscillators known to support consecutive bifurcations in a batch system. The complex reaction behavior showed a strong dependence on the intensity of illumination supplied to the system. Removal of illumination during an oscillatory window affected both the frequency and amplitude of the oscillation but did not fully extinguish them, indicating that the cerium-bromate-4-aminophenol oscillator was photosensitive rather than photo-controlled. A moderate light intensity allowed for a slow evolution of the system, which proved to be critical for the emergence of transient complex oscillations. Variation of individual reaction parameters was carried out, which indicated that the development of complex oscillations occur in a narrow region and a phase diagram in the 4-aminophenol and sulfuric acid plane demonstrated this. Simulations provide strong support that transient complex oscillations observed experimentally arise from the coupling of two autocatalytic cycles.

  7. Kinetics of Cerium(IV) Extraction from H(2)SO(4)-HF Medium with Cyanex 923.

    PubMed

    Liao, Wuping; Yu, Guihong; Yue, Shantang; Li, Deqian

    2002-03-11

    Studies of the extraction kinetics of cerium(IV) from H(2)SO(4)-HF solutions with Cyanex 923 in n-heptane have been carried out using a constant interfacial area cell with laminar flow. The experimental hydrodynamic conditions were chosen so that the contribution of diffusion to the measured rate of reaction was minimized. The data were analyzed in terms of pseudo-first order constants. The results were compared with those of the system without HF. It was concluded that the addition of HF reduces the activation energy for the forward rate from 46.2 to 36.5 kJ mol(-1) while it has an opposite effect on the activation energy for the reverse process(the activation energy increased from 23.3 to 90.8 kJ mol(-1)). Thus, HF can accelerate the rate of cerium(IV) extraction. At the same time, the extraction rate is controlled by a mixed chemical reaction-diffusion rather than by a chemical reaction alone. A rate equation has also been obtained.

  8. A mixed acid based vanadium-cerium redox flow battery with a zero-gap serpentine architecture

    NASA Astrophysics Data System (ADS)

    Leung, P. K.; Mohamed, M. R.; Shah, A. A.; Xu, Q.; Conde-Duran, M. B.

    2015-01-01

    This paper presents the performance of a vanadium-cerium redox flow battery using conventional and zero-gap serpentine architectures. Mixed-acid solutions based on methanesulfonate-sulfate anions (molar ratio 3:1) are used to enhance the solubilities of the vanadium (>2.0 mol dm-3) and cerium species (>0.8 mol dm-3), thus achieving an energy density (c.a. 28 Wh dm-3) comparable to that of conventional all-vanadium redox flow batteries (20-30 Wh dm-3). Electrochemical studies, including cyclic voltammetry and galvanostatic cycling, show that both vanadium and cerium active species are suitable for energy storage applications in these electrolytes. To take advantage of the high open-circuit voltage (1.78 V), improved mass transport and reduced internal resistance are facilitated by the use of zero-gap flow field architecture, which yields a power density output of the battery of up to 370 mW cm-2 at a state-of-charge of 50%. In a charge-discharge cycle at 200 mA cm-2, the vanadium-cerium redox flow battery with the zero-gap architecture is observed to discharge at a cell voltage of c.a. 1.35 V with a coulombic efficiency of up to 78%.

  9. Predicting the Effects of Nano-Scale Cerium Additives in Diesel Fuel on Regional-Scale Air Quality

    EPA Science Inventory

    Diesel vehicles are a major source of air pollutant emissions. Fuel additives containing nanoparticulate cerium (nCe) are currently being used in some diesel vehicles to improve fuel efficiency. These fuel additives also reduce fine particulate matter (PM2.5) emissio...

  10. Surface and redox properties of cobalt-ceria binary oxides: On the effect of Co content and pretreatment conditions

    NASA Astrophysics Data System (ADS)

    Konsolakis, Michalis; Sgourakis, Michalis; Carabineiro, Sónia A. C.

    2015-06-01

    Ceria-based transition metal catalysts have recently received considerable attention both in heterogeneous catalysis and electro-catalysis fields, due to their unique physicochemical characteristics. Their catalytic performance is greatly affected by the surface local chemistry and oxygen vacancies. The present study aims at investigating the impact of Co/Ce ratio and pretreatment conditions on the surface and redox properties of cobalt-ceria binary oxides. Co-ceria mixed oxides with different Co content (0, 20, 30, 60, 100 wt.%) were prepared by impregnation method and characterized by means of N2 adsorption at -196 °C, X-ray diffraction (XRD), H2 temperature-programmed reduction (H2-TPR) and X-ray photoelectron spectroscopy (XPS). The results shown the improved reducibility of Co/CeO2 mixed oxides compared to single oxides, due to a synergistic interaction between cobalt and cerium. Oxidation pretreatment results in a preferential localization of cerium species on the outer surface. In contrast, a uniform distribution of cobalt and cerium species over the entire catalyst surface is obtained by the reduction process, which facilitates the formation of oxygen vacancies though Co3+/Co2+ and Ce3+/Ce4+ redox cycles. Fundamental insights toward tuning the surface chemistry of cobalt-ceria binary oxides are provided, paving the way for real-life industrial applications.

  11. Membraneless, room-temperature, direct borohydride/cerium fuel cell with power density of over 0.25 W/cm2.

    PubMed

    Da Mota, Nicolas; Finkelstein, David A; Kirtland, Joseph D; Rodriguez, Claudia A; Stroock, Abraham D; Abruña, Héctor D

    2012-04-11

    The widespread adoption and deployment of fuel cells as an alternative energy technology have been hampered by a number of formidable technical challenges, including the cost and long-term stability of electrocatalyst and membrane materials. We present a microfluidic fuel cell that overcomes many of these obstacles while achieving power densities in excess of 250 mW/cm(2). The poisoning and sluggish reaction rate associated with CO-contaminated H(2) and methanol, respectively, are averted by employing the promising, high-energy density fuel borohydride. The high-overpotential reaction of oxygen gas at the cathode is supplanted by the high-voltage reduction of cerium ammonium nitrate. Expensive, ineffective membrane materials are replaced with laminar flow and a nonselective, porous convection barrier to separate the fuel and oxidant streams. The result is a Nafion-free, room-temperature fuel cell that has the highest power density per unit mass of Pt catalyst employed for a non-H(2) fuel cell, and exceeds the power density of a typical H(2) fuel cell by 50%.

  12. Post-depositional redistribution processes and their effects on middle rare earth element precipitation and the cerium anomaly in sediments in the South Korea Plateau, East Sea

    NASA Astrophysics Data System (ADS)

    Kang, Jeongwon; Jeong, Kap-Sik; Cho, Jin Hyung; Lee, Jun Ho; Jang, Seok; Kim, Seong Ryul

    2014-03-01

    We sampled two box-core sediments from the slope of the eastern South Korea Plateau (SKP) in the East Sea (Sea of Japan) at water depths of 1400 and 1700 m. Two chemical fractions of extractable (hydroxylamine/acetic acid) and residual rare earth elements (REEs) together with Al, Ca, Fe, Mg, Mn, P, S, As, Mo, and U were analyzed to assess the post-depositional redistribution of REEs. Extractable Fe and Mn are noticeably abundant in the oxic topmost sediment layer (<3 cm). However, some trace elements (e.g., S, As, Mo, U) are more abundant at depth, where redox conditions are different. Analysis of upper continental crust (UCC)-normalized (La/Gd)UCC, (La/Yb)UCC, and (Ce/Ce*)UCC revealed that the extractable REE is characterized by middle REE (MREE) enrichment and a positive cerium (Ce) anomaly, different from the case of the residual fraction which shows slight enrichment in light REEs (LREEs) with no Ce anomaly. The extractable MREEs seem to have been incorporated into high-Mg calcite during reductive dissolution of Fe oxyhydroxides. In the top sediment layer, the positive Ce anomaly is attributed to Ce oxide, which can be mobilized in deeper oxygen-poor environments and redistributed in the sediment column. In addition, differential concentrations of Ce and other LREEs in pore water appear to result in variable (Ce/Ce*)UCC ratios in the extractable fraction at depth.

  13. Lanthanide(III)/actinide(III) differentiation in coordination of azine molecules to tris(cyclopentadienyl) complexes of cerium and uranium.

    PubMed

    Mehdoui, Thouraya; Berthet, Jean-Claude; Thuéry, Pierre; Ephritikhine, Michel

    2004-02-21

    Reaction of azine molecules L with the trivalent metallocenes [M(C5H4R)3](M = Ce, U; R = But, SiMe3) in toluene gave the Lewis base adducts [M(C5H4R)3(L)](L = pyridine, 3-picoline, 3,5-lutidine, 3-chloropyridine, pyridazine, pyrimidine, pyrazine, 3,5-dimethylpyrazine and s-triazine), except in the cases of M = U and L = 3-chloropyridine, pyridazine, pyrazine and s-triazine where oxidation of U(III) was found to occur. In the pairs of analogous compounds of Ce(III) and U(III), i.e.[M(C5H4But)3(L)](L = pyridine, picoline) and [M(C5H4SiMe3)3(L)](L = pyridine, lutidine, pyrimidine and dimethylpyrazine), the M-N and average M-C distances are longer for M = Ce than for M = U; however, within a series of azine adducts of the same metallocene, no significant variation is noted in the M-N and average M-C distances. The equilibria between [M(C5H4R)3], L and [M(C5H4R)3(L)] were studied by 1H NMR spectroscopy. The stability constants of the uranium complexes, KUL, are greater than those of the cerium counterparts, KCeL. The values of KML are much greater for R = SiMe3 than for R = But and a linear correlation is found between the logarithms of KML and the hydrogen-bond basicity pKHB scale of the azines. Thermodynamic parameters indicate that the enthalpy-entropy compensation effect holds for these complexation reactions. Competition reactions of [Ce(C5H4R)3] and [U(C5H4R)3] with L show that the selectivity of L in favour of U(III) increases with the [small pi] donor character of the metallocene and is proportional to the pi accepting ability of the azine molecule, measured by its reduction potential.

  14. Cerium-activated sol-gel silica glasses for radiation dosimetry in harsh environment

    NASA Astrophysics Data System (ADS)

    El Hamzaoui, Hicham; Capoen, Bruno; Helou, Nissrine Al; Bouwmans, Géraud; Ouerdane, Youcef; Boukenter, Aziz; Girard, Sylvain; Marcandella, Claude; Duhamel, Olivier; Chadeyron, Geneviève; Mahiou, Rachid; Bouazaoui, Mohamed

    2016-04-01

    Cerium-doped silica glass has been prepared for ionizing radiation dosimetry applications, using the sol-gel route and densification under different atmospheres. In comparison with the glass densified under air atmosphere, the one obtained after sintering the xerogel under helium gas presents improved optical properties, with an enhancement of the photoluminescence quantum yield up to 33%, which is attributed to a higher Ce3+ ions concentration. Such a glassy rod has been jacketed in a quartz tube and then drawn at high temperature to a cane, which has been used as active material in a fibered remote x-ray radiation dosimeter. The sample exhibited a reversible linear radioluminescence intensity response versus the dose rate up to 30 Gy s-1. These results confirm the potentialities of this material for in vivo or high rate dose remote dosimetry measurements.

  15. Adsorption of Magnesium Sulfate from Desulfurization Industrial Wastewater by Nano-Cerium Loaded Recycled Aggregates.

    PubMed

    Yoon, Hyung-Sun; Bak, Somi; Seo, Seong-Gyu; Choi, Jeongdong; Kim, Eun-Sik

    2016-02-01

    In this research, the recycled aggregates (RAs) from blast furnace were solidified with nano-cerium (Ce), and applied to reduce the ionic species (e.g., magnesium sulfate) in the desulfurization industrial wastewater. Static batch experiments were performed based on different loading of recycled aggregates. Sulfate sorption isotherm studies were performed by Langmuir adsorption model. The physical morphologies were determined using scanning electron microscope. The results presented that the partial ions were captured with the different loading of the recycled aggregates during the batch tests. It was observed that 8 hr batch reaction equilibrated the electrical conductivity reduction, and 13% mass loading was estimated an optimal dosage of adsorbent. This study showed the nano-Ce loaded RAs could reduce ionic species in wastewater, and expected to be an economical adsorbent for wastewater treatment process.

  16. Adsorption of Magnesium Sulfate from Desulfurization Industrial Wastewater by Nano-Cerium Loaded Recycled Aggregates.

    PubMed

    Yoon, Hyung-Sun; Bak, Somi; Seo, Seong-Gyu; Choi, Jeongdong; Kim, Eun-Sik

    2016-02-01

    In this research, the recycled aggregates (RAs) from blast furnace were solidified with nano-cerium (Ce), and applied to reduce the ionic species (e.g., magnesium sulfate) in the desulfurization industrial wastewater. Static batch experiments were performed based on different loading of recycled aggregates. Sulfate sorption isotherm studies were performed by Langmuir adsorption model. The physical morphologies were determined using scanning electron microscope. The results presented that the partial ions were captured with the different loading of the recycled aggregates during the batch tests. It was observed that 8 hr batch reaction equilibrated the electrical conductivity reduction, and 13% mass loading was estimated an optimal dosage of adsorbent. This study showed the nano-Ce loaded RAs could reduce ionic species in wastewater, and expected to be an economical adsorbent for wastewater treatment process. PMID:27433701

  17. Sorptive separation of yttrium and cerium on a weakly basic anionite

    NASA Astrophysics Data System (ADS)

    Cheremisina, O. V.; Ponomareva, M. A.; Chirkst, D. E.; Lobacheva, O. L.; Shul'gin, I. A.

    2015-01-01

    The sorption of complex yttrium ions with Trilon B onto the weakly basic anionite D-403 in nitrate form from an acidic medium at pH 3 with constant ionic strength (NaNO3, 1 mol/kg) is investigated. A thermodynamic evaluation of the sorption isotherm of anionic yttrium complexes is performed using a method based on the linearization of the equation of the law of active mass, modified for ionic exchange reactions. The ionic exchange constant, the Gibbs free energy of ionic exchange, the capacity of the anionite, and the sorption limit of ethylenediaminetetraacetatoyttrate ions (EDTA yttrate ions) are calculated. Using a frontal version of ion exchange chromatography, cerium and yttrium are separated on D-403 anionite with a fraction of pure yttrium at the column outlet of no less than 30%.

  18. Optical Evidence of Itinerant-Localized Crossover of 4f Electrons in Cerium Compounds

    NASA Astrophysics Data System (ADS)

    Kimura, Shin-ichi; Kwon, Yong Seung; Matsumoto, Yuji; Aoki, Haruyoshi; Sakai, Osamu

    2016-08-01

    Cerium (Ce)-based heavy-fermion materials have a characteristic double-peak structure (mid-IR peak) in the optical conductivity [σ(ω)] spectra originating from the strong conduction (c)-f electron hybridization. To clarify the behavior of the mid-IR peak at a low c-f hybridization strength, we compared the σ(ω) spectra of the isostructural antiferromagnetic and heavy-fermion Ce compounds with the calculated unoccupied density of states and the spectra obtained from the impurity Anderson model. With decreasing c-f hybridization intensity, the mid-IR peak shifts to the low-energy side owing to the renormalization of the unoccupied 4f state, but suddenly shifts to the high-energy side owing to the f-f on-site Coulomb interaction at a slight localized side from the quantum critical point (QCP). This finding gives us information on the change in the electronic structure across QCP.

  19. Impact of electrolyte composition on the performance of the zinc-cerium redox flow battery system

    NASA Astrophysics Data System (ADS)

    Nikiforidis, Georgios; Berlouis, Léonard; Hall, David; Hodgson, David

    2013-12-01

    The zinc-cerium redox flow battery has the highest open circuit cell voltage (Ecell = 2.4 V) of all the common redox flow battery (RFB) systems being investigated. In this paper, carbon polymer composite materials based on polyvinyl ester and polyvinylidene difluoride are investigated as the negative electrode for this RFB system. Electrolyte composition, particularly on the negative side, is found to play a key role in maintaining high (˜90%) coulombic efficiencies for the different charge durations, from 10 min to 4 h, examined. Energy efficiencies >60% are obtained for temperatures in the range 45 °C-55 °C when the zinc ion concentration in the methanesulfonic acid electrolyte is 2.5 mol dm-3. No dependence of the energy efficiency on the flow velocity is found, over the range 7.5 cm s-1-13.5 cm-1.

  20. Transition Probabilities for Neutral Cerium from Boltzmann Analysis of Fourier Transform Spectra

    NASA Astrophysics Data System (ADS)

    Nitz, D. E.; Curry, J. J.; Buuck, M. J.; Mitchell, N. P.; Demann, A. D.; Shull, W. E.

    2012-06-01

    The recent availability of a large set of absolute transition probabilities for neutral cerium (Lawler et. al., J. Phys. B 43, 85701 (2010)) makes it possible to investigate the relative populations of the upper levels of these lines in radiometrically-calibrated spectra. In cases where these populations can be characterized by a single effective Boltzmann temperature, applying this temperature enables one to determine additional absolute transition probabilities for observable decay branches of nearby levels. While not as accurate as measurements based on branching fractions and lifetimes, the method can be applied to levels whose lifetimes are not known and does not require accounting for all of the branches. We are analyzing Fourier Transform spectra from NIST and from the National Solar Observatory data archive at Kitt Peak via this technique, seeking to increase the set of known transition probabilities for Ce I by a factor of 2-3. A summary of results obtained to date will be presented.