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.

Preclinical Evaluation to Specifically Target Ovarian Cancer with Folic Acid-Conjugated Nanoceria

DTIC Science & Technology

2014-08-01

cancer . Our experimental nanoparticle is Nanoceria (NCe), a cerium oxide nanoparticle . Nanotechnology -based tools and techniques are rapidly... cancer we proposed the present work, where we are integrating the field of nanotechnology with ovarian cancer cell’s unique property of...overexpressing folic acid receptor alpha (FR-a) to specifically target ovarian cancer . A cerium oxide nanoparticle , called Nanoceria (NCe), that has the ability

Optical properties of cerium oxide (CeO2) nanoparticles synthesized by hydroxide mediated method

NASA Astrophysics Data System (ADS)

Ali, Mawlood Maajal; Mahdi, Hadeel Salih; Parveen, Azra; Azam, Ameer

2018-05-01

The nanoparticles of cerium oxide have been successfully synthesized by hydroxide mediated method, using cerium nitrate and sodium hydroxide as precursors. The microstructural properties were analyzed by X-ray diffraction technique (XRD). The X-ray diffraction results show that the cerium oxide nanoparticles were in cubic structure. The optical absorption spectra of cerium oxide were recorded by UV-VIS spectrophotometer in the range of 320 to 600 nm and photoluminescence spectra in the range of 400-540 nm and have been presented. The energy band gap was determined by Tauc relationship. The crystallite size was determined from Debye-Scherer equation and came out to be 6.4 nm.

Control of cerium oxidation state through metal complex secondary structures

DOE PAGES

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

2015-08-11

A series of alkali metal cerium diphenylhydrazido complexes, M x(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. Reductionmore » 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.« less

Correlation of Non-proportionality and Scintillation Properties with Cerium Concentration in YAlO 3:Ce

DOE PAGES

Donnald, Samuel B.; Williams, Richard; Melcher, Charles L.; ...

2018-04-19

Cerium doped YAlO3 (YAP:Ce) is an interesting oxide scintillator in that it exhibits a wider range of light yield non-proportionality on a sample-to-sample basis than most other well-known oxide scintillators. In general, most oxide materials, such as BGO and LSO:Ce, are thought to have an intrinsic proportional response that is nearly constant between samples and independent of growth conditions. Since light yield nonproportionality is responsible for degrading the achievable energy resolution of all known scintillators, it is important to understand what contributes to the behavior. In this study, in an attempt to understand if the phenomenon can be affected bymore » growth parameters or by other means, seven samples of YAP:Ce were collected from various sources, and eight samples were grown inhouse using the Czochralski method. Based on optical and scintillation measurement as well as direct measurement of the cerium concentration, it was determined that the light yield proportionality in YAlO3:Ce is strongly related to the cerium concentration. Samples that were found to have a higher relative cerium concentration displayed a more proportional light yield response. In addition, it was determined that samples with a higher cerium concentration also exhibit a faster decay time and an enhanced energy resolution when compared to samples with less cerium. Finally, it was also determined that growth in a reducing atmosphere can effectively suppress a parasitic optical absorption band.« less

Correlation of Non-proportionality and Scintillation Properties with Cerium Concentration in YAlO 3:Ce

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

Donnald, Samuel B.; Williams, Richard; Melcher, Charles L.

Cerium doped YAlO3 (YAP:Ce) is an interesting oxide scintillator in that it exhibits a wider range of light yield non-proportionality on a sample-to-sample basis than most other well-known oxide scintillators. In general, most oxide materials, such as BGO and LSO:Ce, are thought to have an intrinsic proportional response that is nearly constant between samples and independent of growth conditions. Since light yield nonproportionality is responsible for degrading the achievable energy resolution of all known scintillators, it is important to understand what contributes to the behavior. In this study, in an attempt to understand if the phenomenon can be affected bymore » growth parameters or by other means, seven samples of YAP:Ce were collected from various sources, and eight samples were grown inhouse using the Czochralski method. Based on optical and scintillation measurement as well as direct measurement of the cerium concentration, it was determined that the light yield proportionality in YAlO3:Ce is strongly related to the cerium concentration. Samples that were found to have a higher relative cerium concentration displayed a more proportional light yield response. In addition, it was determined that samples with a higher cerium concentration also exhibit a faster decay time and an enhanced energy resolution when compared to samples with less cerium. Finally, it was also determined that growth in a reducing atmosphere can effectively suppress a parasitic optical absorption band.« less

Synthesis, characterization and antibacterial activity of hybrid chitosan-cerium oxide nanoparticles: As a bionanomaterials.

PubMed

Senthilkumar, R P; Bhuvaneshwari, V; Ranjithkumar, R; Sathiyavimal, S; Malayaman, V; Chandarshekar, B

2017-11-01

The hybrid chitosan cerium oxide nanoparticles were prepared for the first time by green chemistry approach using plant leaf extract. The intense peak observed around 292nm in the UV-vis spectrum indicate the formation of cerium oxide nanoparticles. The XRD pattern revealed that the hybrid chitosan-cerium oxide nanoparticles have a polycrystalline structure with cubic fluorite phase. The FTIR spectrum of prepared samples showed the formation of Ce-O bonds and chitosan main chains COC and CO. The FESEM image of hybrid chitosan cerium oxide nanoparticles revealed that the particles are spherical in shape with grains size varying from 23.12nm to 89.91nm. EDAX analysis confirmed the presence of Ce, O, C and N elements in the prepared sample. TEM images showed that the prepared hybrid chitosan-cerium oxide nanoparticles are predominantly uniform in size and most of the particles are spherical in shape with less agglomeration and the particles size varies from 3.61nm to 24.40nm. The prepared chitosan cerium oxide nanoparticles of 50μL concentration showed good antibacterial properties against test pathogens, which was confirmed by the FESEM analysis. The prepared small particle size facilitate that these hybrid ChiCO 2 NPs could effectively be used in biomedical applications. Copyright © 2017 Elsevier B.V. All rights reserved.

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

PubMed

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 Ce3+ is introduced into the starting sols, the trivalent state normally prevails in the wet and room temperature-dried gels. Heating in air at >100 degrees C can generate a light yellow coloration with partial oxidation to the tetravalent state. Above 200 degrees C and up to approximately 1000 degrees 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 degrees 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.

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.

Molecular and physiological responses to titanium dioxide and cerium oxide nanoparticles in Arabidopsis

EPA Science Inventory

- Changes in tissue transcriptomes and productivity of Arabidopsis thaliana were investigated during exposure of plants to two widely-used engineered metal oxide nanoparticles, titanium dioxide (nano-titanium) and cerium dioxide (nano-cerium). Microarray analyses confirmed that e...

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.

Experimental Investigation of Performance and emission characteristics of Various Nano Particles with Bio-Diesel blend on Di Diesel Engine

NASA Astrophysics Data System (ADS)

Karthik, N.; Goldwin Xavier, X.; Rajasekar, R.; Ganesh Bairavan, P.; Dhanseelan, S.

2017-05-01

Present study provides the effect of Zinc Oxide (ZnO) and Cerium Oxide (CeO2) nanoparticles additives on the Performance and emission uniqueness of Jatropha. Jatropha blended fuel is prepared by the emulsification technique with assist of mechanical agitator. Nano particles (Zinc Oxide (ZnO)) and Cerium Oxide (CeO2)) mixed with Jatropha blended fuel in mass fraction (100 ppm) with assist of an ultrasonicator. Experiments were conducted in single cylinder constant speed direct injection diesel engine for various test fuels. Performance results revealed that Brake Thermal Efficiency (BTE) of Jatropha blended Cerium Oxide (B20CE) is 3% and 11% higher than Jatropha blended zinc oxide (B20ZO) and Jatropha blended fuel (B20) and 4% lower than diesel fuel (D100) at full load conditions. Emission result shows that HC and CO emissions of Jatropha blended Cerium Oxide (B20CE) are (6%, 22%, 11% and 6%, 15%, 12%) less compared with Jatropha blended Zinc Oxide (B20ZO), diesel (D100) and Jatropha blended fuel (B20) at full load conditions. NOx emissions of Jatropha blended Cerium Oxide is 1 % higher than diesel fuel (D100) and 2% and 5% lower than Jatropha blended Zinc Oxide, and jatropha blended fuel.

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...

Development of High Temperature Superconducting Josephson Junction Device Technology

DTIC Science & Technology

1998-07-09

neodymium gallate , cerium oxide-buffered sapphire, and lanthanum aluminate, are not ideal for an in situ thallium cuprate junction technology. Moreover...determined that the standard HTS substrates, neodymium gallate , cerium oxide-buffered sapphire, and lanthanum aluminate, are not ideal for an in situ...2.2.1. Deposition Uniformity 10 2.2.2. Radiative Element 12 2.3. SUBSTRATES 13 2.3.1. Neodymium gallate 14 2.3.2. Cerium Oxide-Buffered Sapphire 16

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

NASA Astrophysics Data System (ADS)

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

2018-05-01

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

Unusual kinetics of poly(ethylene glycol) oxidation with cerium(IV) ions in sulfuric acid medium and implications for copolymer synthesis.

PubMed

Szymański, Jan K; Temprano-Coleto, Fernando; Pérez-Mercader, Juan

2015-03-14

The cerium(IV)-alcohol couple in an acidic medium is an example of a redox system capable of initiating free radical polymerization. When the alcohol has a polymeric nature, the outcome of such a process is a block copolymer, a member of a class of compounds possessing many useful properties. The most common polymer with a terminal -OH group is poly(ethylene glycol) (PEG); however, the detailed mechanism of its reaction with cerium(IV) remains underexplored. In this paper, we report our findings for this reaction based on spectrophotometric measurements and kinetic modeling. We find that both the reaction order and the net rate constant for the oxidation process depend strongly on the nature of the acidic medium used. In order to account for the experimental observations, we postulate that protonation of PEG decreases its affinity for some of the cerium(IV)-sulfate complexes formed in the system.

Effect of Thickness on the Morphology and Corrosion Behavior of Cerium-Based Conversion Coatings on AZ31B Magnesium Alloy

NASA Astrophysics Data System (ADS)

Castano, Carlos E.; Maddela, Surender; O'Keefe, Matthew J.; Wang, Yar-Ming

Cerium-based conversion coatings (CeCCs) were deposited onto AZ31B magnesium alloy substrates using a spontaneous reaction of CeCl3, H2O2 and gelatin in a water-based solution. The coating thickness was adjusted by controlling the immersion time in the deposition solution. Prior to deposition, the AZ31B substrates were treated using an acid pickling in nitric acid and then an alkaline cleaning in sodium metasilicate pentahydrate. After deposition, the coated samples were immersed in a phosphate bath that converted cerium oxide/hydroxide into cerium phosphate. Electrochemical impedance spectroscopy, potentiodynamic polarization and neutral salt spray testing studies indicated that 100 nm thick CeCC had better corrosion performance than 400 nm coatings. Characterization of the CeCCs by transmission electron microscopy (TEM) revealed a three layer structure with different compositions.

Synthesis of ceria based superhydrophobic coating on Ni20Cr substrate via cathodic electrodeposition.

PubMed

Pedraza, F; Mahadik, S A; Bouchaud, B

2015-12-21

In this work, superhydrophobic cerium oxide coating surface (111) with dual scale texture on Ni20Cr substrate is obtained by combination of electropolishing the substrate and subsequent cathodic electrodeposition and long-term UVH surface relaxation. To form hierarchical structures of CeO2 is controllable by varying the substrate roughness, and electropolishing period. The results indicated that at the optimal condition, the surface of the cerium oxide coating showed a superhydrophobicity with a great water contact angle (151.0 ± 1.4°) with Gecko state. An interface model for electropolishing of substrate surface in cerium nitrate medium is proposed. We expect that this facile process can be readily and widely adopted for the design of superhydrophobic coating on engineering materials.

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. Copyright © 2013 Elsevier Inc. All rights reserved.

Soft Chemical Fabrication of Iron-Based Thin Film Electrocatalyst for Water Oxidation under Neutral pH and Structure-Activity Tuning by Cerium Incorporation.

PubMed

Saha, Jony; Radhakrishnan, T P

2017-08-29

Design of electrocatalysts for the fundamentally important oxygen evolution reaction can be greatly aided by systematic structure-activity tuning via composition variation. We have explored the iron-cerium system as they are the most abundant transition and rare earth metals, and also due to the mutualistic impact of their size and electronic attributes that can induce critical changes in the structure and electrochemical activity. Submicrometer thick films of a series of Fe(III)-Ce(III) phosphate(oxyhydroxide) (FeCePH) are fabricated using a soft chemical strategy involving surfactant-aided assembly, spin-coating, and mild thermal annealing. FT-IR, Raman, and X-ray photoelectron spectroscopies, chemical analysis, X-ray diffraction, and electron microscopy reveal the systematic structural, electronic, and morphological variation, on tuning the iron-cerium composition. Nitrogen adsorption-desorption studies show the surface area increasing and pore size distribution shrinking with the cerium content, indicating its structure-directing role. The electrocatalysis of water oxidation by FeCePH films on FTO-coated glass is studied in neutral pH conditions. The overpotential and Tafel slope decrease with increasing cerium content, reaching minima at the optimal Fe:Ce ratio of 1:0.5; the turnover frequency shows a corresponding increase and maximum. The trends are explained on the basis of the structural changes in the films, and the coupling of Ce 3+ /Ce 4+ with Fe 3+ /Fe 4+ that leads to active state regeneration. This study presents a rational strategy to tune the efficiency of easily fabricated transition metal-based electrocatalyst thin films through rare earth metal incorporation; it should prove useful in the design of cost-effective catalysts for water oxidation.

Optical and electrical studies of cerium mixed oxides

NASA Astrophysics Data System (ADS)

Sherly, T. R.; Raveendran, R.

2014-10-01

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.

IRIS TOXICOLOGICAL REVIEW AND SUMMARY ...

EPA Pesticide Factsheets

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 used in a variety of ways and is present in many products. For example, cerium is used as a catalyst in emission control systems for gasoline engines, and most recently, as a fuel borne catalyst for diesel engines. In addition, cerium is found in carbon arc lamps, the polishing of lens and mirrors, high temperature ceramics, and the printing and lithographic industries. Cerium is released to the environment as salt compounds from the various uses listed above. This assessment will present reference values for the noncancer effects (RfD and RfC), where supported by the available data, and a cancer evaluation of cerium and cerium compounds. The assessment will be subject to internal review and external peer review along with Agency review. The final product will reflect the Agency's opinion on the toxicity of Cerium and cerium compounds. The U.S. EPA is conducting a new health assessment of cerium (stable) and compounds that will appear on the Agency's online database, the Integrated Risk Information System (IRIS). IRIS is an EPA database containing Agency scientific positions on potential adverse human health effects that may result from chronic (or lifetime) exposure to chemicals i

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).

Heteroaggregation of cerium oxide nanoparticles and nanoparticles of pyrolyzed biomass

USDA-ARS?s Scientific Manuscript database

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 ...

Modeling of the steam hydrolysis in a two-step process for hydrogen production by solar concentrated energy

NASA Astrophysics Data System (ADS)

Valle-Hernández, Julio; Romero-Paredes, Hernando; Pacheco-Reyes, Alejandro

2017-06-01

In this paper the simulation of the steam hydrolysis for hydrogen production through the decomposition of cerium oxide is presented. The thermochemical cycle for hydrogen production consists of the endothermic reduction of CeO2 to lower-valence cerium oxide, at high temperature, where concentrated solar energy is used as a source of heat; and of the subsequent steam hydrolysis of the resulting cerium oxide to produce hydrogen. The modeling of endothermic reduction step was presented at the Solar Paces 2015. This work shows the modeling of the exothermic step; the hydrolysis of the cerium oxide (III) to form H2 and the corresponding initial cerium oxide made at lower temperature inside the solar reactor. For this model, three sections of the pipe where the reaction occurs were considered; the steam water inlet, the porous medium and the hydrogen outlet produced. The mathematical model describes the fluid mechanics; mass and energy transfer occurring therein inside the tungsten pipe. Thermochemical process model was simulated in CFD. The results show a temperature distribution in the solar reaction pipe and allow obtaining the fluid dynamics and the heat transfer within the pipe. This work is part of the project "Solar Fuels and Industrial Processes" from the Mexican Center for Innovation in Solar Energy (CEMIE-Sol).

Modeling of a CeO2 thermochemistry reduction process for hydrogen production by solar concentrated energy

NASA Astrophysics Data System (ADS)

Valle-Hernández, Julio; Romero-Paredes, Hernando; Arancibia-Bulnes, Camilo A.; Villafan-Vidales, Heidi I.; Espinosa-Paredes, Gilberto

2016-05-01

In this paper the simulation of the thermal reduction for hydrogen production through the decomposition of cerium oxide is presented. The thermochemical cycle for hydrogen production consists of the endothermic reduction of CeO2 at high temperature, where concentrated solar energy is used as a source of heat; and of the subsequent steam hydrolysis of the resulting cerium oxide to produce hydrogen. For the thermochemical process, a solar reactor prototype is proposed; consisting of a cubic receptacle made of graphite fiber thermally insulated. Inside the reactor a pyramidal arrangement with nine tungsten pipes is housed. The pyramidal arrangement is made respect to the focal point where the reflected energy is concentrated. The solar energy is concentrated through the solar furnace of high radiative flux. The endothermic step is the reduction of the cerium oxide to lower-valence cerium oxide, at very high temperature. The exothermic step is the hydrolysis of the cerium oxide (III) to form H2 and the corresponding initial cerium oxide made at lower temperature inside the solar reactor. For the modeling, three sections of the pipe where the reaction occurs were considered; the carrier gas inlet, the porous medium and the reaction products outlet. The mathematical model describes the fluid mechanics; mass and energy transfer occurring therein inside the tungsten pipe. Thermochemical process model was simulated in CFD. The results show a temperature distribution in the solar reaction pipe and allow obtaining the fluid dynamics and the heat transfer within the pipe. This work is part of the project "Solar Fuels and Industrial Processes" from the Mexican Center for Innovation in Solar Energy (CEMIE-Sol).

The surface chemistry of cerium oxide

DOE PAGES

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 CeO 2 to CeO 2-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

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...

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.

Protective interlayer for high temperature solid electrolyte electrochemical cells

DOEpatents

Singh, P.; Vasilow, T.R.; Richards, V.L.

1996-05-14

The invention is comprised of an electrically conducting doped or admixed cerium oxide composition with niobium oxide and/or tantalum oxide for electrochemical devices, characterized by the general formula: Nb{sub x}Ta{sub y}Ce{sub 1{minus}x{minus}y}O{sub 2} where x is about 0.0 to 0.05, y is about 0.0 to 0.05, and x+y is about 0.02 to 0.05, and where x is preferably about 0.02 to 0.05 and y is 0, and a method of making the same is also described. This novel composition is particularly applicable in forming a protective interlayer of a high temperature, solid electrolyte electrochemical cell, characterized by a first electrode; an electrically conductive interlayer of niobium and/or tantalum doped cerium oxide deposited over at least a first portion of the first electrode; an interconnect deposited over the interlayer; a solid electrolyte deposited over a second portion of the first electrode, the first portion being discontinuous from the second portion; and, a second electrode deposited over the solid electrolyte. The interlayer is characterized as being porous and selected from the group consisting of niobium doped cerium oxide, tantalum doped cerium oxide, and niobium and tantalum doped cerium oxide or admixtures of the same. The first electrode, an air electrode, is a porous layer of doped lanthanum manganite, the solid electrolyte layer is a dense yttria stabilized zirconium oxide, the interconnect layer is a dense, doped lanthanum chromite, and the second electrode, a fuel electrode, is a porous layer of nickel-zirconium oxide cermet. The electrochemical cell can take on a plurality of shapes such as annular, planar, etc. and can be connected to a plurality of electrochemical cells in series and/or in parallel to generate electrical energy. 5 figs.

Enhanced chemiluminescence of cerium(IV)-Tween 85 system and the analytical application.

PubMed

Li, Shifeng; Qian, Li; Zhu, Yan; Liu, Manman; Gao, Yinping; Ni, Yonghong

2013-01-01

The oxidation reaction between cerium(IV) and Tween 85 in sulfuric acid medium produced weak chemiluminescence (CL). In this paper, it was found that citrate could strongly enhance the CL of cerium(IV)-Tween 85-polyphenol system. Based on studies of ultraviolet-visible spectra and CL spectra, the CL enhancement mechanism had been proposed. It was surmised that the light emission was from an excited oxygen molecular pair O2((1)Δg)O2((1)∑g(-)). The maximum emission wavelength was about 478 nm. The effects of 17 amino acids and 29 organic compounds on cerium(IV)-Tween 85-citrate CL were investigated by a flow injection procedure. This study showed the present system had a wide application for the determination of these compounds. Copyright © 2012 John Wiley & Sons, Ltd.

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.

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.

Titrimetric and Spectrophotometric Methods for the Assay of Ketotifen Using Cerium(IV) and Two Reagents

PubMed Central

Raghu, Madihalli Srinivas; Basavaiah, Kanakapura; Prashanth, Kudige Nagaraj; Vinay, Kanakapura Basavaiah

2013-01-01

One titrimetric and two spectrophotometric methods are described for the determination of ketotifen fumarate (KTF) in bulk drug and in tablets using cerium(IV) as the oxidimetric agent. In titrimetry (method A), the drug was treated with a measured excess of cerium(IV) in H2SO4 medium and after a standing time of 10 min, the surplus oxidant was determined by back titration with iron(II). The spectrophotometric procedures involve addition of a known excess of cerium(IV) to KTF in acid medium followed by the determination of unreacted oxidant by reacting with either p-dimethyl amino benzaldehyde and measuring the resulting colour at 460 nm (method B) or o-dianisidine and subsequent measurement of the absorbance of coloured product at 470 nm (method C). Titrimetric assay is based on a 1 : 2 reaction stoichiometry between KTF and cerium(IV) and the method is applicable over 2–18 mg range. In spectrophotometry, regression analysis of Beer's law plots showed a good correlation in 0.4–8.0 and 0.4–10.0 g mL−1 KTF ranges for method B and method C, respectively, and the corresponding molar absorptivity coefficients are calculated to be 4.0 × 104 and 3.7 × 104 L mol−1 cm−1. PMID:24324496

A novel cerium oxide nanoparticles-based colorimetric sensor using tetramethyl benzidine reagent for antioxidant activity assay.

PubMed

Ozdemir Olgun, F Ayca; Üzer, Ayşem; Ozturk, Birsen Demirata; Apak, Reşat

2018-05-15

Antioxidant activity (AOA) assays using nanotechnology are recently developed utilizing nanoparticles of transition metal oxides, especially nanoceria that can switch between trivalent and tetravalent oxidation states of cerium. Cerium oxide nanoparticles (CeO-NPs) may act as both an oxidant and an antioxidant, depending on the preparation method and particle size. A novel colorimetric sensor for AOA assay is proposed with the use of poly(acrylic acid) sodium salt (PAANa)-coated CeO-NPs. PAANa-coated CeO-NPs oxidized tetramethyl benzidine (TMB), a peroxidase substrate, in a slightly acidic solution at pH 4.0 to a blue charge-transfer complex. Antioxidants decreased the color intensity of the nanoceria suspension, and were indirectly determined by absorbance difference. Detection limits, linearity, additivity and precision were calculated, e.g., quercetin quantification with the proposed assay showed a detection limit of 8.25 × 10 -9 mol L -1 . The trolox equivalent antioxidant capacities of hydrophilic and lipophilic antioxidants were compatible with those of conventional antioxidant assays. Potential interferents such as glucose, citric acid, mannitol, sorbitol and benzoic acid did not adversely affect AOA determination. The developed sensor is more sensitive and selective than similar colorimetric sensors relying on the intrinsic color change of nanoceria. The measurement wavelength is sufficiently red-shifted, preventing possible interferences from plant pigments. Copyright © 2018 Elsevier B.V. All rights reserved.

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,...

Multicolored redox active upconverter cerium oxide nanoparticle for bio-imaging and therapeutics†

PubMed Central

Babu, Suresh; Cho, Jung-Hyun; Dowding, Janet M.; Heckert, Eric; Komanski, Chris; Das, Soumen; Colon, Jimmie; Baker, Cheryl H.; Bass, Michael; Self, William T.; Seal, Sudipta

2011-01-01

Cytocompatible, co-doped cerium oxide nanoparticles exhibited strong upconversion properties that were found to kill lung cancer cells by inducing apoptosis thereby demonstrating the potential to be used as clinical contrast agents for imaging and as therapeutic agents for treatment of cancer. PMID:20683524

Intergenerational responses of wheat (Triticum aestivum L.) to cerium oxide nanoparticles exposure

EPA Science Inventory

The intergenerational impact of engineered nanomaterials in plants is a key knowledge gap in the literature. A soil microcosm study was performed to assess the effects of multi-generational exposure of wheat (Triticum aestivum L.) to cerium oxide nanoparticles (CeO2-NPs). Seeds f...

Thermometric titrimetry Studies of the cerium(IV) oxidation of alpha-mercaptocarboxylic acids.

PubMed

Alexander, W A; Mash, C J; McAuley, A

1969-04-01

The cerium(IV) oxidation of thioglycollic, thiolactic and thiomalic acids has been examined by thermometric titration. The titration curves indicate stoichiometries of more than 1 mole of cerium(IV) per mole of alpha-thiol, suggesting possible side-reactions. In the presence of methyl acrylate, however, the expected ratio is observed. The overall heat of each reaction has been derived. Only with a titration method of this kind where allowance can be made for side-reactions can the heats of reaction for these systems be measured.

High rate buffer layer for IBAD MgO coated conductors

DOEpatents

Foltyn, Stephen R [Los Alamos, NM; Jia, Quanxi [Los Alamos, NM; Arendt, Paul N [Los Alamos, NM

2007-08-21

Articles are provided including a base substrate having a layer of an oriented material thereon, and, a layer of hafnium oxide upon the layer of an oriented material. The layer of hafnium oxide can further include a secondary oxide such as cerium oxide, yttrium oxide, lanthanum oxide, scandium oxide, calcium oxide and magnesium oxide. Such articles can further include thin films of high temperature superconductive oxides such as YBCO upon the layer of hafnium oxide or layer of hafnium oxide and secondary oxide.

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.

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.

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.

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

2010-11-23

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.

Effect of Adding Cerium on Microstructure and Morphology of Ce-Based Inclusions Formed in Low-Carbon Steel

PubMed Central

Adabavazeh, Z.; Hwang, W. S.; Su, Y. H.

2017-01-01

Intra-granular Acicular Ferrite (IAF), as one of the most well-known desirable microstructure of ferrite with a chaotic crystallographic orientation, can not only refine the microstructure and retard the propagation of cleavage crack but also provide excellent combination of strength and toughness in steel. The effect of adding cerium on microstructure and controlling proper cerium-based inclusions in order to improve properties in low-carbon commercial steel (SS400) were investigated. The type of inclusions can be controlled by changing S/O ratio and Ce content. Without Ce modification, MnS is a dominate inclusion. After adding Ce, the stable inclusion phases change from AlCeO3 to Ce2O2S. The optimum amount of cerium, 0.0235 wt.%, lead in proper grain refinement and formation of cerium oxide, oxy-sulfide and sulfide inclusions. Having a high amount of cerium results in increasing the number of inclusions significantly as a result it cannot be effective enough and the inclusions will act like barriers for others. It is found that the inclusions with a size of about 4∼7 μm can serve as heterogeneous nucleation sites for AF formation. Thermodynamic calculations have been applied to predict the inclusion formation in this molten steel as well, which show a good agreement with experimental one. PMID:28485376

Liquid-phase oxidation of cyclohexanone over cerium oxide catalyst

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

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

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 reactionmore » 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.« less

Cerium oxide-triggered 'one-to-many' catalytic cycling strategy for in situ amplified electronic signal of low-abundance protein.

PubMed

Tang, Juan; Chen, Xian; Zhou, Jun; Li, Qunfang; Chen, Guonan; Tang, Dianping

2013-08-07

Multifunctionalized thionine-modified cerium oxide (Thi-CeO2) nanostructures with redox ability and catalytic activity were designed as the bionanolabels for in situ amplified electronic signal of low-abundance protein (carcinoembryonic antigen, CEA, used as a model) based on a cerium oxide-triggered 'one-to-many' catalytic cycling strategy. Initially, the carried CeO2 nanoparticles autocatalytically hydrolyzed the phosphate ester bond of l-ascorbic acid 2-phosphate (AAP) to produce a new reactant (l-ascorbic acid, AA), then the generated AA was electrochemically oxidized by the assembled thionine on the Thi-CeO2, and the resultant product was then reduced back to AA by the added tris(2-carboxyethy)phosphine (TCEP). The catalytic cycling could be re-triggered by the thionine and TCEP, resulting in amplification of the electrochemical signal. Under the optimized conditions, the electrochemical immunosensor exhibited a wide linear range of 0.1 pg mL(-1) to 80 ng mL(-1) with a low detection limit of 0.08 pg mL(-1) CEA at the 3σblank level. In addition, the methodology was evaluated for the analysis of clinical serum samples, and was in good accordance with values obtained using the commercialized enzyme-linked immunosorbent assay (ELISA) method.

Determination of chemical speciations of cerium in nuclear waste glasses

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

Gong, Meiling; Li, Hong

1996-12-31

Cerium oxides have been widely used as a surrogate for plutonium in the investigation of the melt and durability behavior of simulated nuclear waste glasses. It is well known that there is a cerous-ceric equilibrium in silicate glasses under normal melting conditions. The position of this equilibrium depends on glass composition, melting temperature, furnace atmosphere, and possibly the total amounts of cerium in glass. The oxidation state of cerium affects total solubility of cerium in glass, solubilities of other components in glass, viscosities and liquidus temperatures of the melts, and the chemical durability of the glasses. A procedure was developedmore » for the determination of the ceric and cerous distribution. The glass was ground to small particles of less than 300 meshes and was dissolved in mixture of HF and H{sub 2}SO{sub 4}. The ceric oxide was graduately reduced to cerous species in the presence of HF acid during the dissolution. To compensate the change of the equilibrium during the dissolution, a calibration curve is made with a mixture of standard solution of ceric sulphate and one gram of glass of the same composition containing no cerium. Boric acid was added to complex the fluoride ions, and the resultant solution was titrated potentiometrically with 0.01 N ferrous ammonium sulphate solution. The corrected ceric concentration was obtained on the calibration curve. The total cerium content in the above solution was analyzed using ICP-AES and the cerous content was the difference between the total Ce and Ce(+4).« less

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...

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...

Coated silicon comprising material for protection against environmental corrosion

NASA Technical Reports Server (NTRS)

Hazel, Brian Thomas (Inventor)

2009-01-01

In accordance with an embodiment of the invention, an article is disclosed. The article comprises a gas turbine engine component substrate comprising a silicon material; and an environmental barrier coating overlying the substrate, wherein the environmental barrier coating comprises cerium oxide, and the cerium oxide reduces formation of silicate glass on the substrate upon exposure to corrodant sulfates.

Effect of the conditions of REM microalloying of steel on the corrosion activity of nonmetallic inclusions

NASA Astrophysics Data System (ADS)

Movenko, D. A.; Kotel'nikov, G. I.; Pavlov, A. V.; Bytsenko, O. A.

2015-11-01

Experimental heats of low-alloy steel are performed under various conditions of rare-earth metal microalloying and aluminum and calcium deoxidation. Electron-probe microanalysis of nonmetallic inclusions and a metallographic investigation of a metal are used to show that, when interacting with water, nonmetallic cerium oxide inclusions do not form hydrates and, correspondingly, are not aggressive. When aluminum, calcium, and cerium additions are sequentially introduced into a melt, a continuous cerium oxide shell forms on calcium aluminates, protects corrosive nonmetallic inclusions against interaction with water, and weakens local metal corrosion.

Protective interlayer for high temperature solid electrolyte electrochemical cells

DOEpatents

Singh, Prabhakar; Vasilow, Theodore R.; Richards, Von L.

1996-01-01

The invention comprises of an electrically conducting doped or admixed cerium oxide composition with niobium oxide and/or tantalum oxide for electrochemical devices, characterized by the general formula: Nb.sub.x Ta.sub.y Ce.sub.1-x-y O.sub.2 where x is about 0.0 to 0.05, y is about 0.0 to 0.05, and x+y is about 0.02 to 0.05, and where x is preferably about 0.02 to 0.05 and y is 0, and a method of making the same. This novel composition is particularly applicable in forming a protective interlayer of a high temperature, solid electrolyte electrochemical cell (10), characterized by a first electrode (12); an electrically conductive interlayer (14) of niobium and/or tantalum doped cerium oxide deposited over at least a first portion (R) of the first electrode; an interconnect (16) deposited over the interlayer; a solid electrolyte (18) deposited over a second portion of the first electrode, the first portion being discontinuous from the second portion; and, a second electrode (20) deposited over the solid electrolyte. The interlayer (14) is characterized as being porous and selected from the group consisting of niobium doped cerium oxide, tantalum doped cerium oxide, and niobium and tantalum doped cerium oxide or admixtures of the same. The first electrode (12), an air electrode, is a porous layer of doped lanthanum manganite, the solid electrolyte layer (18) is a dense yttria stabilized zirconium oxide, the interconnect layer (16) is a dense, doped lanthanum chromite, and the second electrode (20), a fuel electrode, is a porous layer of nickel-zirconium oxide cermet. The electrochemical cell (10) can take on a plurality of shapes such as annular, planar, etc. and can be connected to a plurality of electrochemical cells in series and/or in parallel to generate electrical energy.

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

PubMed

Najafpour, Mohammad Mahdi; Rahimi, Fahime; Fathollahzadeh, Maryam; Haghighi, Behzad; Hołyńska, Małgorzata; Tomo, Tatsuya; Allakhverdiev, Suleyman I

2014-07-28

Herein, we report on nano-sized Mn oxide/carbon nanotubes, graphene and graphene oxide as water-oxidizing compounds in artificial photosynthesis. The composites are synthesized by different and simple procedures and characterized by a number of methods. The water-oxidizing activities of these composites are also considered in the presence of cerium(IV) ammonium nitrate. Some composites are efficient Mn-based catalysts with TOF (mmol O2 per mol Mn per second) ~ 2.6.

Fungus mediated synthesis of biomedically important cerium oxide nanoparticles

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

Khan, Shadab Ali; Ahmad, Absar, E-mail: a.ahmad@ncl.res.in

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 formore » 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, Photoluminescence spectroscopy (PL), Transmission Electron Microscopy (TEM), Fourier Transform Infrared Spectroscopy (FTIR), X-Ray Diffraction (XRD) and X-ray Photoemission Spectroscopy (XPS)« less

Processing and Characterization of Sol-Gel Cerium Oxide Microspheres

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

McClure, Zachary D.; Padilla Cintron, Cristina

Of interest to space exploration and power generation, Radioisotope Thermoelectric Generators (RTGs) can provide long-term power to remote electronic systems without the need for refueling or replacement. Plutonium-238 (Pu-238) remains one of the more promising materials for thermoelectric power generation due to its high power density, long half-life, and low gamma emissions. Traditional methods for processing Pu-238 include ball milling irregular precipitated powders before pressing and sintering into a dense pellet. The resulting submicron particulates of Pu-238 quickly accumulate and contaminate glove boxes. An alternative and dust-free method for Pu-238 processing is internal gelation via sol-gel techniques. Sol-gel methodology createsmore » monodisperse and uniform microspheres that can be packed and pressed into a pellet. For this study cerium oxide microspheres were produced as a surrogate to Pu-238. The similar electronic orbitals between cerium and plutonium make cerium an ideal choice for non-radioactive work. Before the microspheres can be sintered and pressed they must be washed to remove the processing oil and any unreacted substituents. An investigation was performed on the washing step to find an appropriate wash solution that reduced waste and flammable risk. Cerium oxide microspheres were processed, washed, and characterized to determine the effectiveness of the new wash solution.« less

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.

Comparison of Elemental Mercury Oxidation Across Vanadium and Cerium Based Catalysts in Coal Combustion Flue Gas: Catalytic Performances and Particulate Matter Effects.

PubMed

Wan, Qi; Yao, Qiang; Duan, Lei; Li, Xinghua; Zhang, Lei; Hao, Jiming

2018-03-06

This paper discussed the field test results of mercury oxidation activities over vanadium and cerium based catalysts in both coal-fired circulating fluidized bed boiler (CFBB) and chain grate boiler (CGB) flue gases. The characterizations of the catalysts and effects of flue gas components, specifically the particulate matter (PM) species, were also discussed. The catalytic performance results indicated that both catalysts exhibited mercury oxidation preference in CGB flue gas rather than in CFBB flue gas. Flue gas component studies before and after dust removal equipment implied that the mercury oxidation was well related to PM, together with gaseous components such as NO, SO 2 , and NH 3 . Further investigations demonstrated a negative PM concentration-induced effect on the mercury oxidation activity in the flue gases before the dust removal, which was attributed to the surface coverage by the large amount of PM. In addition, the PM concentrations in the flue gases after the dust removal failed in determining the mercury oxidation efficiency, wherein the presence of different chemical species in PM, such as elemental carbon (EC), organic carbon (OC) and alkali (earth) metals (Na, Mg, K, and Ca) in the flue gases dominated the catalytic oxidation of mercury.

Solid-state proton conductors

NASA Astrophysics Data System (ADS)

Jewulski, J. R.; Osif, T. L.; Remick, R. J.

1990-12-01

The purpose of this program was to survey the field of solid-state proton conductors (SSPC), identify conductors that could be used to develop solid-state fuel cells suitable for use with coal derived fuel gases, and begin the experimental research required for the development of these fuel cells. This document covers the following topics: the history of developments and current status of the SSPC, including a review of proton conducting electrolyte structures, the current status of the medium temperature SSPC development, electrodes for moderate temperature (SSPC) fuel cell, basic material and measurement techniques applicable for SSPC development, modeling, and optimization studies. Correlation and optimization studies are described which include correlation studies on proton conduction and oxide cathode optimization for the SSPC fuel cell. Experiments with the SSPC fuel cells are presented which include the fabrication of the electrolyte disks, apparatus for conducting measurements, the strontium-cerium based electrolyte, the barium-cerium based electrolyte with solid foil electrodes, the barium-cerium based electrolyte with porous electrodes, and conduction mechanisms.

Thermodynamic properties of gaseous cerium molybdates and tungstates studied by Knudsen effusion mass spectrometry.

PubMed

Shugurov, S M; Panin, A I; Lopatin, S I

2018-06-21

CeO 2 -WO 3 and CeO 2 -MoO 3 catalysts have shown excellent performance in the selective reduction of NO x by ammonia (NH 3 -selective catalytic reduction) over a wide temperature range. Strong interaction between CeO 2 and WO 3 or MoO 3 might be the dominant reason for the high activity of these mixed oxides. Studies of ceria-containing gaseous salts involve considerable experimental difficulties, since the transition of such salts to vapor requires high temperatures. To predict the possibility of the existence of gaseous associates formed by cerium and molybdenum (tungsten) oxides it is important to know their thermodynamic characteristics. Until the present investigation, gaseous cerium oxyacid salts were unknown. Knudsen effusion mass spectrometry was used to determine the partial pressures of vapor species and the equilibrium constants of gas-phase reactions, as well as the formation and atomization enthalpies of gaseous cerium molybdates and tungstates. CeO 2 was evaporated from molybdenum and tungsten effusion cells containing gold metal as a pressure standard. A theoretical study of gaseous cerium gaseous molybdates and tungstates was performed by several quantum chemical methods. In the temperature range 2050-2400 K, CeO, CeO 2 , XO 2 , XO 3 , CeWO 3 , CeXO 4 , CeXO 5 (X = Mo, W) and CeMo 2 O 7 were found to be the main vapor species over the CeO 2 - Mo (W) systems. On the basis of the equilibrium constants of the gaseous reactions, the standard formation enthalpies of gaseous CeWO 3 , CeXO 4 , CeXO 5 (X = Mo, W) and CeMo 2 O 7 at 298 K were determined. Energetically favorable structures of gaseous cerium salts were found and vibrational frequencies were evaluated in the harmonic approximation. The thermal stability of gaseous cerium oxyacid salts was confirmed by high-temperature mass spectrometry. Reaction enthalpies of the gaseous cerium molybdates and tungstates from gaseous cerium, molybdenum and tungsten oxides were evaluated theoretically and the obtained values are in reasonable agreement with the experimental one. This article is protected by copyright. All rights reserved.

Development and Validation of Spectrofluorimetric Method for Determination of Biotin in Bulk and Pharmaceutical Preparations via its Oxidation with Cerium (IV)

PubMed Central

Walash, M. I.; Rizk, M.; Sheribah, Z. A.; Salim, M. M.

2010-01-01

A simple and sensitive spectrofluorimetric method was developed for the determination of biotin in pure form and in pharmaceutical preparations. The proposed method is based on the oxidation of the drug with cerium (IV) ammonium sulfate in acidic medium. The fluorescence of the produced Cerium (III) was measured at 365 nm after excitation at 255 nm. The different experimental parameters affecting the development and stability of the reaction were carefully studied and optimized. The method is applicable over the concentration range of 30-120 ng/mL with correlation coefficient of 0.9998. The detection limit (LOD) of biotin was 2.41 ng/mL while quantitation limit (LOQ) was 7.29 ng/mL. The proposed procedure was successfully applied for the determination of biotin in pharmaceutical preparations with mean recoveries of 99.55 ± 0.83 and 101.67 ± 1.53 for biotin ampoules and capsules, respectively. The results obtained were in good agreement with those obtained using the official method. PMID:23675202

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.

Nanostructured cerium oxide: preparation, characterization, and application in energy and environmental catalysis

DOE PAGES

Tang, Wen-Xiang; Gao, Pu-Xian

2016-11-10

Nanostructured cerium oxide (CeO 2) with outstanding physical and chemical properties has attracted extensive interests over the past few decades in environment and energy-related applications. With controllable synthesis of nanostructured CeO 2, much more features were technologically brought out from defect chemistry to structure-derived effects. This paper highlights recent progress on the synthesis and characterization of nanostructured ceria-based materials as well as the traditional and new applications. Specifically, several typical applications based on the desired ceria nanostructures are focused to showcase the importance of nanostructure-derived effects. Moreover, some challenges and perspectives on the nanostructured ceria are presented, such as defectsmore » controlling and retainment, scale-up fabrication, and monolithic devices. Hopefully, this paper can provide an improved understanding of nanostructured CeO 2 and offer new opportunities to promote the further research and applications in the future.« less

The effect of cerium oxide argon-annealed coatings on the high temperature oxidation of a FeCrAl alloy

NASA Astrophysics Data System (ADS)

Nguyen, C. T.; Buscail, H.; Cueff, R.; Issartel, C.; Riffard, F.; Perrier, S.; Poble, O.

2009-09-01

Ceria coatings were applied in order to improve the adherence of alumina scales developed on a model Fe-20Cr-5Al alloy during oxidation at high temperature. These coatings were performed by argon annealing of a ceria sol-gel coating at temperatures ranging between 600 and 1000 °C. The influence of these coatings on the alloy oxidation behaviour was studied at 1100 °C. In situ X-ray diffraction (XRD) was performed to characterize the coating crystallographic nature after annealing and during the oxidation process. The alumina scale morphologies were studied by means of scanning electron microscopy (SEM) coupled with energy dispersive X-ray spectroscopy (EDS). The present work shows that the alumina scale morphology observed on cerium sol-gel coated alloy was very convoluted. On the cerium sol-gel coated alloy, argon annealing results in an increase of the oxidation rate in air, at 1100 °C. The 600 °C argon annealing temperature results in a good alumina scale adherence under thermal cycling conditions at 1100 °C.

Effect of support size on the catalytic activity of metal-oxide-doped silica particles in the glycolysis of polyethylene terephthalate.

PubMed

Wi, Rinbok; Imran, Muhammad; Lee, Kyoung G; Yoon, Sun Hong; Cho, Bong Gyoo; Kim, Do Hyun

2011-07-01

Zinc oxide (ZnO) and cerium oxide (CeO2) nanoparticles were deposited on the surface of preformed silica spheres with diameters ranging from 60 to 750 nm. Ultrasonic irradiation was employed to promote the deposition of the metal oxide nanoparticles on the surface of silica. Silica-supported zinc oxide or cerium oxide was used as a catalyst in the glycolysis of polyethylene terephthalate, one of the key processes in the depolymerization of polyethylene terephthalate. The effect of the support size on the catalytic activity was studied in terms of monomer yield, and the monomer concentration was analyzed via high-performance liquid chromatography (HPLC). The morphologies and surface properties of the catalysts were characterized using a scanning electron microscope, a transmission electron microscope, and a BET surface area analyzer, while the monomer was characterized via HPLC and nuclear-magnetic-resonance spectroscopy. Both the zinc oxide and cerium oxide deposited on a smaller support showed better distribution and less aggregation. The high specific surface area of the smaller support catalysts provided a large number of active sites. The highest monomer yield was obtained with a catalyst of 60-nm silica support.

High-temperature fabricable nickel-iron aluminides

DOEpatents

Liu, Chain T.

1988-02-02

Nickel-iron aluminides are described that are based on Ni.sub.3 Al, and have significant iron content, to which additions of hafnium, boron, carbon and cerium are made resulting in Ni.sub.3 Al base alloys that can be fabricated at higher temperatures than similar alloys previously developed. Further addition of molybdenum improves oxidation and cracking resistance. These alloys possess the advantages of ductility, hot fabricability, strength, and oxidation resistance.

Manganese-cerium oxide catalysts prepared by non-thermal plasma for NO oxidation: Effect of O2 in discharge atmosphere

NASA Astrophysics Data System (ADS)

Liu, Lu; Zheng, Chenghang; Wu, Shenghao; Gao, Xiang; Ni, Mingjiang; Cen, Kefa

2017-09-01

Non-thermal plasma with different O2 concentration in discharge atmosphere was applied to synthesize manganese and cerium mixed-oxides catalysts, which were compared in NO oxidation activity. Discharge atmosphere displayed a crucial influence on the performance of the catalysts prepared by plasma. Relatively low O2 concentration in discharge atmosphere allows synthesizing manganese-cerium oxides catalysts in a moderate environment and therefore is favorable for better physicochemical properties which lead to superior catalytic behavior. The best catalyst was obtained by treatment with 10% O2/N2 plasma and presented over 80% NO conversion in the temperature range of 275-325 °C, whereas catalyst prepared in pure O2 discharge atmosphere had the same activity with a catalyst prepared by calcinations. A correlation between the surface properties of the plasma prepared catalysts and its catalytic activity in NO oxidation is proposed. The amount of the surface adsorbed oxygen has an obvious linear correlation with the amount of Ce3+, the H2 consumption at low temperatures and the catalytic performance. The superior catalytic performance is mainly attributed to the stronger interaction between manganese oxides and ceria, and the formation of poorly crystallized Mn-O-Ce phase in the catalyst which resulted from the slow decomposition of nitrates and organics during plasma treatment. Catalysts prepared in relatively low O2 concentration have large specific surface area and is abundant in Ce3+ species and active oxygen species. The study suggests that plasma treatment with proper discharge gas components is a promising method to prepare effective manganese- cerium oxides catalyst for NO oxidation.

Bio-sensing applications of cerium oxide nanoparticles: Advantages and disadvantages.

PubMed

Charbgoo, Fahimeh; Ramezani, Mohammad; Darroudi, Majid

2017-10-15

Cerium oxide nanoparticles (CNPs) contain several properties such as catalytic activity, fluorescent quencher and electrochemical, high surface area, and oxygen transfer ability, which have attracted considerable attention in developing high-sensitive biosensors. CNPs can be used as a whole sensor or a part of recognition or transducer element. However, reports have shown that applying these nanoparticles in sensor design could remarkably enhance detection sensitivity. CNP's outstanding properties in biosensors which go from high catalytic activity and surface area to oxygen transfer and fluorescent quenching capabilities are also highlighted. Herein, we discuss the advantages and disadvantages of CNPs-based biosensors that function through various detection modes including colorimetric, electrochemistry, and chemoluminescent regarding the detection of small organic chemicals, metal ions and biomarkers. Copyright © 2017 Elsevier B.V. All rights reserved.

Synthesis & characterization of Bi7.38Ce0.62O12.3 and its optical and electrocatalytic property

NASA Astrophysics Data System (ADS)

Padmanaban, A.; Dhanasekaran, T.; Kumar, S. Praveen; Gnanamoorthy, G.; Stephen, A.; Narayanan, V.

2017-05-01

Bismuth cerium oxide was synthesized by thermal decomposition method. The material was characterized by X-ray diffraction technique, DRS UV-Vis, Raman spectral methods and FE-SEM. The electrocatalytic sensing activity of bismuth cerium oxide modified GCE toward 4-nitrophenol exhibits better activity than the bare GCE. The modified electrode shows higher anodic current response with lower potential.

High Temperature Oxidation and Electrochemical Studies Related to Hot Corrosion

DTIC Science & Technology

1992-05-01

sulfidation. In sulfidation, NaCI reacts with sulfur found in the fuel to form Na2SO4. The sodium sulfate reacts with the protective oxide scale resulting...fluxing or acid -base reaction model. In sufidation, 4 Bornstein explains that the oxide scales are insoluble in stoichiometric sodium sulfate , but due to...oxygen partial pressures an electron hopping mechanism dominates. Reduced cerium ions and Ce3+- oxygen vacancy associates generate these conducting

Oxygen evolution reaction catalysis

DOEpatents

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

2016-09-06

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

Induction of pulmonary fibrosis by cerium oxide nanoparticles

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

Ma, Jane Y., E-mail: jym1@cdc.gov; Mercer, Robert R.; Barger, Mark

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 macrophagesmore » (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. ► Cerium oxide particles were detected in lung tissue and AM. ► Cerium oxide caused lung fibrosis in a dose- and time-dependent manner.« less

Catalyst and method for reduction of nitrogen oxides

DOEpatents

Ott, Kevin C [Los Alamos, NM

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).

Catalyst and method for reduction of nitrogen oxides

DOEpatents

Ott, Kevin C [Los Alamos, NM

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).

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).

Portable system of programmable syringe pump with potentiometer for determination of promethazine in pharmaceutical applications.

PubMed

Saleh, Tawfik A; Abulkibash, A M; Ibrahim, Atta E

2012-04-01

A simple and fast-automated method was developed and validated for the assay of promethazine hydrochloride in pharmaceutical formulations, based on the oxidation of promethazine by cerium in an acidic medium. A portable system, consisting of a programmable syringe pump connected to a potentiometer, was constructed. The developed change in potential during promethazine oxidation was monitored. The related optimum working conditions, such as supporting electrolyte concentration, cerium(IV) concentration and flow rate were optimized. The proposed method was successfully applied to pharmaceutical samples as well as synthetic ones. The obtained results were realized by the official British pharmacopoeia (BP) method and comparable results were obtained. The obtained t-value indicates no significant differences between the results of the proposed and BP methods, with the advantages of the proposed method being simple, sensitive and cost effective.

Cerium nanoparticle effect on sensitivity of Fricke gel dosimeter: Initial investigation

NASA Astrophysics Data System (ADS)

Ebenezer Suman Babu, S.; Peace Balasingh, S. Timothy; Benedicta Pearlin, R.; Rabi Raja Singh, I.; Ravindran, B. Paul

2017-05-01

Fricke gel dosimeters (FXGs) have been the preferred dosimeters because of its ease in preparation and water and tissue equivalency. Visible changes happen three dimensionally in the dosimeter as the ferrous (Fe2+) ions change into ferric (Fe3+) ions upon irradiation and the measure of this change can be correlated to the dose absorbed. Nanoparticles are promising entities that can improve the sensitivity of the gel dosimeter. Cerium Oxide nanoparticle was investigated for possible enhancement of absorbed dose in the FXG. Various concentrations of the nanoparticle based gel dosimeters were prepared and irradiated for a clinical dose range of 0-3 Gy in a telegamma unit. The optimal concentration of 0.1 mM nanoparticle incorporated in the FXG enhances the radiation sensitivity of the unmodified FXG taken as reference without modifying the background absorbance prior to irradiation. The gel recipe consisted of 5% (wt) gelatin, 50 mM Sulphuric acid, 0.05 mM Xylenol Orange, 0.5 mM Ferrous Ammonium Sulphate and 0.1 mM Cerium (IV) Oxide nanoparticle (< 25 nm particle size) and triple distilled water. The FXGs with nanoparticle showed linear dose response in the dose range tested.

Solar hydrogen production with cerium oxides thermochemical cycle

NASA Astrophysics Data System (ADS)

Binotti, Marco; Di Marcoberardino, Gioele; Biassoni, Mauro; Manzolini, Giampaolo

2017-06-01

This paper discusses the hydrogen production using a solar driven thermochemical cycle. The thermochemical cycle is based on nonstoichiometric cerium oxides redox and the solar concentration system is a solar dish. Detailed optical and redox models were developed to optimize the hydrogen production performance as function of several design parameters (i.e. concentration ratio, reactor pressures and temperatures) The efficiency of the considered technology is compared against two commercially available technologies namely PV + electrolyzer and Dish Stirling + electrolyzer. Results show that solar-to-fuel efficiency of 21.2% can be achieved at design condition assuming a concentration ratio around 5000, reduction and oxidation temperatures of 1500°C and 1275 °C. When moving to annual performance, the annual yield of the considered approach can be as high as 16.7% which is about 43% higher than the best competitive technology. The higher performance implies that higher installation costs around 40% can be accepted for the innovative concept to achieve the same cost of hydrogen.

Investigating effects of nano cerium oxide reinforcement on mechanical properties of composite based on natural rubber

NASA Astrophysics Data System (ADS)

Bao, Le Quoc; Phan, Vu Hoang Giang; Khuyen, Nguyen Quang

2018-04-01

Polymer nanocomposites that based on combination of nanomaterials (such as nanoparticles, nanotubes, nanorods, nanofibers, and nanosheets) and polymeric matrices are receiving great attention in research and application. However, separate and homogenous dispersion rather than aggregates of nanoparticles into matrices meet big difficulty due to large interaction between nanoparticles. The poor dispersion leads to low properties of nanocomposites. In this study, we find out the appropriate method to separately disperse cerium oxides (CeO2) nanoparticles into natural rubber, aiming to increase mechanical properties of natural rubber. The SEM images were used to evaluate the dispersion of nano CeO2 in natural rubber matrix. The mechanical properties of nanocomposites were measured after vulcanization to investigate effects of nano CeO2 amount on prepared composite. The findings exhibited that the addition of CeO2 by dispersion of nano CeO2 in water via ultrasonication before mixing with rubber latex, significantly increase modulus, tear and wear resistance of natural rubber.

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

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

Gaynor, James D.; Karakoti, Ajay S.; Inerbaev, Talgat

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.

Synthesis of nanocrystalline Ni/Ce-YSZ powder via a polymerization route

NASA Astrophysics Data System (ADS)

Abolghasemi, Z.; Tamizifar, M.; Arzani, K.; Nemati, A.; Khanfekr, A.; Bolandi, M.

2013-08-01

Pechini process was used for preparation of three kinds of nanocrystalline powders of yttria-stabilized zirconia (YSZ): doped with 1.5 mol% nickel oxide, doped with 15 mol% ceria, and doped with 1.5 mol% nickel oxide plus 15 mol% ceria. Zirconium chloride, yttrium nitrate, cerium nitrate, nickel nitrate, citric acid and ethylene glycol were polymerized at 80 °C to produce a gel. XRD, SEM and TEM analyses were used to investigate the crystalline phases and microstructures of obtained compounds. The results of XRD revealed the formation of nanocrystalline powder at 900 °C. Morphology of the powder calcined at 900 °C, examined with a scanning electron microscope, showed that the presence of nickel and cerium inhibited the grain growth in the system. The average crystallite size of the material doped with nickel oxide (9.33 nm) was bigger than the one doped with cerium oxide (9.29 nm), while the YSZ doping with the two oxides simultaneously promoted the grain growth with crystallite size of 11.37 nm. Yttria-stabilized zirconia powder with a mean crystallite size of 9.997 nm was prepared successfully by this method.

Stabilized tin-oxide-based oxidation/reduction catalysts

NASA Technical Reports Server (NTRS)

Watkins, Anthony Neal (Inventor); Oglesby, Donald M. (Inventor); Gulati, Suresh T. (Inventor); Summers, Jerry C. (Inventor); Schryer, David R. (Inventor); Davis, Patricia P. (Inventor); Leighty, Bradley D. (Inventor); Jordan, Jeffrey D. (Inventor); Schryer, Jacqueline L. (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.

Liquid Metal Anode for JP-8 Fuel Cell

DTIC Science & Technology

2009-01-15

bases. They react preferentially with acidic sulfur and its compounds, S, SO2 and H2S. These reactions of cerium oxides with sulfur and its...by sulfur . The dominating thermodynamic reaction is the formation of metal sulfides or sulfates , not the desired electrochemical reduction...oxidation of sulfur to make sulfuric acid . Vanadium carbide used as a fuel cell anode has been evaluated by Japanese researchers and CellTech Power. Its

Increased viability of fibroblasts when pretreated with ceria nanoparticles during serum deprivation.

PubMed

Genier, Francielli S; Bizanek, Maximilian; Webster, Thomas J; Roy, Amit K

2018-01-01

Conditions of cellular stress are often the cause of cell death or dysfunction. Sustained cell stress can lead to several health complications, such as extensive inflammatory responses, tumor growth, and necrosis. To prevent disease and protect human tissue during these conditions and to avoid medication side effects, nanomaterials with unique characteristics have been applied to biological systems. This paper introduces the pretreatment in human dermal fibroblasts with cerium oxide nanoparticles during nutritional stress. For this purpose, human dermal fibroblast cells received cell culture media with concentrations of 250 µg/mL and 500 µg/mL of nano-cerium oxide before being exposed to 24, 48, and 72 hours of serum starvation. Contrast images demonstrated higher cell confluence and cell integrity in cells pretreated with ceria nanoparticles compared to untreated cells. It was confirmed by MTS assay after 72 hours of serum starvation that higher cell viability was achieved with ceria nanoparticles. The results demonstrate the potential of cerium oxide nanoparticles as protective agents during cellular starvation.

Threshold Ionization and Spin-Orbit Coupling of Cerium Monoxide

NASA Astrophysics Data System (ADS)

Cao, Wenjin; Zhang, Yuchen; Wu, Lu; Yang, Dong-Sheng

2017-06-01

Cerium oxides are widely used in heterogeneous catalysis due to their ability to switch between different oxidation states. We report here the mass-analyzed threshold ionization (MATI) spectroscopy of cerium monoxide (CeO) produced by laser ablating a Ce rod in a molecular beam source. The MATI spectrum in the range of 40000-45000 \\wn exhibits several band systems with similar vibrational progressions. The strongest band is at 43015 (5) \\wn, which can be assigned as the adiabatic ionization energy of the neutral species. The spectrum also shows Ce-O stretching frequencies of 817 and 890 \\wn in the neutral and ion states, respectively. By comparing with spin-orbit coupled multireference quasi-degenerate perturbation theory (SO-MCQDPT) calculations, the observed band systems are assigned to transitions from various low-energy spin-orbit levels of the neutral oxide to the two lowest spin-orbit levels of the corresponding ion. The current work will also be compared with previous experimental and computational studies on the neutral species.

Preparation of core-shell Ag@CeO2 nanocomposite by LSPR photothermal induced interface reaction

NASA Astrophysics Data System (ADS)

Zhong, H. X.; Wei, Y.; Yue, Y. Z.; Zhang, L. H.; Liu, Y.

2016-04-01

The core-shell structure of Ag@CeO2 was prepared by a novel and facile method, which was based on the photothermal effect of localized surface plasmon resonance (LSPR). Nanoparticles (NPs) of Ag were dispersed in a solution containing citric acid, ethylene glycol and cerium nitrate, then under irradiation, Ag NPs generated heat from LSPR and the heat-induced polymerization reaction in the interface between Ag and the sol resulted in cerium gel formation only on the surface of the Ag NPs. After calcination, Ag@CeO2 was successfully obtained, then Ag@CeO2/SiO2 was prepared by loading Ag@CeO2 on SiO2. The resultant catalyst exhibited favorable activity and stability for CO oxidation. The preparation method proposed here should be extendable to other composites with metallic cores and oxide shells in which the metallic nanoparticle possesses LSPR properties.

Portable system of programmable syringe pump with potentiometer for determination of promethazine in pharmaceutical applications

PubMed Central

Saleh, Tawfik A.; Abulkibash, A.M.; Ibrahim, Atta E.

2011-01-01

A simple and fast-automated method was developed and validated for the assay of promethazine hydrochloride in pharmaceutical formulations, based on the oxidation of promethazine by cerium in an acidic medium. A portable system, consisting of a programmable syringe pump connected to a potentiometer, was constructed. The developed change in potential during promethazine oxidation was monitored. The related optimum working conditions, such as supporting electrolyte concentration, cerium(IV) concentration and flow rate were optimized. The proposed method was successfully applied to pharmaceutical samples as well as synthetic ones. The obtained results were realized by the official British pharmacopoeia (BP) method and comparable results were obtained. The obtained t-value indicates no significant differences between the results of the proposed and BP methods, with the advantages of the proposed method being simple, sensitive and cost effective. PMID:23960787

In-situ surface science studies of the interaction between sulfur dioxide and two-dimensional palladium loaded-cerium/zirconium mixed metal oxide model catalysts

NASA Astrophysics Data System (ADS)

Romano, Esteban Javier

2005-07-01

Cerium and zirconium oxides are important materials in industrial catalysis. Particularly, the great advances attained in the past 30 years in controlling levels of gaseous pollutants released from internal combustion engines can be attributed to the development of catalysts employing these materials. Unfortunately, oxides of sulfur are known threats to the longevity of many catalytic systems by irreversibly interacting with catalytic materials. In this work, polycrystalline cerium-zirconium mixed-metal-oxide (MMO) solid solutions were synthesized. High resolution x-ray photoelectron spectroscopy (XPS) spectral data was collected and examined for revelation of the surface species that form on these metal oxides after in-situ exposures to sulfur dioxide. The model catalysts were exposed to sulfur dioxide using a custom modified in-situ reaction cell and platen heater. The results of this study demonstrate the formation of sulfate and sulfite surface sulfur species. Temperature and compositional dependencies were displayed, with higher temperatures and ceria molar ratios displaying a larger propensity for forming surface sulfur species. In addition to analysis of sulfur photoemission, the photoemission regions of oxygen, zirconium, and cerium were examined for the materials used in this study before and after the aforementioned treatments with sulfur dioxide. The presence of surface hydroxyl groups was observed and metal oxidation state changes were probed to further enhance the understanding of sulfur dioxide adsorption on the synthesized materials. Palladium loaded mixed-metal oxides were synthesized using a unique solid-state methodology to probe the effect of palladium addition on sulfur dioxide adsorption. The addition of palladium to this model system is shown to have a strong effect on the magnitude of adsorption for sulfur dioxide on some material/exposure condition combinations. Ceria/zirconia sulfite and sulfate species are identified on the palladium-loaded MMO materials with adsorption sites located on the exposed oxide sites.

Study on the poisoning effect-of non-vanadium catalysts by potassium

NASA Astrophysics Data System (ADS)

Zeng, Huanmu; Liu, Ying; Yu, Xiaowei; Lin, Yasi

2018-02-01

The poisoning effect of catalyst by alkali metals is one of the problems in the selective catalytic reduction (SCR) of NO by NH3. Serious deactivation by alkali poisoning have been proved to take place in the commercial vanadium catalyst. Recently, non-vanadium catalysts such as copper oxides, manganese oxides, chromium oxides and cerium oxides have attracted special attentions in SCR application. However, their tolerance in the presence of alkali metals is still doubtful. In this paper, copper oxides, manganese oxides, chromium oxides and cerium oxides supported on TiO2 nanoparticle was prepared by impregnating method. Potassium nitrate was chosen as the precursor of poisoner. Catalytic activities of these catalysts were evaluated before and after the addition of potassium. Some characterization methods including X-ray diffraction and temperature programmed desorption was utilized to reveal the main reason of alkali deactivation.

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...

Low temperature solid oxide electrolytes (LT-SOE): A review

NASA Astrophysics Data System (ADS)

Singh, B.; Ghosh, S.; Aich, S.; Roy, B.

2017-01-01

Low temperature solid oxide fuel cell (LT-SOFC) can be a source of power for vehicles, online grid, and at the same time reduce system cost, offer high reliability, and fast start-up. A huge amount of research work, as evident from the literature has been conducted for the enhancement of the ionic conductivity of LT electrolytes in the last few years. The basic conduction mechanisms, advantages and disadvantages of different LT oxide ion conducting electrolytes {BIMEVOX systems, bilayer systems including doped cerium oxide/stabilised bismuth oxide and YSZ/DCO}, mixed ion conducting electrolytes {doped cerium oxides/alkali metal carbonate composites}, and proton conducting electrolytes {doped and undoped BaCeO3, BaZrO3, etc.} are discussed here based on the recent research articles. Effect of various material aspects (composition, doping, layer thickness, etc.), fabrication methods (to achieve different microstructures and particle size), design related strategies (interlayer, sintering aid etc.), characterization temperature & environment on the conductivity of the electrolytes and performance of the fuel cells made from these electrolytes are shown in tabular form and discussed. The conductivity of the electrolytes and performance of the corresponding fuel cells are compared. Other applications of the electrolytes are mentioned. A few considerations regarding the future prospects are pointed.

Advanced development of non-discoloring EVA-based PV encapsulants

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

Holley, W.H.; Galica, J.P.; Argo, S.C.

1996-01-01

The purpose of this investigation was to better define the problem of field yellowing of EVA-based PV encapsulant, through laboratory study of probable chemical mechanisms and the development of stabilization strategies for protecting EVA from discoloration. EVA from fielded modules was analyzed for vinyl acetate content, unsaturation, and additive levels. These test results were then compared to results from Xenon Arc Weather-Ometer aged glass/EVA/glass laminates made in the laboratory. Variables evaluated in Weather-Ometer aged laminates included ``standard-cure`` A9918P EVA, ``fast-cure`` 15295P EVA, low iron glass superstrate containing cerium oxide, and systematic elimination or addition of specific additives. Six significant findingsmore » were revealed: 1) Improved ``standard-cure`` and ``fast-cure`` type EVA encapsulants, formulations X9903P and X15303P, respectively, showed little or no yellowing after extended Weather-Ometer exposure; 2) The use of {open_quote}{open_quote}fast-cure{close_quote}{close_quote} EVA reduced discoloration when compared with {open_quote}{open_quote}standard-cure{close_quote}{close_quote} A9918P EVA; 3) Glass superstrate containing cerium oxide resulted in a reduced rate of EVA discoloration; 4) {open_quote}{open_quote}Fast-cure{close_quote}{close_quote} EVA used with glass superstrate containing cerium oxide showed no visible yellowing after 32 weeks in the Weather-Ometer{emdash}a period estimated to be roughly equivalent to 20{endash}30 years of exposure in the Southwest; 5) Severely discolored EVA samples from the field showed no measurable loss of acetate group and little detectable unsaturation; and 6) EVA encapsulant with a Tefzel cover exhibited no yellowing after extended Weather-Ometer exposure. {copyright} {ital 1996 American Institute of Physics.}« less

Mesoporous CeO2 nanoparticles synthesized by an inverse miniemulsion technique and their catalytic properties in methane oxidation

NASA Astrophysics Data System (ADS)

Nabih, Nermeen; Schiller, Renate; Lieberwirth, Ingo; Kockrick, Emanuel; Frind, Robert; Kaskel, Stefan; Weiss, Clemens K.; Landfester, Katharina

2011-04-01

Cerium(IV) oxide nanoparticles were synthesized using an inverse miniemulsion technique with cerium nitrate hexahydrate as precursor. The resulting nanocrystallites are as small as 5 nm with a specific surface area of 158 m2 g - 1 after calcination at 400 °C. With the addition of cetyltrimethylammonium bromide (CTAB) or (poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide)) triblock copolymers (PEO-PPO-PEO) as template in the miniemulsion droplets, the specific surface area can be increased up to 255 m2 g - 1. The miniemulsions were characterized by dynamic light scattering (DLS) and the obtained oxides were examined by x-ray diffraction (XRD), nitrogen sorption (BET and BJH), and transmission electron microscopy (TEM). The catalytic activity of the resulting ceria was investigated for the temperature-programmed oxidation (TPO) of methane.

Cerium(IV)-mediated oxidation of flavonol with relevance to flavonol 2,4-dioxygenase. Direct evidence for spin delocalization in the flavonoxy radical.

PubMed

Kaizer, József; Ganszky, Ildikó; Speier, Gábor; Rockenbauer, Antal; Korecz, László; Giorgi, Michel; Réglier, Marius; Antonczak, Serge

2007-06-01

The cerium(IV)-mediated oxidation of 3-hydroxy-4'-methylflavone (1) proceeds by H-atom abstraction forming the flavonoxy radical (7), and the subsequent combination of its resonance forms leads to the 3-hydroxy-4'-methylflavone dehydro dimer (9). The above system serves as direct evidence for the intermediacy of the flavonoxy radical, its spin delocalization, and also indirect evidence for valence tautomerism as a key step on the substrate activation both in the quercetinase and its biomimic model system.

Thermal decomposition kinetics of hydrazinium cerium 2,3-Pyrazinedicarboxylate hydrate: a new precursor for CeO2.

PubMed

Premkumar, Thathan; Govindarajan, Subbiah; Coles, Andrew E; Wight, Charles A

2005-04-07

The thermal decomposition kinetics of N(2)H(5)[Ce(pyrazine-2,3-dicarboxylate)(2)(H(2)O)] (Ce-P) have been studied by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC), for the first time; TGA analysis reveals an oxidative decomposition process yielding CeO(2) as the final product with an activation energy of approximately 160 kJ mol(-1). This complex may be used as a precursor to fine particle cerium oxides due to its low temperature of decomposition.

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); Leighty, Bradley D. (Inventor); Watkins, Anthony N. (Inventor); Summers, Jerry C. (Inventor); Davis, Patricia P. (Inventor); Oglesby, Donald M. (Inventor); Schryer, Jacqueline L. (Inventor); Gulati, Suresh T. (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.

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 ...

Biomineralization-Inspired Synthesis of Cerium-Doped Carbonaceous Nanoparticles for Highly Hydroxyl Radical Scavenging Activity

NASA Astrophysics Data System (ADS)

Zou, Shenqiang; Zhu, Xiaofang; Zhang, Lirong; Guo, Fan; Zhang, Miaomiao; Tan, Youwen; Gong, Aihua; Fang, Zhengzou; Ju, Huixiang; Wu, Chaoyang; Du, Fengyi

2018-03-01

Cerium oxide nanoparticles recently have received extensive attention in biomedical applications due to their excellent anti-oxidation performance. In this study, a simple, mild, and green approach was developed to synthesize cerium-doped carbonaceous nanoparticles (Ce-doped CNPs) using bio-mineralization of bull serum albumin (BSA) as precursor. The resultant Ce-doped CNPs exhibited uniform and ultrasmall morphology with an average size of 14.7 nm. XPS and FTIR results revealed the presence of hydrophilic group on the surface of Ce-doped CNPs, which resulted in excellent dispersity in water. The CCK-8 assay demonstrated that Ce-doped CNPs possessed favorable biocompatibility and negligible cytotoxicity. Using H2O2-induced reactive oxygen species (ROS) as model, Ce-doped CNPs showed highly hydroxyl radical scavenging capability. Furthermore, flow cytometry and live-dead staining results indicated that Ce-doped CNPs protected cells from H2O2-induced damage in a dose-dependent effect, which provided a direct evidence for anti-oxidative performance. These findings suggest that Ce-doped CNPs as novel ROS scavengers may provide a potential therapeutic prospect in treating diseases associated with oxidative stress.

Tuning the Selectivity of Catalytic Carbon Dioxide Hydrogenation over Iridium/Cerium Oxide Catalysts with a Strong Metal-Support Interaction.

PubMed

Li, Siwei; Xu, Yao; Chen, Yifu; Li, Weizhen; Lin, Lili; Li, Mengzhu; Deng, Yuchen; Wang, Xiaoping; Ge, Binghui; Yang, Ce; Yao, Siyu; Xie, Jinglin; Li, Yongwang; Liu, Xi; Ma, Ding

2017-08-28

A one-step ligand-free method based on an adsorption-precipitation process was developed to fabricate iridium/cerium oxide (Ir/CeO 2 ) nanocatalysts. Ir species demonstrated a strong metal-support interaction (SMSI) with the CeO 2 substrate. The chemical state of Ir could be finely tuned by altering the loading of the metal. In the carbon dioxide (CO 2 ) hydrogenation reaction it was shown that the chemical state of Ir species-induced by a SMSI-has a major impact on the reaction selectivity. Direct evidence is provided indicating that a single-site catalyst is not a prerequisite for inhibition of methanation and sole production of carbon monoxide (CO) in CO 2 hydrogenation. Instead, modulation of the chemical state of metal species by a strong metal-support interaction is more important for regulation of the observed selectivity (metallic Ir particles select for methane while partially oxidized Ir species select for CO production). The study provides insight into heterogeneous catalysts at nano, sub-nano, and atomic scales. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Protective effects of Curcuma longa against neurobehavioral and neurochemical damage caused by cerium chloride in mice.

PubMed

Kadri, Yamina; Nciri, Riadh; Brahmi, Noura; Saidi, Saber; Harrath, Abdel Halim; Alwasel, Saleh; Aldahmash, Waleed; El Feki, Abdelfatteh; Allagui, Mohamed Salah

2018-05-07

Cerium chloride (CeCl 3 ) is considered an environmental pollutant and a potent neurotoxic agent. Medicinal plants have many bioactive compounds that provide protection against damage caused by such pollutants. Curcuma longa is a bioactive compound-rich plant with very important antioxidant properties. To study the preventive and healing effects of Curcuma longa on cerium-damaged mouse brains, we intraperitoneally injected cerium chloride (CeCl 3 , 20 mg/kg BW) along with Curcuma longa extract, administrated by gavage (100 mg/kg BW), into mice for 60 days. We then examined mouse behavior, brain tissue damage, and brain oxidative stress parameters. Our results revealed a significant modification in the behavior of the CeCl 3 -treated mice. In addition, CeCl 3 induced a significant increment in lipid peroxidation, carbonyl protein (PCO), and advanced oxidation protein product levels, as well as a significant reduction in superoxide dismutase (SOD) and glutathione peroxidase (GPx) activities. Acetylcholinesterase (AChE) activity remarkably increased in the brain of CeCl 3 -treated mice. Histopathological observations confirmed these results. Curcuma longa attenuated CeCl 3 -induced oxidative stress and increased the activities of antioxidant enzymes. It also decreased AChE activity in the CeCl 3 -damaged mouse brain that was confirmed by histopathology. In conclusion, this study suggests that Curcuma longa has a neuroprotective effect against CeCl 3 -induced damage in the brain.

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.

Spectroscopic Study of Local Interactions of Platinum in Small [CexOy]Ptx' - Clusters

NASA Astrophysics Data System (ADS)

Ray, Manisha; Kafader, Jared O.; Chick Jarrold, Caroline

2016-06-01

Cerium oxide is a good ionic conductor, and the conductivity can be enhanced with oxygen vacancies and doping. This conductivity may play an important role in the enhancement of noble or coinage metal toward the water-gas shift reaction when supported by cerium oxide. The ceria-supported platinum catalyst in particular has received much attention because of higher activity at lower temperatures (LT) compared to the most common commercial LT-WGS catalyst. We have used a combination of anion photoelectron spectroscopy and density functional theory calculations to study the interesting molecular and electronic structures and properties of cluster models of ceria-supported platinum. [CexOy]Ptx' - (x,x'=1,2 ; y≤2x') clusters exhibit evidence of ionic bonding possible because of the high electron affinity of Pt and the low ionization potential of cerium oxide clusters. In addition, Pt- is a common daughter ion resulting from photodissociation of [CexOy]Ptx' - clusters. Finally, several of the anion and neutral clusters have profoundly different structures. These features may play a role in the enhancement of catalytic activity toward the water-gas shift reaction.

Effect of the Cerium Oxide (CeO2) on the Structural and Electrochemical Properties of the LaNi5Ce Metal Hydride Anode

NASA Astrophysics Data System (ADS)

Utami Hapsari, Ade; Zulfia, Anne; Raharjo, Jarot; Agustanhakri

2017-07-01

One of negative electrode, AB5-type alloy electrodes, have been extensively studied and applied in rechargeable Ni-MH batteries due to their excellent electrochemical characteristics. Some researchers have found that addition of rare earth oxides (La, Ce, Pr, Er, Tm, Yb) to AB5-type alloy (MH) electrode improves battery performance significantly. Cerium Oxide (CeO2) is a light rare earth oxide is widely obtained from the processing of tailings in mining activities. During this time, there is still little data for research applications of cerium oxide for electrode materials. In this paper, the effects of adding CeO2 on the performance metal hydride electrode were investigated. In order to study the effects of CeO2 on the performance of anode material, 1%, 2%, and 3% of weight ratio CeO2 was mixed to LaNi5 as an negative electrode. The powder mixtures were mechanically milled at a speed of rpm 240 for 2 hours using ball mill. The powder mixtures were characterized by X-Ray Diffraction (XRD) and Scanning Electron Microscope (SEM). Electrochemical characteristics were measured using electrochemical impedance spectroscopy (EIS). The powder mixing showed the presence of Ce atom substitution into LaNi5 structures that affect the electrochemical properties of the material. The addition of cerium oxide at LaNi5 increase of the value of impedance. However, the addition of the value of impedance at 1% CeO2 is not significant when compared with the addition of 2% and 3% CeO2 that actually make the electrochemical properties of LaNi5 worst. Although the addition of 1% CeO2 also slightly increases the impedance value of LaNi5, but the addition of 1% CeO2 showed increase the corrosion resistance than without the addition of CeO2 and the addition of 2% and 3% CeO2.

Atomic layer deposition of cerium oxide for potential use in diesel soot combustion

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

Ivanova, Tatiana V., E-mail: tatiana.ivanova@lut.fi, E-mail: ivanova.tatyana.v@gmail.com; Toivonen, Jenni; Maydannik, Philipp S.

The particulate soot emission from diesel motors has a severe impact on the environment and people's health. The use of catalytic convertors is one of the ways to minimize the emission and decrease the hazard level. In this paper, the activity of cerium oxide for catalytic combustion of diesel soot was studied. Thin films of cerium dioxide were synthesized by atomic layer deposition using tetrakis(2,2,6,6-tetramethyl-3,5-heptanedionato)cerium [Ce(thd){sub 4}] and ozone as precursors. The characteristics of the films were studied as a function of deposition conditions within the reaction temperature range of 180–350 °C. Thickness, crystallinity, elemental composition, and morphology of the CeO{submore » 2} films deposited on Si (100) were characterized by ellipsometry, x-ray diffraction, x-ray photoelectron spectroscopy, atomic force microscopy, and field emission scanning electron microscopy, respectively. The growth rate of CeO{sub 2} was observed to be 0.30 Å/cycle at temperatures up to 250 °C with a slight increase to 0.37 Å/cycle at 300 °C. The effect of CeO{sub 2} films grown on stainless steel foil supports on soot combustion was measured with annealing tests. Based on the analysis of these, in catalytic applications, CeO{sub 2} has been shown to be effective in lowering the soot combustion temperature from 600 °C for the uncoated substrates to 370 °C for the CeO{sub 2} coated ones. It was found that the higher deposition temperatures had a positive effect on the catalyst performance.« less

Cerium-based metal organic frameworks with UiO-66 architecture: synthesis, properties and redox catalytic activity.

PubMed

Lammert, Martin; Wharmby, Michael T; Smolders, Simon; Bueken, Bart; Lieb, Alexandra; Lomachenko, Kirill A; Vos, Dirk De; Stock, Norbert

2015-08-14

A series of nine Ce(iv)-based metal organic frameworks with the UiO-66 structure containing linker molecules of different sizes and functionalities were obtained under mild synthesis conditions and short reaction times. Thermal and chemical stabilities were determined and a Ce-UiO-66-BDC/TEMPO system was successfully employed for the aerobic oxidation of benzyl alcohol.

Development studies for a novel wet oxidation process

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

Dhooge, P.M.; Hakim, L.B.

1994-01-01

A catalytic wet oxidation process (DETOX), which uses an acidic iron solution to oxidize organic compounds to carbon dioxide, water, and other simple products, was investigated as a potential method for the treatment of multicomponent hazardous and mixed wastes. The organic compounds picric acid, poly(vinyl chloride), tetrachlorothiophene, pentachloropyridine, Aroclor 1260 (a polychlorinated biphenyl), and hexachlorobenzene were oxidized in 125 ml reaction vessels. The metals arsenic, barium, beryllium, cadmium, cerium (as a surrogate for plutonium), chromium, lead, mercury, neodymium (as a surrogate for uranium), nickel, and vanadium were tested in the DETOX solution. Barium, beryllium, cerium, chromium, mercury, neodymium, nickel, andmore » vanadium were all found to be very soluble (>100 g/l) in the DETOX chloride-based solution. Arsenic, barium, cadmium, and lead solubilities were lower. Lead could be selectively precipitated from the DETOX solution. Chromium(VI) was reduced to relatively non-toxic chromium(III) by the solution. Six soils were contaminated with arsenic, barium, beryllium, chromium, lead, and neodymium oxides at approximately 0.1% by weight, and benzene, trichloroethene, mineral oil, and Aroclor 1260 at approximately 5% by weight total, and 5.g amounts treated with the DETOX solution in unstirred 125. ml reaction bombs. It is felt that soil treatment in a properly designed system is entirely possible despite incomplete oxidation of the less volatile organic materials in these unstirred tests.« less

Development and Validation of New Spectrophotometric Methods to Determine Enrofloxacin in Pharmaceuticals

NASA Astrophysics Data System (ADS)

Rajendraprasad, N.; Basavaiah, K.

2015-07-01

Four spectrophotometric methods, based on oxidation with cerium(IV), are investigated and developed to determine EFX in pure form and in dosage forms. The frst and second methods (Method A and method B) are direct, in which after the oxidation of EFX with cerium(IV) in acid medium, the absorbance of reduced and unreacted oxidant is measured at 275 and 320 nm, respectively. In the third (C) and fourth (D) methods after the reaction between EFX and oxidant is ensured to be completed the surplus oxidant is treated with either N-phenylanthranilic acid (NPA) or Alizarin Red S (ARS) dye and the absorbance of the oxidized NPA or ARS is measured at 440 or 420 nm. The methods showed good linearity over the concentration ranges of 0.5-5.0, 1.25-12.5, 10.0-100.0, and 6.0-60.0 μg/ml, for method A, B, C and D, respectively, with apparent molar absorptivity values of 4.42 × 10 4 , 8.7 × 10 3 , 9.31 × 10 2 , and 2.28 × 10 3 l/(mol· cm). The limits of detection (LOD), quantification (LOQ), and Sandell's sensitivity values and other validation results have also been reported. The proposed methods are successfully applied to determine EFX in pure form and in dosage forms.

UV-vis spectroscopic studies of CaF2 photo-thermo-refractive glass

NASA Astrophysics Data System (ADS)

Stoica, Martina; Herrmann, Andreas; Hein, Joachim; Rüssel, Christian

2016-12-01

A photo-thermo-refractive glass based on the system Na2O/K2O/CaO/CaF2/Al2O3/ZnO/SiO2 doped with Ag2O, CeO2, SnO2, Sb2O3 and KBr was investigated. This glass undergoes a permanent refractive index change after UV irradiation and subsequent two step heat treatment at temperatures above Tg. This is due to the formation of Ag metal clusters which act as nucleation centers for CaF2 crystallization. Oxidation of Ce3+ by UV light is the initial reaction and acts as photosensitizer in the glass. The UV-vis absorption spectra during this photo-induced crystallization process were measured. The spectral components that form the absorption spectra of cerium were studied in detail by a band separation with Gaussian functions. Deconvolution of the cerium absorption bands shows an envelope of five spectral components for the trivalent cerium due to the 4f-5d transitions and two spectral components for the tetravalent cerium caused by charge transfer transitions. The effect of different dopants and melting conditions on the photo-thermal process were studied to investigate the influence of glass technology on the photoprocess.

Metal Oxide Nanoparticles: The Importance of Size, Shape, Chemical Composition, and Valence State in Determining Toxicity

NASA Astrophysics Data System (ADS)

Dunnick, Katherine

Nanoparticles, which are defined as a structure with at least one dimension between 1 and 100 nm, have the potential to be used in a variety of consumer products due to their improved functionality compared to similar particles of larger size. Their small size is associated with increased strength, improved catalytic properties, and increased reactivity; however, their size is also associated with increased toxicity in vitro and in vivo. Numerous toxicological studies have been conducted to determine the properties of nanomaterials that increase their toxicity in order to manufacture new nanomaterials with decreased toxicity. Data indicates that size, shape, chemical composition, and valence state of nanomaterials can dramatically alter their toxicity profile. Therefore, the purpose of this dissertation was to determine how altering the shape, size, and chemical composition of various metal oxide nanoparticles would affect their toxicity. Metal oxides are used in variety of consumer products, from spray-sun screens, to food coloring agents; thus, understanding the toxicity of metal oxides and determining which aspects affect their toxicity may provide safe alternatives nanomaterials for continued use in manufacturing. Tungstate nanoparticles toxicity was assessed in an in vitro model using RAW 264.7 cells. The size, shape, and chemical composition of these nanomaterials were altered and the effect on reactive oxygen species and general cytotoxicity was determined using a variety of techniques. Results demonstrate that shape was important in reactive oxygen species production as wires were able to induce significant reactive oxygen species compared to spheres. Shape, size, and chemical composition did not have much effect on the overall toxicity of these nanoparticles in RAW 264.7 cells over a 72 hour time course, implicating that the base material of the nanoparticles was not toxic in these cells. To further assess how chemical composition can affect toxicity, cerium oxide nanoparticles were chemically modified using a process known as doping, to alter their valence state. The size and shape of the cerium oxide nanoparticles remained constant. Overall, results indicated that cerium oxide was not toxic in both RLE-6TN and NR8383 pulmonary rat cells, however, chemically modifying the valence state of the nanomaterial did affect the antioxidant potential. To determine if this trend was measureable in vivo, rats were exposed to various cerium oxide nanoparticles via intratracheal instillation and damage, changes in pulmonary cell differentials, and phagocytic cell activity were assessed. Results implicate that chemically modifying the nanoparticles had an effect on the overall damage induced by the material but did not dramatically affect inflammatory potential or phagocytic cell activity. Overall the data from these studies imply that size, shape, chemical composition, and valence state of nanomaterials can be manipulated to alter their toxicity.

Redox-active cerium oxide nanoparticles protect human dermal fibroblasts from PQ-induced damage.

PubMed

von Montfort, Claudia; Alili, Lirija; Teuber-Hanselmann, Sarah; Brenneisen, Peter

2015-01-01

Recently, it has been published that cerium (Ce) oxide nanoparticles (CNP; nanoceria) are able to downregulate tumor invasion in cancer cell lines. Redox-active CNP exhibit both selective pro-oxidative and antioxidative properties, the first being responsible for impairment of tumor growth and invasion. A non-toxic and even protective effect of CNP in human dermal fibroblasts (HDF) has already been observed. However, the effect on important parameters such as cell death, proliferation and redox state of the cells needs further clarification. Here, we present that nanoceria prevent HDF from reactive oxygen species (ROS)-induced cell death and stimulate proliferation due to the antioxidative property of these particles. Copyright © 2014 The Authors. Published by Elsevier B.V. All rights reserved.

High-strength, creep-resistant molybdenum alloy and process for producing the same

DOEpatents

Bianco, R.; Buckman, R.W. Jr.; Geller, C.B.

1999-02-09

A wet-doping process for producing an oxide-dispersion strengthened (ODS), creep-resistant molybdenum alloy is disclosed. The alloy is made by adding nitrate or acetate salts of lanthanum, cerium, thorium, or yttrium to molybdenum oxide to produce a slurry, heating the slurry in a hydrogen atmosphere to produce a powder, mixing and cold isostatically pressing the powder, sintering in a hydrogen atmosphere, and thermomechanically processing (swaging, extruding, cold drawing) the product. The ODS molybdenum alloy produced by the process contains 2--4% by volume (ca. 1--4% by weight) of an oxide of lanthanum, cerium, thorium, or yttrium. The alloy has high strength and improved creep-resistance at temperatures greater than 0.55T{sub m} of molybdenum. 10 figs.

High-strength, creep-resistant molybdenum alloy and process for producing the same

DOEpatents

Bianco, Robert; Buckman, Jr., R. William; Geller, Clint B.

1999-01-01

A wet-doping process for producing an oxide-dispersion strengthened (ODS), creep-resistant molybdenum alloy is disclosed. The alloy is made by adding nitrate or acetate salts of lanthanum, cerium, thorium, or yttrium to molybdenum oxide to produce a slurry, heating the slurry in a hydrogen atmosphere to produce a powder, mixing and cold isostatically pressing the powder, sintering in a hydrogen atmosphere, and thermomechanically processing (swaging, extruding, cold drawing) the product. The ODS molybdenum alloy produced by the process contains 2-4% by volume (.about.1-4% by weight) of an oxide of lanthanum, cerium, thorium, or yttrium. The alloy has high strength and improved creep-resistance at temperatures greater than 0.55T.sub.m of molybdenum.

Effects of Cerium Oxide Nanoparticles on the Growth of Keratinocytes, Fibroblasts and Vascular Endothelial Cells in Cutaneous Wound Healing

PubMed Central

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

2012-01-01

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. PMID:23266256

Investigation of the Ligand-Nanoparticle Interface: A Cryogenic Approach for Preserving Surface Chemistry

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

Karakoti, Ajay S.; Yang, Ping; Wang, Weina

2018-02-15

Ligand functionalized nanoparticles have replaced bare nanoparticles from most biological applications. These applications require tight control over size and stability of nanoparticles in aqueous medium. Understanding the mechanism of interaction of nanoparticle surfaces with functional groups of different organic ligands such as carboxylic acids is confounding despite the two decades of research on nanoparticles because of the inability to characterize their surfaces in their immediate environment. Often the surface interaction is understood by correlating the information available, in a piecemeal approach, from surface sensitive spectroscopic information of ligands and the bulk and surface information of nanoparticles. In present study wemore » report the direct interaction of 5-7 nm cerium oxide nanoparticles surface with acetic acid. In-situ XPS study was carried out by freezing the aqueous solution of nanoparticles to liquid nitrogen temperatures. Analysis of data collected concurrently from the ligands as well as functionalized frozen cerium oxide nanoparticles show that the acetic acid binds to the ceria surface in both dissociated and molecular state with equal population over the surface. The cerium oxide surface was populated predominantly with Ce4+ ions consistent with the thermal hydrolysis synthesis. DFT calculations reveal that the acetate ions bind more strongly to the cerium oxide nanoparticles as compared to the water and can replace the hydration sphere of nanoparticles resulting in high acetate/acetic surface coverage. These findings reveal molecular level interaction between the nanoparticle surfaces and ligands giving a better understanding of how materials behave in their immediate aqueous environment. This study also proposes a simple and elegant methodology to directly study the surface functional groups attached to nanoparticles in their immediate aqueous environment.« less

Investigation of the Ligand–Nanoparticle Interface: A Cryogenic Approach for Preserving Surface Chemistry

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

Karakoti, Ajay S.; Yang, Ping; Wang, Weina

Ligand functionalized nanoparticles have replaced bare nanoparticles from most biological applications. These applications require tight control over size and stability of nanoparticles in aqueous medium. Understanding the mechanism of interaction of nanoparticle surfaces with functional groups of different organic ligands such as carboxylic acids is confounding despite the two decades of research on nanoparticles because of the inability to characterize their surfaces in their immediate environment. Often the surface interaction is understood by correlating the information available, in a piecemeal approach, from surface sensitive spectroscopic information of ligands and the bulk and surface information of nanoparticles. In present study wemore » report the direct interaction of 5-7 nm cerium oxide nanoparticles surface with acetic acid. In-situ XPS study was carried out by freezing the aqueous solution of nanoparticles to liquid nitrogen temperatures. Analysis of data collected concurrently from the ligands as well as functionalized frozen cerium oxide nanoparticles show that the acetic acid binds to the ceria surface in both dissociated and molecular state with equal population over the surface. The cerium oxide surface was populated predominantly with Ce4+ ions consistent with the thermal hydrolysis synthesis. DFT calculations reveal that the acetate ions bind more strongly to the cerium oxide nanoparticles as compared to the water and can replace the hydration sphere of nanoparticles resulting in high acetate/acetic surface coverage. These findings reveal molecular level interaction between the nanoparticle surfaces and ligands giving a better understanding of how materials behave in their immediate aqueous environment. This study also proposes a simple and elegant methodology to directly study the surface functional groups attached to nanoparticles in their immediate aqueous environment.« less

Titanium-doped cerium oxide nanoparticles protect cells from hydrogen peroxide-induced apoptosis

PubMed Central

Clark, Andrea; Zhu, Aiping; Petty, Howard R.

2014-01-01

To develop new nanoparticle materials possessing anti-oxidative capacity with improved physical characteristics, we have studied titanium-doped cerium oxide (CeTiO2) nanoparticles. CeTiO2 nanoparticles had a mode diameter of 15-20 nm. These nanoparticles demonstrated catalase activity, and did not promote the activation of hemolytic or cytolytic pathways in living cells. Using surface plasmon resonance enhanced microscopy, we find that these nanoparticles associate with cells. Transmission electron microscopy studies demonstrated that these nanoparticles accumulate within the vacuolar compartment of cells. Importantly, CeTiO2 nanoparticles decrease hydrogen peroxide-mediated apoptosis of cells as judged by the reduced cleavage of a caspase 3-sensitive label. CeTiO2 nanoparticles may contribute to deflecting tissue damage in a broad spectrum of oxidant-mediated diseases, such as macular degeneration and Alzheimer's disease. PMID:24791147

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...

Low-temperature abatement of toluene over Mn-Ce oxides catalysts synthesized by a modified hydrothermal approach

NASA Astrophysics Data System (ADS)

Du, Jinpeng; Qu, Zhenping; Dong, Cui; Song, Lixin; Qin, Yuan; Huang, Na

2018-03-01

Mn-Ce oxides catalysts were synthesized by a novel method combining redox-precipitation and hydrothermal approach. The results indicate that the ratio between manganese and cerium plays a crucial role in the formation of catalysts, and the textual properties as well as catalytic activity are remarked affected. Mn0.6Ce0.4O2 possesses a predominant catalytic activity in the oxidation of toluene, over 70% of toluene is converted at 200 °C, and the complete conversion temperature is 210 °C. The formation of Mn-Ce solid solution markedly improves the surface area as well as pore volume of Mn-Ce oxide catalyst, and Mn0.6Ce0.4O2 possesses the largest surface area of 298.5 m2/g. The abundant Ce3+ and Mn3+ on Mn0.6Ce0.4O2 catalyst facilitate the formation of oxygen vacancies, and improve the transfer of oxygen in the catalysts. Meanwhile, it is found that cerium in Mn-Ce oxide plays a key role in the adsorption of toluene, while manganese is proved to be crucial in the oxidation of toluene, the cooperation between manganese and cerium improves the catalytic reaction process. In addition, the reaction process is investigated by in situ DRIFT measurement, and it is found that the adsorbed toluene could be oxidized to benzyl alcohol as temperature rises around 80-120 °C that can be further be oxidized to benzoic acid. Then benzoic acid could be decomposed to formate and/or carbonate species as temperature rises to form CO2 and H2O. In addition, the formed by-product phenol could be further oxidized into CO2 and H2O when the temperature is high enough.

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.

Lead-Free Sn-Ce-O Composite Coating on Cu Produced by Pulse Electrodeposition from an Aqueous Acidic Sulfate Electrolyte

NASA Astrophysics Data System (ADS)

Sharma, Ashutosh; Das, Karabi; Das, Siddhartha

2017-10-01

Pulse-electrodeposited Sn-Ce-O composite solder coatings were synthesized on a Cu substrate from an aqueous acidic solution containing stannous sulfate (SnSO4·3H2O), sulfuric acid (H2SO4), and Triton X-100 as an additive. The codeposition was achieved by adding nano-cerium oxide powder in varying concentrations from 5 g/L to 20 g/L into the electrolytic bath. Microstructural characterization was carried out using x-ray diffraction (XRD), scanning electron microscopy, and transmission electron microscopy. The XRD analysis showed that the deposits consist mainly of tetragonal β (Sn) with reduced cerium oxide species. The composite coatings thus obtained exhibit a smaller grain size, possess higher microhardness, and a lower melting point than the monolithic Sn coating. The electrical resistivity of the developed composites increases, however, but lies within the permissible limits for current lead-free solder applications. Also, an optimum balance of properties in terms of microhardness, adhesion, melting point and resistivity can be obtained with 0.9 wt.% cerium oxide in the Sn matrix, which enables potential applications in solder joints and packaging.

Alkali metal hafnium oxide scintillators

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

Bourret-Courchesne, Edith; Derenzo, Stephen E.; Taylor, Scott Edward

The present invention provides for a composition comprising an inorganic scintillator comprising an alkali metal hafnate, optionally cerium-doped, having the formula A 2HfO 3:Ce; wherein A is an alkali metal having a valence of 1, such as Li or Na; and the molar percent of cerium is 0% to 100%. The alkali metal hafnate are scintillators and produce a bright luminescence upon irradiation by a suitable radiation.

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

Environmental geochemistry of cerium: applications and toxicology of cerium oxide nanoparticles.

PubMed

Dahle, Jessica T; Arai, Yuji

2015-01-23

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.

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.

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

Campbell, Keri R.; Judge, Elizabeth J.; Barefield, James E.

We show the analysis of light water reactor simulated used nuclear fuel using laser-induced breakdown spectroscopy (LIBS) is explored using a simplified version of the main oxide phase. The main oxide phase consists of the actinides, lanthanides, and zirconium. The purpose of this study is to develop a rapid, quantitative technique for measuring zirconium in a uranium dioxide matrix without the need to dissolve the material. A second set of materials including cerium oxide is also analyzed to determine precision and limit of detection (LOD) using LIBS in a complex matrix. Two types of samples are used in this study:more » binary and ternary oxide pellets. The ternary oxide, (U,Zr,Ce)O 2 pellets used in this study are a simplified version the main oxide phase of used nuclear fuel. The binary oxides, (U,Ce)O 2 and (U,Zr)O 2 are also examined to determine spectral emission lines for Ce and Zr, potential spectral interferences with uranium and baseline LOD values for Ce and Zr in a UO 2 matrix. In the spectral range of 200 to 800 nm, 33 cerium lines and 25 zirconium lines were identified and shown to have linear correlation values (R 2) > 0.97 for both the binary and ternary oxides. The cerium LOD in the (U,Ce)O 2 matrix ranged from 0.34 to 1.08 wt% and 0.94 to 1.22 wt% in (U,Ce,Zr)O 2 for 33 of Ce emission lines. The zirconium limit of detection in the (U,Zr)O 2 matrix ranged from 0.84 to 1.15 wt% and 0.99 to 1.10 wt% in (U,Ce,Zr)O 2 for 25 Zr lines. Finally, the effect of multiple elements in the plasma and the impact on the LOD is discussed.« less

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

Marker Exchange Mutagenesis of mxaF, Encoding the Large Subunit of the Mxa Methanol Dehydrogenase, in Methylosinus trichosporium OB3b

PubMed Central

Farhan Ul Haque, Muhammad; Gu, Wenyu; DiSpirito, Alan A.

2015-01-01

Methanotrophs have remarkable redundancy in multiple steps of the central pathway of methane oxidation to carbon dioxide. For example, it has been known for over 30 years that two forms of methane monooxygenase, responsible for oxidizing methane to methanol, exist in methanotrophs, i.e., soluble methane monooxygenase (sMMO) and particulate methane monooxygenase (pMMO), and that expression of these two forms is controlled by the availability of copper. Specifically, sMMO expression occurs in the absence of copper, while pMMO expression increases with increasing copper concentrations. More recently, it was discovered that multiple forms of methanol dehydrogenase (MeDH), Mxa MeDH and Xox MeDH, also exist in methanotrophs and that the expression of these alternative forms is regulated by the availability of cerium. That is, expression of Xox MeDH increases in the presence of cerium, while Mxa MeDH expression decreases in the presence of cerium. As it had been earlier concluded that pMMO and Mxa MeDH form a supercomplex in which electrons from Mxa MeDH are back donated to pMMO to drive the initial oxidation of methane, we speculated that Mxa MeDH could be rendered inactive through marker-exchange mutagenesis but growth on methane could still be possible if cerium was added to increase the expression of Xox MeDH under sMMO-expressing conditions. Here we report that mxaF, encoding the large subunit of Mxa MeDH, could indeed be knocked out in Methylosinus trichosporium OB3b, yet growth on methane was still possible, so long as cerium was added. Interestingly, growth of this mutant occurred in both the presence and the absence of copper, suggesting that Xox MeDH can replace Mxa MeDH regardless of the form of MMO expressed. PMID:26712545

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

PubMed

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

2012-05-01

Cerium oxide (CeO(2)) nanoparticles improve the burning efficiency of fuel, however, little is known about health impacts of altered emissions from the vehicles. Atherosclerosis-prone apolipoprotein E knockout (ApoE(-/-)) mice were exposed by inhalation to diluted exhaust (1.7 mg/m(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. Addition of CeO(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. These results imply that addition of CeO(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. Copyright © 2012 Elsevier Inc. All rights reserved.

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.

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.

[Removal Characteristics of Elemental Mercury by Mn-Ce/molecular Sieve].

PubMed

Tan, Zeng-qiang; Niu, Guo-ping; Chen, Xiao-wen; An, Zhen

2015-06-01

The impregnation method was used to support molecular sieve with active manganese and cerium components to obtain a composite molecular sieve catalyst. The mercury removal performance of the catalyst was studied with a bench-scale setup. XPS analysis was used to characterize the sample before and after the modification in order to study the changes in the active components of the catalyst prepared. The results showed that the catalyst carrying manganese and cerium components had higher oxidation ability of elemental mercury in the temperature range of 300 degrees C - 450 degrees C, especially at 450 degrees C, the oxidation efficiency of elemental mercury was kept above 80%. The catalyst had more functional groups that were conducive to the oxidation of elemental mercury, and the mercury removal mainly depended on the chemical adsorption. The SO2 and NO in flue gas could inhibit the oxidation of elemental mercury to certain extent.

Electrochemical characterization of cerium-based conversion coatings on aluminum alloy 7075-T6

NASA Astrophysics Data System (ADS)

Joshi, Simon

This research used electrochemical techniques to characterize the deposition and corrosion protection behavior of cerium-based conversion coatings on Al 7075-T6. Alkaline activation decreased native oxide impedance (5.9 kO-cm2) by ˜25% promoting deposition of 250--500 nm coatings. Activation in NaOH solutions deposited coatings with large cracks and craters, whereas Na2CO3 activation resulted in uniform coatings, i.e., fewer cracks and almost no craters. Uniformly deposited coatings exhibited better cathodic inhibition and higher impedance (˜200 kO-cm 2) than on NaOH activated substrates (˜100 kO-cm 2). Subsurface crevices, caused by Cl- and H 2O2 in the deposition solution, were found under large cracks and craters. Thus, Na2CO3 activation produced fewer subsurface crevices. To reduce subsurface crevice formation, Ce(NO3) 3 and CeCl3 were used in different ratios. Coatings made using 100% Ce(NO3)3 solutions were ˜60 nm thick without subsurface crevices, but the coatings offered little corrosion protection. Despite formation of subsurface crevices, Cl- was necessary as impedance increased linearly with Cl- concentration in the deposition solution. To characterize the different non-uniform features of the coatings, microelectrochemical testing was performed and it showed three distinct regions: active, intermediate, and passive. Humidity experiments were performed to understand the effect of moisture during salt spray testing and showed an increase in coating impedance by making the exposed substrate oxide more passive. However, this passive oxide could not provide corrosion resistance in a chloride environment. Dissolution studies showed that cerium migration was only possible at pH ≤2. Overall, deposition of uniform 250--500 nm thick outings was essential to make it an effective barrier to Cl - attach and prevent subsurface crevices on Al 7075-T6.

Corrosion protection properties and interfacial adhesion mechanism of an epoxy/polyamide coating applied on the steel surface decorated with cerium oxide nanofilm: Complementary experimental, molecular dynamics (MD) and first principle quantum mechanics (QM) simulation methods

NASA Astrophysics Data System (ADS)

Bahlakeh, Ghasem; Ramezanzadeh, Bahram; Saeb, Mohammad Reza; Terryn, Herman; Ghaffari, Mehdi

2017-10-01

The effect of cerium oxide treatment on the corrosion protection properties and interfacial interaction of steel/epoxy was studied by electrochemical impedance spectroscopy, (EIS) classical molecular dynamics (MD) and first principle quantum mechanics (QM) simulation methods X-ray photoelectron spectroscopy (XPS) was used to verify the chemical composition of the Ce film deposited on the steel. To probe the role of the curing agent in epoxy adsorption, computations were compared for an epoxy, aminoamide and aminoamide modified epoxy. Moreover, to study the influence of water on interfacial interactions the MD simulations were executed for poly (aminoamide)-cured epoxy resin in contact with the different crystallographic cerium dioxide (ceria, CeO2) surfaces including (100), (110), and (111) in the presence of water molecules. It was found that aminoamide-cured epoxy material was strongly adhered to all types of CeO2 substrates, so that binding to ceria surfaces followed the decreasing order CeO2 (111) > CeO2 (100) > CeO2 (110) in both dry and wet environments. Calculation of interaction energies noticed an enhanced adhesion to metal surface due to aminoamide curing of epoxy resin; where facets (100) and (111) revealed electrostatic and Lewis acid-base interactions, while an additional hydrogen bonding interaction was identified for CeO2 (110). Overall, MD simulations suggested decrement of adhesion to CeO2 in wet environment compared to dry conditions. Additionally, contact angle, pull-off test, cathodic delamination and salt spray analyses were used to confirm the simulation results. The experimental results in line with modeling results revealed that Ce layer deposited on steel enhanced substrate surface free energy, work of adhesion, and interfacial adhesion strength of the epoxy coating. Furthermore, decrement of adhesion of epoxy to CeO2 in presence of water was affirmed by experimental results. EIS results revealed remarkable enhancement of the corrosion resistance of epoxy coating applied on the steel specimens treated by cerium oxide.

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.

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.

Zirconia-molybdenum disilicide composites

DOEpatents

Petrovic, John J.; Honnell, Richard E.

1991-01-01

Compositions of matter comprised of molybdenum disilicide and zirconium oxide in one of three forms: pure, partially stabilized, or fully stabilized and methods of making the compositions. The stabilized zirconia is crystallographically stabilized by mixing it with yttrium oxide, calcium oxide, cerium oxide, or magnesium oxide and it may be partially stabilized or fully stabilized depending on the amount of stabilizing agent in the mixture.

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

DOEpatents

Willigan, Rhonda R [Manchester, CT; Vanderspurt, Thomas Henry [Glastonbury, CT; Tulyani, Sonia [Manchester, CT; Radhakrishnan, Rakesh [Vernon, CT; Opalka, Susanne Marie [Glastonbury, CT; Emerson, Sean C [Broad Brook, CT

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.

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.

Balancing surface adsorption and diffusion of lithium-polysulfides on nonconductive oxides for lithium–sulfur battery design

DOE PAGES

Tao, Xinyong; Wang, Jianguo; Liu, Chong; ...

2016-04-05

Lithium–sulfur batteries have attracted attention due to their six-fold specific energy compared with conventional lithium-ion batteries. Dissolution of lithium polysulfides, volume expansion of sulfur and uncontrollable deposition of lithium sulfide are three of the main challenges for this technology. State-of-the-art sulfur cathodes based on metal-oxide nanostructures can suppress the shuttle-effect and enable controlled lithium sulfide deposition. However, a clear mechanistic understanding and corresponding selection criteria for the oxides are still lacking. Herein, various nonconductive metal-oxide nanoparticle-decorated carbon flakes are synthesized via a facile biotemplating method. The cathodes based on magnesium oxide, cerium oxide and lanthanum oxide show enhanced cycling performance.more » Adsorption experiments and theoretical calculations reveal that polysulfide capture by the oxides is via monolayered chemisorption. Moreover, we show that better surface diffusion leads to higher deposition efficiency of sulfide species on electrodes. Lastly, oxide selection is proposed to balance optimization between sulfide-adsorption and diffusion on the oxides.« less

Balancing surface adsorption and diffusion of lithium-polysulfides on nonconductive oxides for lithium-sulfur battery design

NASA Astrophysics Data System (ADS)

Tao, Xinyong; Wang, Jianguo; Liu, Chong; Wang, Haotian; Yao, Hongbin; Zheng, Guangyuan; Seh, Zhi Wei; Cai, Qiuxia; Li, Weiyang; Zhou, Guangmin; Zu, Chenxi; Cui, Yi

2016-04-01

Lithium-sulfur batteries have attracted attention due to their six-fold specific energy compared with conventional lithium-ion batteries. Dissolution of lithium polysulfides, volume expansion of sulfur and uncontrollable deposition of lithium sulfide are three of the main challenges for this technology. State-of-the-art sulfur cathodes based on metal-oxide nanostructures can suppress the shuttle-effect and enable controlled lithium sulfide deposition. However, a clear mechanistic understanding and corresponding selection criteria for the oxides are still lacking. Herein, various nonconductive metal-oxide nanoparticle-decorated carbon flakes are synthesized via a facile biotemplating method. The cathodes based on magnesium oxide, cerium oxide and lanthanum oxide show enhanced cycling performance. Adsorption experiments and theoretical calculations reveal that polysulfide capture by the oxides is via monolayered chemisorption. Moreover, we show that better surface diffusion leads to higher deposition efficiency of sulfide species on electrodes. Hence, oxide selection is proposed to balance optimization between sulfide-adsorption and diffusion on the oxides.

Balancing surface adsorption and diffusion of lithium-polysulfides on nonconductive oxides for lithium-sulfur battery design.

PubMed

Tao, Xinyong; Wang, Jianguo; Liu, Chong; Wang, Haotian; Yao, Hongbin; Zheng, Guangyuan; Seh, Zhi Wei; Cai, Qiuxia; Li, Weiyang; Zhou, Guangmin; Zu, Chenxi; Cui, Yi

2016-04-05

Lithium-sulfur batteries have attracted attention due to their six-fold specific energy compared with conventional lithium-ion batteries. Dissolution of lithium polysulfides, volume expansion of sulfur and uncontrollable deposition of lithium sulfide are three of the main challenges for this technology. State-of-the-art sulfur cathodes based on metal-oxide nanostructures can suppress the shuttle-effect and enable controlled lithium sulfide deposition. However, a clear mechanistic understanding and corresponding selection criteria for the oxides are still lacking. Herein, various nonconductive metal-oxide nanoparticle-decorated carbon flakes are synthesized via a facile biotemplating method. The cathodes based on magnesium oxide, cerium oxide and lanthanum oxide show enhanced cycling performance. Adsorption experiments and theoretical calculations reveal that polysulfide capture by the oxides is via monolayered chemisorption. Moreover, we show that better surface diffusion leads to higher deposition efficiency of sulfide species on electrodes. Hence, oxide selection is proposed to balance optimization between sulfide-adsorption and diffusion on the oxides.

Balancing surface adsorption and diffusion of lithium-polysulfides on nonconductive oxides for lithium–sulfur battery design

PubMed Central

Tao, Xinyong; Wang, Jianguo; Liu, Chong; Wang, Haotian; Yao, Hongbin; Zheng, Guangyuan; Seh, Zhi Wei; Cai, Qiuxia; Li, Weiyang; Zhou, Guangmin; Zu, Chenxi; Cui, Yi

2016-01-01

Lithium–sulfur batteries have attracted attention due to their six-fold specific energy compared with conventional lithium-ion batteries. Dissolution of lithium polysulfides, volume expansion of sulfur and uncontrollable deposition of lithium sulfide are three of the main challenges for this technology. State-of-the-art sulfur cathodes based on metal-oxide nanostructures can suppress the shuttle-effect and enable controlled lithium sulfide deposition. However, a clear mechanistic understanding and corresponding selection criteria for the oxides are still lacking. Herein, various nonconductive metal-oxide nanoparticle-decorated carbon flakes are synthesized via a facile biotemplating method. The cathodes based on magnesium oxide, cerium oxide and lanthanum oxide show enhanced cycling performance. Adsorption experiments and theoretical calculations reveal that polysulfide capture by the oxides is via monolayered chemisorption. Moreover, we show that better surface diffusion leads to higher deposition efficiency of sulfide species on electrodes. Hence, oxide selection is proposed to balance optimization between sulfide-adsorption and diffusion on the oxides. PMID:27046216

Scandia-Stabilized Zirconia Coating for Composites.

DTIC Science & Technology

1990-04-03

are present as oxides, acids and as in U.S. Pat. No. 4,328,285, describes some of the prior free sulfur . art attempts to coat engine parts with ceramic...base Because vanadium pentoxide (V205 ) is an acidic ox- materials, and Siemers teaches using cerium oxide or ide, it reacts with Na2O (a highly...surfaces exposed to vanadium and compounds decreases with the V2Os/Na2O ratio from sulfur compound corrosion. Na2V 120 31 (most acidic ) to Na3VO4(least

Adsorption of cadmium on cerium oxide nanoparticles and oyster shells

NASA Astrophysics Data System (ADS)

Ji, Yongbo; Liu, Zhuomiao; Dang, Yonghui; Xu, Lina; Ning, Fangyuan; Xue, Yinhao; Wei, Yongpeng; Dai, Yanhui

2018-03-01

This study investigated the adsorption of cadmium (Cd(II)) by cerium oxide nanoparticles (CeO2 NPs) and oyster shells in seawater. The results showed that the addition of Cd(II) significantly inhibited the agglomeration of CeO2 NPs both in DI water and seawater, increased the positive charges of CeO2 NPs in DI water and neutralized the negative charges of CeO2 NPs in seawater. Additionally, CeO2 NPs could adsorb Cd and the bioavailability of Cd was reduced in the presence of oyster shells. This study demonstrated that the adsorption of metals on shells should not be neglected for the accumulation of metals by shellfish.

Titanium-doped cerium oxide nanoparticles protect cells from hydrogen peroxide-induced apoptosis

NASA Astrophysics Data System (ADS)

Clark, Andrea; Zhu, Aiping; Petty, Howard R.

2013-12-01

To develop new nanoparticle materials possessing antioxidative capacity with improved physical characteristics, we have studied titanium-doped cerium oxide (CeTiO2) nanoparticles. CeTiO2 nanoparticles had mode diameters in the range of 15-20 nm. These nanoparticles demonstrated catalase activity, and did not promote the activation of hemolytic or cytolytic pathways in living cells. Using surface plasmon resonance-enhanced microscopy, we find that these nanoparticles associate with cells. Transmission electron microscopy studies demonstrated that these nanoparticles accumulate within the vacuolar compartment of cells. Importantly, CeTiO2 nanoparticles decrease hydrogen peroxide-mediated apoptosis of cells as judged by the reduced cleavage of a caspase 3-sensitive label. CeTiO2 nanoparticles may contribute to deflecting tissue damage in a broad spectrum of oxidant-mediated diseases, such as macular degeneration and Alzheimer's disease.

Zinc-doped cerium oxide nanoparticles: Sol-gel synthesis, characterization, and investigation of their in vitro cytotoxicity effects

NASA Astrophysics Data System (ADS)

Akbari, Alireza; Khammar, Mansoureh; Taherzadeh, Danial; Rajabian, Arezoo; Khorsand Zak, Ali; Darroudi, Majid

2017-12-01

Zinc-doped cerium oxide nanoparticles (Zn-doped CeO2-NPs) with Ce1-xZnxO2 composition, where x equals to 0.0, 0.01, 0.03, and 0.05 are synthesized through a green based sol-gel method from nitrate precursors and gelatin at the fixed calcination temperature of 600 °C maintained for 2 h. The powder X-ray diffraction (PXRD) patterns displayed the single-crystalline structure of these particular samples, which seemed to be completely indexed with the cubic fluorite phase. The evolution of crystalline phases in Ce1-xZnxO2 are assured by the observed broadening in PXRD peaks, while the field emission scanning electron microscopy (FE-SEM) images revealed that the spherical-shaped single-crystalline NPs do exist and confirmed the size estimations that were obtained from the Scherrer's equation. A dose dependent toxicity with non-toxic effects of concentrations up to 31.25 μg/ml is illustrated through the In vitro cytotoxicity studies regarding Neuro2A cells.

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

Use of boiled hexamethylenetetramine and urea to increase the porosity of cerium dioxide microspheres formed in the internal gelation process

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

Hunt, R. D.; Collins, J. L.; Cowell, B. S.

Cerium dioxide (CeO 2) is a commonly used simulant for plutonium dioxide and for plutonium (Pu) in a mixed uranium (U) and Pu oxide [(U, Pu)O 2] in nuclear fuel development. This effort developed CeO 2 microspheres with different porosities and diameters for use in a crush-strength study. The internal gelation technique has produced CeO 2 microspheres with limited initial porosity. When an equal molar solution of urea and hexamethylenetetramine (HMTA) is gently boiling for 1 hr and used in the gelation process, the crystallite size and porosity of mixed U and thorium oxide microspheres and the (U, Pu)O 2more » microspheres increased significantly. In this study with cerium, the combination of ammonium cerium nitrate and 1-h boiled HMTA-urea failed to produce a stable feed broth. However, when the 1-h heated HMTA-urea was combined with unheated HMTA-urea in 1 to 3 volume ratio or the boiling time of the HMTA-urea was reduced to 15-20 min, a stable solution of HMTA, urea, and Ce was formed at 273 K. This new Ce solution produced CeO 2 microspheres with much higher initial porosities. Intermediate porosities were possible when the heated HMTA/urea was aged prior to use.« less

Use of boiled hexamethylenetetramine and urea to increase the porosity of cerium dioxide microspheres formed in the internal gelation process

DOE PAGES

Hunt, R. D.; Collins, J. L.; Cowell, B. S.

2017-05-13

Cerium dioxide (CeO 2) is a commonly used simulant for plutonium dioxide and for plutonium (Pu) in a mixed uranium (U) and Pu oxide [(U, Pu)O 2] in nuclear fuel development. This effort developed CeO 2 microspheres with different porosities and diameters for use in a crush-strength study. The internal gelation technique has produced CeO 2 microspheres with limited initial porosity. When an equal molar solution of urea and hexamethylenetetramine (HMTA) is gently boiling for 1 hr and used in the gelation process, the crystallite size and porosity of mixed U and thorium oxide microspheres and the (U, Pu)O 2more » microspheres increased significantly. In this study with cerium, the combination of ammonium cerium nitrate and 1-h boiled HMTA-urea failed to produce a stable feed broth. However, when the 1-h heated HMTA-urea was combined with unheated HMTA-urea in 1 to 3 volume ratio or the boiling time of the HMTA-urea was reduced to 15-20 min, a stable solution of HMTA, urea, and Ce was formed at 273 K. This new Ce solution produced CeO 2 microspheres with much higher initial porosities. Intermediate porosities were possible when the heated HMTA/urea was aged prior to use.« less

Surface-charge-dependent cell localization and cytotoxicity of cerium oxide nanoparticles.

PubMed

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

2010-09-28

Cerium oxide nanoparticles (nanoceria) have shown great potential as antioxidant and radioprotective agents for applications in cancer therapy. Recently, various polymer-coated nanoceria preparations have been developed to improve their aqueous solubility and allow for surface functionalization of these nanoparticles. However, the interaction of polymer-coated nanoceria with cells, their uptake mechanism, and subcellular localization are poorly understood. Herein, we engineered polymer-coated cerium oxide nanoparticles with different surface charges (positive, negative, and neutral) and studied their internalization and toxicity in normal and cancer cell lines. The results showed that nanoceria with a positive or neutral charge enters most of the cell lines studied, while nanoceria with a negative charge internalizes mostly in the cancer cell lines. Moreover, upon entry into the cells, nanoceria is localized to different cell compartments (e.g., cytoplasm and lysosomes) depending on the nanoparticle's surface charge. The internalization and subcellular localization of nanoceria plays a key role in the nanoparticles' cytotoxicity profile, exhibiting significant toxicity when they localize in the lysosomes of the cancer cells. In contrast, minimal toxicity is observed when they localize into the cytoplasm or do not enter the cells. Taken together, these results indicate that the differential surface-charge-dependent localization of nanoceria in normal and cancer cells plays a critical role in the nanoparticles' toxicity profile.

The Role of Dextran Coatings on the Cytotoxicity Properties of Ceria Nanoparticles Toward Bone Cancer Cells

NASA Astrophysics Data System (ADS)

Yazici, Hilal; Alpaslan, Ece; Webster, Thomas J.

2015-04-01

Cerium oxide nanoparticles have demonstrated great potential as antioxidant and radioprotective agents for nanomedicine applications especially for cancer therapy. The surface chemistry of nanoparticles is an important property that has a significant effect on their performance in biological applications including cancer diagnosis, cancer treatment, and bacterial infection. Recently, various nanosized cerium oxide particles with different types of polymer coatings have been developed to improve aqueous solubility and allow for surface functionalization for distinct applications. In this study, the role of ceria nanoparticles coated with dextran on the cytotoxicity properties of bone cancer cells was shown. Specifically, 0.1 M and 0.01 M dextran-coated, <5-nm ceria nanoparticles, were synthesized. The cytotoxicity of 0.1 M and 0.01 M dextran-coated ceria nanoparticles was evaluated against osteosarcoma cells. A change in cell viability was observed when treating osteosarcoma cells with 0.1 M dextran-coated ceria nanoparticles in the 250 -1000 μg/mL concentration range. In contrast, minimal toxicity to bone cancer cells was observed for the 0.01 M dextran coating after 3 days compared with the 0.1 M dextran coating. These results indicated that surface dextran functionalization had a positive impact on the cytotoxicity of cerium oxide nanoparticles against osteosarcoma cells.

Biogeochemistry of the rare-earth elements with particular reference to hickory trees

USGS Publications Warehouse

Robinson, W.O.; Bastron, H.; Murata, K.J.

1958-01-01

Hickory trees concentrate the rare-earth elements in their leaves to a phenomenal degree and may contain as much as 2300 p.p.m. of total rare earths based on the dry weight of the leaves. The average proportions of the individual elements (atomic percent of the total rare-earth elements) in the leaves are: Y 36, La 16, Ce 14, Pr 2, Nd 20, Sm 1, Eu 0.7, Gd 3, Tb 0.6, Dy 3, Ho 0.7, Er 2, Tm 0.2, Yb 1, and Lu 0.2. The similarity in the proportions of the rare-earth elements in the leaves and in the exchange complex of the soil on which the hickory trees grow indicates that the trees do not fractionate the rare earths appreciably. The variation of the rare-earth elements in the leaves and soils can be explained generally in terms of the relative abundance of the cerium group and the yttrium group, except for the element cerium. The large fluctuations in the proportion of cerium [Ce/(La + Nd) atomic ratios of 0.16 to 0.86] correlate with oxidation-reduction conditions in the soil profile. The substitution of dilute H2SO3 for dilute HC1 in the determination of available rare-earth elements brings about a large increase in the proportion of cerium that is extracted from an oxygenated subsoil. These relationships strongly suggest that quadrivalent cerium is present in oxygenated subsoil and is less available to plants than the other rare-earth elements that do not undergo such a change in valence. A few parts per billion of rare-earth elements have been detected in two samples of ground water. ?? 1958.

Bioavailability of cerium oxide nanoparticles to Raphanus sativus L. in two soils.

PubMed

Zhang, Weilan; Musante, Craig; White, Jason C; Schwab, Paul; Wang, Qiang; Ebbs, Stephen D; Ma, Xingmao

2017-01-01

Cerium oxide nanoparticles (CeO 2 NP) are a common component of many commercial products. Due to the general concerns over the potential toxicity of engineered nanoparticles (ENPs), the phytotoxicity and in planta accumulation of CeO 2 NPs have been broadly investigated. However, most previous studies were conducted in hydroponic systems and with grain crops. For a few studies performed with soil grown plants, the impact of soil properties on the fate and transport of CeO 2 NPs was generally ignored even though numerous previous studies indicate that soil properties play a critical role in the fate and transport of environmental pollutants. The objectives of this study were to evaluate the soil fractionation and bioavailability of CeO 2 NPs to Raphanus sativus L (radish) in two soil types. Our results showed that the silty loam contained slightly higher exchangeable fraction (F1) of cerium element than did loamy sand soil, but significantly lower reducible (F2) and oxidizable (F3) fractions as CeO 2 NPs concentration increased. CeO 2 NPs associated with silicate minerals or the residue fraction (F4) dominated in both soils. The cerium concentration in radish storage root showed linear correlation with the sum of the first three fractions (r 2  = 0.98 and 0.78 for loamy sand and silty loam respectively). However, the cerium content in radish shoots only exhibited strong correlations with F1 (r 2  = 0.97 and 0.89 for loamy sand and silty loam respectively). Overall, the results demonstrated that soil properties are important factors governing the distribution of CeO 2 NPs in soil and subsequent bioavailability to plants. Copyright © 2015 Elsevier Masson SAS. All rights reserved.

One-step synthesis and characterizations of cerium oxide nanoparticles in an ambient temperature via Co-precipitation method

NASA Astrophysics Data System (ADS)

Pujar, Malatesh S.; Hunagund, Shirajahammad M.; Desai, Vani R.; Patil, Shivaprasadgouda; Sidarai, Ashok H.

2018-04-01

We report the simple Co-precipitation method for the synthesis of Cerium oxide (CeO2) nanoparticles (NPs) in an ambient temperature. We have taken the Cerium (III) nitrate hexahydrate (Ce(NO3)3.6H2O) and Sodium hydroxide (NaOH) as the precursors. The obtained NPs were analyzed using the UV-Vis spectrophotometer, Fourier transform infrared spectroscopy (FT-IR) and X-ray diffraction (XRD). The obtained results signify that UV-Vis spectrum exhibited a well-defined absorption peak at 274 nm and the estimated energy gap (Eg) is 4.05 eV. The FT-IR analysis provides the supporting evidence for the presence of bonding of O-H, nitrates, alcohols and O-Ce-O vibrations. The XRD result reveals that the synthesized CeO2 NPs was crystallite with cubic phase structure and the estimated average crystallite size of CeO2 NPs using Scherer's and W-H method was significantly different due to their assumptions. Further, it is purposed to study their photocatalytic biological activities.

Virus Removal by Biogenic Cerium

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

De Gusseme, B.; Du Laing, G; Hennebel, T

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 ofmore » 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.« less

Laser-induced breakdown spectroscopy of light water reactor simulated used nuclear fuel: Main oxide phase

DOE PAGES

Campbell, Keri R.; Judge, Elizabeth J.; Barefield, James E.; ...

2017-04-22

We show the analysis of light water reactor simulated used nuclear fuel using laser-induced breakdown spectroscopy (LIBS) is explored using a simplified version of the main oxide phase. The main oxide phase consists of the actinides, lanthanides, and zirconium. The purpose of this study is to develop a rapid, quantitative technique for measuring zirconium in a uranium dioxide matrix without the need to dissolve the material. A second set of materials including cerium oxide is also analyzed to determine precision and limit of detection (LOD) using LIBS in a complex matrix. Two types of samples are used in this study:more » binary and ternary oxide pellets. The ternary oxide, (U,Zr,Ce)O 2 pellets used in this study are a simplified version the main oxide phase of used nuclear fuel. The binary oxides, (U,Ce)O 2 and (U,Zr)O 2 are also examined to determine spectral emission lines for Ce and Zr, potential spectral interferences with uranium and baseline LOD values for Ce and Zr in a UO 2 matrix. In the spectral range of 200 to 800 nm, 33 cerium lines and 25 zirconium lines were identified and shown to have linear correlation values (R 2) > 0.97 for both the binary and ternary oxides. The cerium LOD in the (U,Ce)O 2 matrix ranged from 0.34 to 1.08 wt% and 0.94 to 1.22 wt% in (U,Ce,Zr)O 2 for 33 of Ce emission lines. The zirconium limit of detection in the (U,Zr)O 2 matrix ranged from 0.84 to 1.15 wt% and 0.99 to 1.10 wt% in (U,Ce,Zr)O 2 for 25 Zr lines. Finally, the effect of multiple elements in the plasma and the impact on the LOD is discussed.« less

Preparation and characterization of PANI@G/CWO nanocomposite for enhanced 2-nitrophenol sensing

NASA Astrophysics Data System (ADS)

Khan, Anish; Khan, Aftab Aslam Parwaz; Rahman, Mohammed M.; Asiri, Abdullah M.; Inamuddin; Alamry, Khalid A.; Hameed, Salem A.

2018-03-01

A new material by polymer insertion via graphene oxide into cerium tungstate was prepared by very simple oxidation-reduction method. Aniline polymerization was done on the surface of graphene oxide (GO) which was reduced to graphene (G) simultaneously mixed with separately prepared inorganic matrices of cerium tungstate (Ce2(WO4)3 (CWO)). PANI@G/CWO was characterized by various spectroscopic methods as SEM, FTIR, TGA, XRD and XPS to confirm its possibilities. Selective 2-nitrophenol sensor was fabricated on flat glassy carbon electrode (GCE) and PANI@G/CWO nanocomposites in the form of thin layer. It was found excellent sensitivity as well as long life spam with broad dynamic concentration range (LDR) that showed efficient electrochemical performance towards 2-nitrophenol on fabricated chemical sensor by PANI@G/CWO. The linear calibration curve (r2 = 0.9914) with wide range of 2-nitrophenol concentration (1.0 nM-1.0 mM) was found having the detection limit of 0.87 nM while the sensitivity of the sensor was around 1.229 μ A μM-1 cm-2. It was introduced a new route for the development of a versatile phenolic sensor based on PANI@G/CWO nanocomposites by I-V method that is proved more selective and sensitive for environmental toxic materials.

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.

Nanoporous cerium oxide thin film for glucose biosensor.

PubMed

Saha, Shibu; Arya, Sunil K; Singh, S P; Sreenivas, K; Malhotra, B D; Gupta, Vinay

2009-03-15

Nanoporous cerium oxide (CeO(2)) thin film deposited onto platinum (Pt) coated glass plate using pulsed laser deposition (PLD) has been utilized for immobilization of glucose oxidase (GOx). Atomic force microscopy studies reveal the formation of nanoporous surface morphology of CeO(2) thin film. Response studies carried out using differential pulsed voltammetry (DPV) and optical measurements show that the GOx/CeO(2)/Pt bio-electrode shows linearity in the range of 25-300 mg/dl of glucose concentration. The low value of Michaelis-Menten constant (1.01 mM) indicates enhanced enzyme affinity of GOx to glucose. The observed results show promising application of the nanoporous CeO(2) thin film for glucose sensing application without any surface functionalization or mediator.

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. Published by Elsevier B.V.

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 levels, reduced albumin levels, a diminished sodium-potassium ratio and decreased serum triglyceride levels. Consistent with these data, rats exposed to CeO2 nanoparticles also exhibited reductions in liver weight and dose dependent hydropic degeneration, hepatocyte enlargement, sinusoidal dilatation and the accumulation of granular material in the hepatocytes. In a follow-up study, we next examined if CeO2 deposition in the liver is characterized by increased oxidative stress and apoptosis. Our data demonstrate that increased cerium in the liver is associated with increased oxidative stress and apoptosis as assessed from hydroethidium staining, the analysis of lipid peroxidation, and TUNEL staining. In addition, increased cerium concentration in the liver was associated with an increased Bax to Bcl-2 ratio, elevated caspase-9 and elevated caspase-3 protein levels. Taken together, these data suggest that exposure to CeO 2 nanoparticles is associated with increased oxidative stress and cellular apoptosis in the lungs. It is also evident that CeO2 nanoparticles can translocate to liver and induce hepatic damage. The hepatic damage induced by CeO2 nanoparticles is associated with increased oxidative stress and apoptosis in the liver.

Nutritional quality assessment of tomato fruits after exposure to uncoated and citric acid coated cerium oxide nanoparticles, bulk cerium oxide, cerium acetate and citric acid.

PubMed

Barrios, Ana Cecilia; Medina-Velo, Illya A; Zuverza-Mena, Nubia; Dominguez, Osvaldo E; Peralta-Videa, Jose R; Gardea-Torresdey, Jorge L

2017-01-01

Little is known about the effects of surface modification on the interaction of nanoparticles (NPs) with plants. Tomato (Solanum lycopersicum L.) plants were cultivated in potting soil amended with bare and citric acid coated nanoceria (nCeO 2, nCeO 2 +CA), cerium acetate (CeAc), bulk cerium oxide (bCeO 2 ) and citric acid (CA) at 0-500 mg kg -1 . Fruits were collected year-round until the harvesting time (210 days). Results showed that nCeO 2 +CA at 62.5, 250 and 500 mg kg -1 reduced dry weight by 54, 57, and 64% and total sugar by 84, 78, and 81%. At 62.5, 125, and 500 mg kg -1 nCeO 2 +CA decreased reducing sugar by 63, 75, and 52%, respectively and at 125 mg kg -1 reduced starch by 78%, compared to control. The bCeO 2 at 250 and 500 mg kg -1 , increased reducing sugar by 67 and 58%. In addition, when compared to controls, nCeO 2 at 500 mg kg -1 reduced B (28%), Fe (78%), Mn (33%), and Ca (59%). At 125 mg kg -1 decreased Al by 24%; while nCeO 2 +CA at 125 and 500 mg kg -1 increased B by 33%. On the other hand, bCeO 2 at 62.5 mg kg -1 increased Ca (267%), but at 250 mg kg -1 reduced Cu (52%), Mn (33%), and Mg (58%). Fruit macromolecules were mainly affected by nCeO 2 +CA, while nutritional elements by nCeO 2 ; however, all Ce treatments altered, in some way, the nutritional quality of tomato fruit. To our knowledge, this is the first study comparing effects of uncoated and coated nanoceria on tomato fruit quality. Copyright © 2016 Elsevier Masson SAS. All rights reserved.

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.

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.

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.

A XAS study of the local environments of cations in (U, Ce)O 2

NASA Astrophysics Data System (ADS)

Martin, Philippe; Ripert, Michel; Petit, Thierry; Reich, Tobias; Hennig, Christoph; D'Acapito, Francesco; Hazemann, Jean Louis; Proux, Olivier

2003-01-01

Mixed oxide (MOX) fuel is usually considered as a solid solution formed by uranium and plutonium dioxides. Nevertheless, some physico-chemical properties of (U 1- y, Pu y)O 2 samples manufactured under industrial conditions showed anomalies in the domain of plutonium contents ranging between 3 and 15 at.%. Cerium is commonly used as an inactive analogue of plutonium in preliminary studies on MOX fuels. Extended X-ray Absorption Fine Structure (EXAFS) measurements performed at the European Synchrotron Radiation Facility (ESRF) at the cerium and uranium edges on (U 1- y, Ce y)O 2 samples are presented and discussed. They confirmed on an atomic scale the formation of an ideal solid solution for cerium concentrations ranging between 0 and 50 at.%.

Trapped in the coordination sphere: Nitrate ion transfer driven by the cerium(III/IV) redox couple

DOE PAGES

Ellis, Ross J.; Bera, Mrinal K.; Reinhart, Benjamin; ...

2016-11-07

Redox-driven ion transfer between phases underpins many biological and technological processes, including industrial separation of ions. Here we investigate the electrochemical transfer of nitrate anions between oil and water phases, driven by the reduction and oxidation of cerium coordination complexes in oil phases. We find that the coordination environment around the cerium cation has a pronounced impact on the overall redox potential, particularly with regard to the number of coordinated nitrate anions. Our results suggest a new fundamental mechanism for tuning ion transfer between phases; by 'trapping' the migrating ion inside the coordination sphere of a redox-active complex. Here, thismore » presents a new route for controlling anion transfer in electrochemically-driven separation applications.« less

Destruction of organic pollutants by cerium(IV) MEO process: a study on the influence of process conditions for EDTA mineralization.

PubMed

Balaji, Subramanian; Chung, Sang Joon; Matheswaran, Manickam; Vasilivich, Kokovkin Vasily; Moon, Il Shik

2008-02-11

The mediated electrochemical oxidation (MEO) process with cerium(IV) and nitric acid as the oxidizing medium was employed for the destruction of various model organic pollutants in continuous organic feeding mode. A near complete destruction was observed for all the organics studied. The effects of various experimental conditions were evaluated with respect to EDTA mineralization. The key parameters varied in the process were concentration of EDTA (67-268 mM), temperature (70, 80 and 95 degrees C), concentrations of Ce(IV) (0.7, 0.8 and 0.95 M), nitric acid (2, 3 and 4M) and duration of organic addition (30 and 120 min). Under the experimental conditions of 80 degrees C and 0.95 M Ce(IV) in 3 M nitric acid, nearly 90% destruction was achieved based on CO(2) production and 95% based on TOC analyses for all the organic compounds studied. The in situ regeneration of mediator ion by the electrochemical cell was found to be good during the organic destruction within the range of experimental conditions studied. In the case of long term organic feeding (120 min) the destruction was calculated after the CO(2) evolution attained the steady state and under this condition the destruction efficiency was found to be 85% based on CO(2) evolution.

Effect of ultrasound treatment on the morpho-structural and luminescent characteristics of cerium doped yttrium silicate phosphors

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

Muresan, L.E., E-mail: laura_muresan2003@yahoo.com; Cadis, A.I.; Perhaita, I.

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 amore » 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.« less

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. The synthesis and characterization of a new magnesium MOCVD precursor, Mg(dpm)2(TMEDA) is detailed. It is shown that the donating ligand TMEDA prevents oligomerization and subsequent volatility depression as observed in the commonly used [Mg(dpm)2]2. The superiority of Mg(dpm)2(TMEDA) as an MOCVD precursor is explicitly demonstrated by growth of epitaxial MgO thin films on single-crystal SrTiO3 substrates.

Applying the Ce-in-zircon oxygen geobarometer to diverse silicic magmatic systems

NASA Astrophysics Data System (ADS)

Claiborne, L. L.; Miller, C. F.

2012-12-01

Zircon provides information on age, temperature, and composition of the magma from which it grew. In systems such as Mount St. Helens, where zircon is not coeval with the rest of the crystal cargo, it provides the only accessible record of the extended history of the magmatic system, including cycles of intrusion, crystallization and rejuvenation beneath an active volcano (Claiborne et al., 2010). The rare earth elements, which are present in measureable quantities in zircon, provide information about the composition of the magma from which zircon grew. Unique among the generally trivalent rare earth elements, cerium can exist as either trivalent or tetravalent, depending on the oxidation state of the magma. The tetravalent ion is highly compatible in zircon, in the site that usually hosts tetravalent zirconium, and so the amount of Cerium in zircon relative (relative to what would be expected of trivalent Ce) depends the oxidation state of the magma from which it grew. Trail et al. (2011) proposed a calibration based on experimental data that uses the Ce anomaly in zircon as a direct proxy for magma oxidation (fugacity), describing the relationship between Ce in zircon and magma oxygen fugacity as ln(Ce/Ce*)D = (0.1156±0.0050)xln(fO2)+(13860±708)/T-(6.125±0.484). For systems like Mount St. Helens, where the major minerals record only events in the hundreds to thousands of years leading to eruption, (including the Fe-Ti oxides traditionally relied upon for records of oxidation state of the magmas), this presents a novel approach for understanding more extended histories of oxidation of magmas in the tens and hundreds of thousands of years of magmatism at a volcanic center. This calibration also promises to help us better constrain conditions of crystallization in intrusive portions of volcanic systems, as well as plutonic bodes. We apply this new oxygen geobarometer to natural volcanic and plutonic zircons from a variety of tectonic settings, and compare to existing indicators of oxidation state for each system, as available. Zircons included this study are from Mount St. Helens (ΔNNO +1.5 log units; Smith, 1984), the Peach Spring Tuff and Spirit Mountain Batholith (sphene-bearing, silicic, Miocene-aged rocks from the Colorado River Extensional Corridor), Alid Volcano in Eritrea, and rhyolites and granites from Iceland. Median log fO2 for these systems, calculated from the Cerium anomaly in zircons following Trail et al. (2011) using temperatures from Ti-in-zircon thermometry (Ferry and Watson, 2007) are as follows: Alid -12 bars (ΔNNO +3 log units) at 750 degrees C; Iceland -11 bars (ΔNNO +3 log units) at 800 degrees C; Mount St. Helens -8.6 bars (ΔNNO +6 log units) at 750 degrees C; Peach Spring Tuff -3.4 (ΔNNO +10 log units) at 830 degrees C. While ubiquitous sphene in the Spirit Mountain granites suggest relatively high fO2, calculations based on the cerium anomaly in zircon suggest median log fO2 of >0 at 770 degrees C, which is certainly erroneous. While median values for our natural zircons are, for the most part, above expected fugacities for each system when compared with other indicators, and extreme values for each system are almost certainly erroneous, many are within expected values for terrestrial magmas and they vary relative to one another as might be expected given the magma types and tectonic settings.

Altering properties of cerium oxide thin films by Rh doping

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

Ševčíková, Klára, E-mail: klarak.sevcikova@seznam.cz; NIMS Beamline Station at SPring-8, National Institute for Materials Science, Sayo, Hyogo 679-5148; Nehasil, Václav, E-mail: nehasil@mbox.troja.mff.cuni.cz

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 diffractionmore » 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.« less

The impact of cerium oxide nanoparticles on the physiology of soybean (Glycine max (L.) Merr.) under different soil moisture conditions.

PubMed

Cao, Zhiming; Rossi, Lorenzo; Stowers, Cheyenne; Zhang, Weilan; Lombardini, Leonardo; Ma, Xingmao

2018-01-01

The ongoing global climate change raises concerns over the decreasing moisture content in agricultural soils. Our research investigated the physiological impact of two types of cerium oxide nanoparticles (CeO 2 NPs) on soybean at different moisture content levels. One CeO 2 NP was positively charged on the surface and the other negatively charged due to the polyvinylpyrrolidone (PVP) coating. The results suggest that the effect of CeO 2 NPs on plant photosynthesis and water use efficiency (WUE) was dependent upon the soil moisture content. Both types of CeO 2 NPs exhibited consistently positive impacts on plant photosynthesis at the moisture content above 70% of field capacity (θ fc ). Similar positive impact of CeO 2 NPs was not observed at 55% θ fc , suggesting that the physiological impact of CeO 2 NPs was dependent upon the soil moisture content. The results also revealed that V Cmax (maximum carboxylation rate) was affected by CeO 2 NPs, indicating that CeO 2 NPs affected the Rubisco activity which governs carbon assimilation in photosynthesis. In conclusion, CeO 2 NPs demonstrated significant impacts on the photosynthesis and WUE of soybeans and such impacts were affected by the soil moisture content. Graphical abstract Soil moisture content affects plant cerium oxide nanoparticle interactions.

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. Copyright © 2016 Elsevier B.V. All rights reserved.

Spectrophotometric and spectrofluorimetric methods for determination of certain biologically active phenolic drugs in their bulk powders and different pharmaceutical formulations

NASA Astrophysics Data System (ADS)

Omar, Mahmoud A.; Badr El-Din, Kalid M.; Salem, Hesham; Abdelmageed, Osama H.

2018-03-01

Two simple and sensitive spectrophotometric and spectrofluorimetric methods for the determination of terbutaline sulfate, fenoterol hydrobromide, etilefrine hydrochloride, isoxsuprine hydrochloride, ethamsylate, doxycycline hyclate have been developed. Both methods were based on the oxidation of the cited drugs with cerium (IV) in acid medium. The spectrophotometric method was based on measurement of the absorbance difference (ΔA), which represents the excess cerium (IV), at 317 nm for each drug. On the other hand, the spectrofluorimetric method was based on measurement of the fluorescent of the produced cerium (III) at emission wavelength 354 nm (λexcitation = 255 nm) for the concentrations studied for each drug. For both methods, the variables affecting the reactions were carefully investigated and the conditions were optimized. Linear relationships were found between either ΔA or the fluorescent of the produced cerium (III) values and the concentration of the studied drugs in a general concentration range of 2.0-24.0 μg mL- 1, 20.0-24.0 ng mL- 1 with good correlation coefficients in the following range 0.9990-0.9999, 0.9990-0.9993 for spectrophotometric and spectrofluorimetric methods respectively. The limits of detection and quantitation of spectrophotometric method were found in general concentration range 0.190-0.787 and 0.634-2.624 μg mL- 1respectively. For spectrofluorimetric method, the limits of detection and quantitation were found in general concentration range 4.77-9.52 and 15.91-31.74 ng mL- 1 respectively. The stoichiometry of the reaction was determined, and the reactions pathways were postulated. The analytical performance of the methods, in terms of accuracy and precision, were statistically validated and the results obtained were satisfactory. The methods have been successfully applied to the determination of the cited drugs in their commercial pharmaceutical formulations. Statistical comparison of the results with the reference methods showed excellent agreement and proved that no significant difference in the accuracy and precision.

Geometry of electromechanically active structures in Gadolinium - doped Cerium oxides

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

Li, Yuanyuan; Zacharowicz, Renee; Frenkel, Anatoly I., E-mail: igor.lubomirsky@weizmann.ac.il, E-mail: anatoly.frenkel@yu.edu

2016-05-15

Local distortions from average structure are important in many functional materials, such as electrostrictors or piezoelectrics, and contain clues about their mechanism of work. However, the geometric attributes of these distortions are exceedingly difficult to measure, leading to a gap in knowledge regarding their roles in electromechanical response. This task is particularly challenging in the case of recently reported non-classical electrostriction in Cerium-Gadolinium oxides (CGO), where only a small population of Ce-O bonds that are located near oxygen ion vacancies responds to external electric field. We used high-energy resolution fluorescence detection (HERFD) technique to collect X-ray absorption spectra in CGOmore » in situ, with and without an external electric field, coupled with theoretical modeling to characterize three-dimensional geometry of electromechanically active units.« less

Determination of Organothiophosphate Insecticides in Environmental Water Samples by a Very Simple and Sensitive Spectrofluorimetric Method.

PubMed

Bavili Tabrizi, Ahad; Abdollahi, Ali

2015-10-01

A simple, rapid and sensitive spectrofluorimetric method was developed for the determination of di-syston, ethion and phorate in environmental water samples. The procedure is based on the oxidation of these pesticides with cerium (IV) to produce cerium (III), and its fluorescence was monitored at 368 ± 3 nm after excitation at 257 ± 3 nm. The variables effecting oxidation of each pesticide were studied and optimized. Under the experimental conditions used, the calibration graphs were linear over the range 0.2-15, 0.1-13, 0.1-13 ng mL(-1) for di-syston, ethion and phorate, respectively. The limit of detection and quantification were in the range 0.034-0.096 and 0.112-0.316 ng mL(-1), respectively. Intra- and inter-day assay precisions, expressed as the relative standard deviation (RSD), were lower than 5.2 % and 6.7 %, respectively. Good recoveries in the range 86 %-108 % were obtained for spiked water samples. The proposed method was applied to the determination of studied pesticides in environmental water samples.

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

Jaques, Brian; Butt, Darryl P.; Marx, Brian M.

A carbothermic reduction of the metal oxides in a hydrogen/nitrogen mixed gas stream prior to nitriding in a nitrogen gas stream was used to synthesize uranium nitride at 1500 deg. C, cerium nitride at 1400 deg. C, and dysprosium nitride at 1500 deg. C. Cerium nitride and dysprosium nitride were also synthesized via hydriding and nitriding the metal shavings at 900 deg. C and 1500 deg. C, respectively. Also, a novel ball-milling synthesis route was used to produce cerium nitride and dysprosium nitride from the metal shavings at room temperature. Dysprosium nitride was also produced by reacting the metal shavingsmore » in a high purity nitrogen gas stream at 1300 deg. C. All materials were characterized by phase analysis via X-ray diffraction. Only the high purity materials were further analyzed via chemical analysis to characterize the trace oxygen concentration. (authors)« less

Stabilization of 238Pu-contaminated combustible waste by molten salt oxidation

NASA Astrophysics Data System (ADS)

Stimmel, Jay J.; Remerowski, Mary Lynn; Ramsey, Kevin B.; Heslop, J. Mark

2000-07-01

Surrogate studies were conducted using the molten salt oxidation system at the Naval Surface Warfare Center-Indian Head Division. This system uses a rotary feed system and an alumina molten salt oxidation vessel. The combustible materials were tested individually and together in a homogenized mixture. A slurry containing pyrolyzed cheesecloth ash spiked with cerium oxide, which is used as a surrogate for plutonium, and ethylene glycol were also treated in the molten salt oxidation vessel.

Antimicrobial cerium ion-chitosan crosslinked alginate biopolymer films: A novel and potential wound dressing.

PubMed

Kaygusuz, Hakan; Torlak, Emrah; Akın-Evingür, Gülşen; Özen, İlhan; von Klitzing, Regine; Erim, F Bedia

2017-12-01

Wound dressings require good antiseptic properties, mechanical strength and, more trustably, natural material ingredients. Antimicrobial properties of cerium ions and chitosan are known and alginate based wound dressings are commercially available. In this study, the advantages of these materials were combined and alginate films were crosslinked with cerium(III) solution and chitosan added cerium(III) solution. Films were characterized by Fourier transform infrared spectroscopy (FTIR), light transmittance, scanning electron microscopy (SEM), swelling experiments, water vapor transmittance tests, and mechanical stretching tests. The antibacterial and physical properties of the films were compared with those of conventional calcium alginate films. Both cerium ion crosslinked and cerium ion-chitosan crosslinked alginate films gained antibacterial activity against Gram-negative (Escherichia coli) and Gram-positive (Staphylococcus aureus) bacteria. Cerium alginate-chitosan films showed high resistance to being deformed elastically. Results show that cerium alginate-chitosan films can be flexible, ultraviolet-protecting, and antibacterial wound dressings. Copyright © 2017 Elsevier B.V. All rights reserved.

Molecular Dynamics Modeling and Simulation of Diamond Cutting of Cerium.

PubMed

Zhang, Junjie; Zheng, Haibing; Shuai, Maobing; Li, Yao; Yang, Yang; Sun, Tao

2017-12-01

The coupling between structural phase transformations and dislocations induces challenges in understanding the deformation behavior of metallic cerium at the nanoscale. In the present work, we elucidate the underlying mechanism of cerium under ultra-precision diamond cutting by means of molecular dynamics modeling and simulations. The molecular dynamics model of diamond cutting of cerium is established by assigning empirical potentials to describe atomic interactions and evaluating properties of two face-centered cubic cerium phases. Subsequent molecular dynamics simulations reveal that dislocation slip dominates the plastic deformation of cerium under the cutting process. In addition, the analysis based on atomic radial distribution functions demonstrates that there are trivial phase transformations from the γ-Ce to the δ-Ce occurred in both machined surface and formed chip. Following investigations on machining parameter dependence reveal the optimal machining conditions for achieving high quality of machined surface of cerium.

Molecular Dynamics Modeling and Simulation of Diamond Cutting of Cerium

NASA Astrophysics Data System (ADS)

Zhang, Junjie; Zheng, Haibing; Shuai, Maobing; Li, Yao; Yang, Yang; Sun, Tao

2017-07-01

The coupling between structural phase transformations and dislocations induces challenges in understanding the deformation behavior of metallic cerium at the nanoscale. In the present work, we elucidate the underlying mechanism of cerium under ultra-precision diamond cutting by means of molecular dynamics modeling and simulations. The molecular dynamics model of diamond cutting of cerium is established by assigning empirical potentials to describe atomic interactions and evaluating properties of two face-centered cubic cerium phases. Subsequent molecular dynamics simulations reveal that dislocation slip dominates the plastic deformation of cerium under the cutting process. In addition, the analysis based on atomic radial distribution functions demonstrates that there are trivial phase transformations from the γ-Ce to the δ-Ce occurred in both machined surface and formed chip. Following investigations on machining parameter dependence reveal the optimal machining conditions for achieving high quality of machined surface of cerium.

Cerium Improves Growth of Maize Seedlings via Alleviating Morphological Structure and Oxidative Damages of Leaf under Different Stresses.

PubMed

Hong, Fashui; Qu, Chunxiang; Wang, Ling

2017-10-18

It had been indicated that cerium (Ce) could promote maize growth involving photosynthetic improvement under potassium (K) deficiency, salt stress, and combined stress of K + deficiency and salt stress. However, whether the improved growth is related to leaf morphological structure, oxidative stress in maize leaves is not well understood. The present study showed that K + deficiency, salt stress, and their combined stress inhibited growth of maize seedlings, affecting the formation of appendages of leaf epidermal cells, and stomatal opening, which may be due to increases in H 2 O 2 and malondialdehyde levels, and reductions in Ca 2+ content, ratios of glutathione/oxidized glutathione, ascorbic acid/dehydroascorbic acid, and the activities of superoxide dismutase, catalase, ascorbic acid peroxidase, guaiacol peroxidase, and glutathione reductase in leaves under different stresses. The adverse effects caused by combined stress were higher than those of single stress. Furthermore, our findings demonstrated that adding Ce 3+ could significantly promote seedling growth, and alleviate morphological and structural damage of leaf, decrease oxidative stress and increase antioxidative capacity in maize leaves caused by different stresses.

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 carbon-platinum-cerium has better catalytic activity than platinum-carbon. Due to the hybridization behavior of C and Ce could arise charge transfer, both carbon and cerium to the Platinum. Ce-C→Pt charge transfer could occur at the Ce-C/Pt interface. Thus, results in an increase in the catalytic activity of platinum-cerium-carbon when compared with carbon-platinum.

Characterization of metal-ferroelectric-insulator-semiconductor structures based on ferroelectric Langmuir-Blodgett polyvinylidene fluoride copolymer films for nondestructive random access memory applications

NASA Astrophysics Data System (ADS)

Reece, Timothy James

Ferroelectric field effect transistors (FeFETs) have attracted much attention recently because of their ability to combine high speed, low power consumption, and fast nondestructive readout with the potential for high density nonvolatile memory. The polarization of the ferroelectric is used to switch the channel at the silicon surface between states of high and low conductance. Among the ferroelectric thin films used in FET devices; the ferroelectric copolymer of Polyvinylidene fluoride, PVDF (C2H2F 2), with trifluoroethylene, TrFE (C2HF3), has distinct advantages, including low dielectric constant, low processing temperature, low cost and compatibility with organic semiconductors. By employing the Langmuir-Blodgett technique, films as thin as 1.8 nm can be deposited, reducing the operating voltage. An MFIS structure consisting of aluminum, 170 nm P(VDF-TrFE), 100 nm silicon oxide and n-type silicon exhibited low leakage current (˜1x10 -8 A/cm2), a large memory window (4.2 V) and operated at 35 Volts. The operating voltage was lowered through use of high k insulators like cerium oxide. A sample consisting of 25 nm P(VDF-TrFE), 30 nm cerium oxide and p-type silicon exhibited a 1.9 V window with 7 Volt gate amplitude. The leakage current in this case was considerably higher (1x10 -6 A/cm2). The characterization, modeling, and fabrication of metal-ferroelectricinsulator semiconductor (MFIS) structures based on these films are discussed.

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. Copyright © 2010 Elsevier B.V. All rights reserved.

Effect of oxidizer to fuel molar ratio on particle size and DC conductivity of CeO{sub 2} nanoparticles

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

Harish, B. M.; Rajeeva, M. P.; Naveen, C. S.

2016-05-06

Cerium oxide nanoparticles were synthesized by solution combustion method with varying the oxidizer (cerium nitrate hexa hydrate) to fuel (Glycine) molar ratio. The prepared samples were characterized by UV-visible spectrometer, X-ray diffractometer (XRD), Scanning electron microscope (SEM) and Energy dispersive X-Ray analysis (EDAX). XRD pattern reveals the formation of cubic fluorite structure of CeO{sub 2}. It was observed that finest crystallites were found at extreme fuel-deficient condition and it is good enough to produce favorable powder characteristics. The average crystallite size was found to be 14.46 nm to 21.57 nm. The temperature dependent dc conductivity was carried out using Keithleymore » source meter between the temperature range from 300 K to 573 K. From this study it was found that the conductivity increases with increase of temperature due to semiconducting behavior of CeO{sub 2} and it decreases with particle size due to increase in the energy band gap.« less

Non-Enzymatic Glucose Biosensor Based on CuO-Decorated CeO2 Nanoparticles

PubMed Central

Guan, Panpan; Li, Yongjian; Zhang, Jie; Li, Wei

2016-01-01

Copper oxide (CuO)-decorated cerium oxide (CeO2) nanoparticles were synthesized and used to detect glucose non-enzymatically. The morphological characteristics and structure of the nanoparticles were characterized through transmission electron microscopy, X-ray photoelectron spectroscopy, and X-ray diffraction. The sensor responses of electrodes to glucose were investigated via an electrochemical method. The CuO/CeO2 nanocomposite exhibited a reasonably good sensitivity of 2.77 μA mM−1cm−2, an estimated detection limit of 10 μA, and a good anti-interference ability. The sensor was also fairly stable under ambient conditions. PMID:28335287

Geometry of electromechanically active structures in Gadolinium - doped Cerium oxides

DOE PAGES

Li, Yuanyuan; Kraynis, Olga; Kas, Joshua; ...

2016-05-20

Local distortions from average structure are important in many functional materials, such as electrostrictors or piezoelectrics, and contain clues about their mechanism of work. However, the geometric attributes of these distortions are exceedingly difficult to measure, leading to a gap in knowledge regarding their roles in electromechanical response. This task is particularly challenging in the case of recently reported non-classical electrostriction in Cerium-Gadolinium oxides (CGO), where only a small population of Ce-O bonds that are located near oxygen ion vacancies responds to external electric field. In this study, we used high-energy resolution fluorescence detection (HERFD) technique to collect X-ray absorptionmore » spectra in CGO in situ, with and without an external electric field, coupled with theoretical modeling to characterize three-dimensional geometry of electromechanically active units.« less

METHOD OF PROCESSING MONAZITE SAND

DOEpatents

Welt, M.A.; Smutz, M.

1958-08-26

A process is described for recovering thorium, uranium, and rare earth values from monazite sand. The monazite sand is first digested with sulfuric acid and the resulting "monazite sulfate" solution is adjusted to a pH of between 0.4 and 3.0, and oxalate anions are added causing precipitation of the thorium and the rare earths as the oxalates. The oxalate precipitate is separated from the uranium containing supernatant solution, and is dried and calcined to the oxides. The thorium and rare earth oxides are then dissolved in nitric acid and the solution is contacted with tribntyl phosphate whereby an organic extract phase containing the cerium and thorium values is obtained, together with an aqueous raffinate containing the other rare earth values. The organic phase is then separated from the aqueous raffinate and the cerium and thorium are back extracted with an aqueous medium.

Interactions between sub-10-nm iron and cerium oxide nanoparticles and 3T3 fibroblasts: the role of the coating and aggregation state

NASA Astrophysics Data System (ADS)

Safi, M.; Sarrouj, H.; Sandre, O.; Mignet, N.; Berret, J.-F.

2010-04-01

Recent nanotoxicity studies revealed that the physico-chemical characteristics of engineered nanomaterials play an important role in the interactions with living cells. Here, we report on the toxicity and uptake of cerium and iron oxide sub-10-nm nanoparticles by NIH/3T3 mouse fibroblasts. Coating strategies include low-molecular weight ligands (citric acid) and polymers (poly(acrylic acid), MW = 2000 g mol - 1). Electrostatically adsorbed on the surfaces, the organic moieties provide a negatively charged coating in physiological conditions. We find that most particles were biocompatible, as exposed cells remained 100% viable relative to controls. Only the bare and the citrate-coated nanoceria exhibit a slight decrease in mitochondrial activity at very high cerium concentrations (>1 g l - 1). We also observe that the citrate-coated particles are internalized/adsorbed by the cells in large amounts, typically 250 pg/cell after 24 h incubation for iron oxide. In contrast, the polymer-coated particles are taken up at much lower rates (<30 pg/cell). The strong uptake shown by the citrated particles is related to the destabilization of the dispersions in the cell culture medium and their sedimentation down to the cell membranes. In conclusion, we show that the uptake of nanomaterials by living cells depends on the coating of the particles and on its ability to preserve the colloidal nature of the dispersions.

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

A sub-1-volt analog metal oxide memristive-based synaptic device with large conductance change for energy-efficient spike-based computing systems

NASA Astrophysics Data System (ADS)

Hsieh, Cheng-Chih; Roy, Anupam; Chang, Yao-Feng; Shahrjerdi, Davood; Banerjee, Sanjay K.

2016-11-01

Nanoscale metal oxide memristors have potential in the development of brain-inspired computing systems that are scalable and efficient. In such systems, memristors represent the native electronic analogues of the biological synapses. In this work, we show cerium oxide based bilayer memristors that are forming-free, low-voltage (˜|0.8 V|), energy-efficient (full on/off switching at ˜8 pJ with 20 ns pulses, intermediate states switching at ˜fJ), and reliable. Furthermore, pulse measurements reveal the analog nature of the memristive device; that is, it can directly be programmed to intermediate resistance states. Leveraging this finding, we demonstrate spike-timing-dependent plasticity, a spike-based Hebbian learning rule. In those experiments, the memristor exhibits a marked change in the normalized synaptic strength (>30 times), when the pre- and post-synaptic neural spikes overlap. This demonstration is an important step towards the physical construction of high density and high connectivity neural networks.

Direct hydrothermal growth of GDC nanorods for low temperature solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Hong, Soonwook; Lee, Dohaeng; Yang, Hwichul; Kim, Young-Beom

2018-06-01

We report a novel synthesis technique of gadolinia-doped ceria (GDC) nano-rod (NRs) via direct hydrothermal process to enhance performance of low temperature solid oxide fuel cell by increasing active reaction area and ionic conductivity at interface between cathode and electrolyte. The cerium nitrate hexahydrate, gadolinium nitrate hexahydrate and urea were used to synthesis GDC NRs for growth on diverse substrate. The directly grown GDC NRs on substrate had a width from 819 to 490 nm and height about 2200 nm with a varied urea concentration. Under the optimized urea concentration of 40 mMol, we confirmed that GDC NRs able to fully cover the substrate by enlarging active reaction area. To maximize ionic conductivity of GDC NRs, we synthesis varied GDC NRs with different ratio of gadolinium and cerium precursor. Electrochemical analysis revealed a significant enhanced performance of fuel cells applying synthesized GDC NRs with a ratio of 2:8 gadolinium and cerium precursor by reducing polarization resistance, which was chiefly attributed to the enlarged active reaction area and enhanced ionic conductivity of GDC NRs. This method of direct hydrothermal growth of GDC NRs enhancing fuel cell performance was considered to apply other types of catalyzing application using nano-structure such as gas sensing and electrolysis fields.

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.

Quantitative depth profiling of Ce(3+) in Pt/CeO2 by in situ high-energy XPS in a hydrogen atmosphere.

PubMed

Kato, Shunsuke; Ammann, Markus; Huthwelker, Thomas; Paun, Cristina; Lampimäki, Markus; Lee, Ming-Tao; Rothensteiner, Matthäus; van Bokhoven, Jeroen A

2015-02-21

The redox property of ceria is a key factor in the catalytic activity of ceria-based catalysts. The oxidation state of well-defined ceria nanocubes in gas environments was analysed in situ by a novel combination of near-ambient pressure X-ray Photoelectron Spectroscopy (XPS) and high-energy XPS at a synchrotron X-ray source. In situ high-energy XPS is a promising new tool to determine the electronic structure of matter under defined conditions. The aim was to quantitatively determine the degree of cerium reduction in a nano-structured ceria-supported platinum catalyst as a function of the gas environment. To obtain a non-destructive depth profile at near-ambient pressure, in situ high-energy XPS analysis was performed by varying the kinetic energy of photoelectrons from 1 to 5 keV, and, thus, the probing depth. In ceria nanocubes doped with platinum, oxygen vacancies formed only in the uppermost layers of ceria in an atmosphere of 1 mbar hydrogen and 403 K. For pristine ceria nanocubes, no change in the cerium oxidation state in various hydrogen or oxygen atmospheres was observed as a function of probing depth. In the absence of platinum, hydrogen does not dissociate and, thus, does not lead to reduction of ceria.

Spectrophotometric determination of ofloxacin in pharmaceuticals by redox reaction

NASA Astrophysics Data System (ADS)

Ramesh, P. J.; Basavaiah, K.; Rajendraprasad, N.; Devi, O. Zenita; Vinay, K. B.

2011-07-01

Two simple spectrophotometric methods have been developed to analyze ofloxacin (OFX) in pharmaceuticals. The methods are based on the oxidation of OFX by a measured excess of cerium(IV) sulfate in H2SO4 medium. This was followed by the determination of the unreacted oxidant by reacting it with either p-toluidine ( p-TD) and measuring the absorbance at 525 nm (method A) or o-dianisidine ( o-DA) and measuring the absorbance at 470 nm (method B). In both methods, the amount of cerium(IV) sulfate reacted corresponds to the amount of OFX. Calibration graphs were linear over the ranges of 0-120 and 0-4 g/ml OFX for methods A and B, respectively. The calculated molar absorptivity (2.34ṡ103 and 5.99ṡ104), Sandell sensitivity, and limit of quantification for the methods are reported. The intra-day precision (%RSD) and accuracy (%RE) were < 8.0 and ≤ 4.0%, respectively, and the inter-day RSD and RE values were within 5 and 4.0%, respectively. The applicability of the methods was demonstrated by determining OFX in tablets with an accuracy (%RE) of < 3% and precision (%RSD) of ≤2.65%. The accuracy of the methods was further ascertained by recovery experiments via a standard-addition procedure.

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.

Microstructure, texture evolution and magnetic properties of strip-casting non-oriented 6.5 wt.% Si electrical steel doped with cerium

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

Li, Hao-Ze, E-mail: lhzqq83@163.com; Liu, Hai-Tao; Liu, Zhen-Yu, E-mail: zyliu@mail.neu.edu.cn

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 //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.« less

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

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.

Protection from radiation-induced pneumonitis using cerium oxide nanoparticles.

PubMed

Colon, Jimmie; Herrera, Luis; Smith, Joshua; Patil, Swanand; Komanski, Chris; Kupelian, Patrick; Seal, Sudipta; Jenkins, D Wayne; Baker, Cheryl H

2009-06-01

In an effort to combat the harmful effects of radiation exposure, we propose that rare-earth cerium oxide (CeO(2)) nanoparticles (free-radical scavengers) protect normal tissue from radiation-induced damage. Preliminary studies suggest that these nanoparticles may be a therapeutic regenerative nanomedicine that will scavenge reactive oxygen species, which are responsible for radiation-induced cell damage. The effectiveness of CeO(2) nanoparticles in radiation protection in murine models during high-dose radiation exposure is investigated, with the ultimate goal of offering a new approach to radiation protection, using nanotechnology. We show that CeO(2) nanoparticles are well tolerated by live animals, and they prevent the onset of radiation-induced pneumonitis when delivered to live animals exposed to high doses of radiation. In the end, these studies provide a tremendous potential for radioprotection and can lead to significant benefits for the preservation of human health and the quality of life for humans receiving radiation therapy.

Dip-coating of nano-sized CeO2 on SiC membrane and its effect on thermal diffusivity.

PubMed

Park, Jihye; Jung, Miewon

2014-05-01

CeO2-SiC mixed composite membrane was fabricated with porous SiC ceramic and cerium oxide powder synthesized by sol-gel process. This CeO2-SiC membrane and SiC membrane which is made by the purified SiC ceramic were pressed and sintered in Ar atmosphere. And then, the SiC membrane was dip-coated by cerium oxide precursor sol solution and heat-treated in air. The surface morphology, particle size, porosity and structure analysis of the mixing and dip-coating SiC membrane were monitored by FE-SEM and X-ray diffraction analysis. Surface area, pore volume and pore diameter were determined by BET instrument. Thermal diffusivity was measured by laser flash method with increasing temperature. The relation between porosity and thermal diffusivity from different preparation process has been discussed on this study.

The formation of cobalt-bearing ferromanganese crusts under fluid destruction of silicate matter

NASA Astrophysics Data System (ADS)

Maksimov, S. O.; Safronov, P. P.

2016-02-01

The processes of fluid destruction of various silicate rocks under diffusion of flows of compressed gases (mainly carbonaceous) were studied. The gas condensate nature was ascertained for the forming alumoslilicate and ore (cobalt-iron-manganese hydroxide) substances produced under this fluid destruction in the forms of microcrusts and microconcretions. The ore condensates contained in high concentrations the typomorphic elements of oceanic ferromanganese formations (Mn, Co, Ni, Cu, Pb, Ce, and Pt). The elemental composition of the ore oxide substance formed under the destruction of various silicate matrices exhibits a definite degree of endemism with prevalence of the Co-Mn association. The pronounced concentration of barium is related to the substantially carbonaceous composition of the fluid systems. A cerium paradox is revealed: Ce3+ is oxidized into Ce4+ and absorbed by ferromanganese hydrogel and the minimum of cerium appears in rare-earth phosphates.

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

Synthesis and structural studies on cerium substituted La0.4Ca0.6MnO3 as solid oxide fuel cell electrode material

NASA Astrophysics Data System (ADS)

Singh, Monika; Kumar, Dinesh; Singh, Akhilesh Kumar

2018-04-01

For solid oxide fuel cell electrode material, calcium doped lanthanum manganite La0.4Ca0.6MnO3 (LCMO) and cerium-incorporated on Ca-site with composition La0.40Ca0.55Ce0.05MnO3 (LCCMO) were synthesized using most feasible and efficient glycine-nitrate method. The formation of crystalline single phase was confirmed by x-ray diffraction (XRD). The Rietveld analysis reveals that both systems crystallize into orthorhombic crystal structure with Pnma space group. Additionally, 8 mole % Y2O3 stabilized ZrO2 (8YSZ) solid electrolyte was also synthesized using high energy ball mill to check the reaction with electrode materials. It was found that the substitution of Ce+4 cations in LCMO perovskite suppressed formation of undesired insulating CaZrO3 phase.

Chemiluminescence from an oxidation reaction of rhodamine B with cerium(IV) in a reversed micellar medium of cetyltrimethylammonium chloride in 1-hexanol-cyclohexane/water.

PubMed

Hasanin, Tamer H A; Tsunemine, Yusuke; Tsukahara, Satoshi; Okamoto, Yasuaki; Fujiwara, Terufumi

2011-01-01

The chemiluminescence (CL) emission, observed when rhodamine B (RB) in 1-hexanol-cyclohexane was mixed with cerium(IV) sulfate in sulfuric acid dispersed in a reversed micellar medium of cetyltrimethylammonium chloride (CTAC) in 1-hexanol-cyclohexane/water, was investigated using a flow-injection system. The CL emission from the oxidation reaction of RB with Ce(IV) was found to be stronger in the CTAC reversed micellar solution compared with an aqueous solution. Bearing on the enhancement effect of the CTAC reverse micelles on the RB-Ce(IV) CL, several studies including stopped-flow, fluorescence and electron spin resonance (ESR) spectrometries were performed. Rapid spectral changes of an intermediate in the RB-Ce(IV) reaction in the aqueous and reversed micellar solutions were successfully observed using a stopped-flow method. The effect of the experimental variables, i.e., oxidant concentration, sulfuric acid concentration, the mole fraction of 1-hexanol, water-to-surfactant molar concentration ratio, flow rate, upon the CL intensity was evaluated. Under the experimental conditions optimized for a flow-injection determination of RB based on the new reversed micellar-mediated CL reaction with Ce(IV), a detection limit of 0.08 µmol dm(-3) RB was achieved, and a linear calibration graph was obtained with a dynamic range from 0.5 to 20 µmol dm(-3). The relative standard deviation (n = 6) obtained at an RB concentration of 3 µmol dm(-3) was 3%.

Flow injection chemiluminescent determination of tetracycline using a tris(2,2'-bipyridine)ruthenium(II)-cerium(IV) sulphate system.

PubMed

Guo, Liangqia; Xie, Zenghong; Lin, Xucong; Liu, Xiaohua; Zhang, Weilin; Chen, Guonan

2004-01-01

A flow-injection chemiluminescence method for the determination of tetracycline was developed. The method is based on an enhancement by tetracycline of the chemiluminescence light emission of tris(2,2'-bipyridine)ruthenium(II). In sulphuric acid medium, the chemiluminescence is generated by the continuous oxidation of tris(2,2'-bipyridine)ruthenium(II) by cerium (IV) sulphate. The light-emission intensity is greatly enhanced in the presence of tetracycline. Under the optimum conditions, the calibration curve is linear over the range 3.75 x 10(-8) g/mL-1.5 x 10(-5) g/mL for tetracycline with the linear equation: deltaINT = 205.898 x C - 20.442 (R2 = 0.9974). The detection limit is 3.27 x 10(-8) g/mL. The proposed method was also successfully used to determine tetracycline in pharmaceutical formulation (mean recovery of tetracycline, 100.7%). Copyright 2004 John Wiley & Sons, Ltd.

Catalysts for the decomposition of hydrazine and its derivatives and a method for its production

NASA Technical Reports Server (NTRS)

Sasse, R.

1986-01-01

Catalysts of various types are used to decompose hydrazine and its derivatives. One type of catalyst is made as follows: the aluminum is dissolved out of an alloy of cobalt or nickel/aluminum so that a structure is produced that is chemically active for the monergol and that has a large active surface. The objective was to avoid difficulties and to create a catalyst that not only has a short start time but that can also be manufactured easily and relatively inexpensively. The solution to this task is to coat the base structure of the catalyst with oxides of copper, cobalt and cerium or oxides of copper, cobalt and cerite earth.

Spectrophotometric and spectrofluorimetric methods for determination of certain biologically active phenolic drugs in their bulk powders and different pharmaceutical formulations.

PubMed

Omar, Mahmoud A; Badr El-Din, Kalid M; Salem, Hesham; Abdelmageed, Osama H

2018-03-05

Two simple and sensitive spectrophotometric and spectrofluorimetric methods for the determination of terbutaline sulfate, fenoterol hydrobromide, etilefrine hydrochloride, isoxsuprine hydrochloride, ethamsylate, doxycycline hyclate have been developed. Both methods were based on the oxidation of the cited drugs with cerium (IV) in acid medium. The spectrophotometric method was based on measurement of the absorbance difference (ΔA), which represents the excess cerium (IV), at 317nm for each drug. On the other hand, the spectrofluorimetric method was based on measurement of the fluorescent of the produced cerium (III) at emission wavelength 354nm (λ excitation =255nm) for the concentrations studied for each drug. For both methods, the variables affecting the reactions were carefully investigated and the conditions were optimized. Linear relationships were found between either ΔA or the fluorescent of the produced cerium (III) values and the concentration of the studied drugs in a general concentration range of 2.0-24.0μgmL -1 , 20.0-24.0ngmL -1 with good correlation coefficients in the following range 0.9990-0.9999, 0.9990-0.9993 for spectrophotometric and spectrofluorimetric methods respectively. The limits of detection and quantitation of spectrophotometric method were found in general concentration range 0.190-0.787 and 0.634-2.624μgmL -1 respectively. For spectrofluorimetric method, the limits of detection and quantitation were found in general concentration range 4.77-9.52 and 15.91-31.74ngmL -1 respectively. The stoichiometry of the reaction was determined, and the reactions pathways were postulated. The analytical performance of the methods, in terms of accuracy and precision, were statistically validated and the results obtained were satisfactory. The methods have been successfully applied to the determination of the cited drugs in their commercial pharmaceutical formulations. Statistical comparison of the results with the reference methods showed excellent agreement and proved that no significant difference in the accuracy and precision. Copyright © 2017 Elsevier B.V. All rights reserved.

Characterization of the corrosion protection mechanism of cerium-based conversion coatings on high strength aluminum alloys

NASA Astrophysics Data System (ADS)

Pinc, William Ross

The aim of the work presented in this dissertation is to investigate the corrosion protection mechanism of cerium-based conversion coatings (CeCCs) used in the corrosion protection of high strength aluminum alloys. The corrosion resistance of CeCCs involves two general mechanisms; barrier and active. The barrier protection mechanism was influenced by processing parameters, specifically surface preparation, post-treatment, and the use of gelatin. Post-treatment and the addition of gelatin to the coating solution resulted in fewer cracks and transformation of the coating to CePO4, which increased the corrosion resistance by improving the barrier aspect of CeCCs. CeCCs were found to best act as barriers when crack size was limited and CePO4 was present in the coating. CeCCs were found to protect areas of the substrate that were exposed in the coating, indicating that the coatings were more than simple barriers. CeCCs contained large cracks, underneath which subsurface crevices were connected to the surface by the cracks. Despite the observation that no cerium was present in crevices, coatings with crevices exhibited significant corrosion protection. The impedance of post-treated coatings with crevices increased during salt spray exposure. The increase in impedance was associated with the formation of protective oxides / hydroxides; however, crevice-free coatings also exhibited active protection leading to the conclusion that the formation of interfacial layers between the CeCC and the substrate also contributed to the active protection. Based on the overall results of the study, the optimal corrosion protection of CeCCs occurred when processing conditions produced coatings with morphologies and compositions that facilitated both the barrier and active protection mechanisms.

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

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

Szymanski, Craig J.; Munusamy, Prabhakaran; Mihai, Cosmin

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 quantifiedmore » 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.« less

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. Copyright © 2015 Elsevier B.V. All rights reserved.

Gold-supported cerium-doped NiO x catalysts for water oxidation

DOE PAGES

Ng, Jia Wei Desmond; García-Melchor, Max; Bajdich, Michal; ...

2016-04-29

Here, 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 NiO x films resulting from the combined effects of using cerium as a dopant and gold as a metal support. This NiCeO x–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 highlymore » 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 NiCeO x–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.« less

Corrosion resistance of BIS 2062-grade steel coated with nano-metal-oxide mixtures of iron, cerium, and titanium in the marine environment

NASA Astrophysics Data System (ADS)

Ashraf, P. Muhamed; Anuradha, R.

2018-02-01

BIS 2062-grade carbon steel is extensively used for fishing boat construction. The steel is highly susceptible to corrosion on the hull and welding joints under marine environment. Here, we demonstrate the application of a novel multifunctional nano-metal-oxide mixture comprised of iron, titanium, and cerium as a marine coating to prevent corrosion. The electrochemical performance of nano-metal-oxide mixture coatings, applied over boat-building steel, was evaluated at 3.5% NaCl medium. The nano-mixture surface coatings showed an efficient corrosion resistance with increased polarization resistance of 6043 Ω cm2 and low corrosion current density of 3.53 × 10-6 A cm-2. The electrochemical impedance spectral data exhibited improvement in the polarization resistance of outermost surface and internal layers. The coating responded faster recovery to normal state when subjected to an induced stress over the coating. The nano-material in the coating behaves as a semiconductor; this enhanced electronic activity over the surface of the steel.

Deactivation of Ceria Supported Palladium through C–C Scission during Transfer Hydrogenation of Phenol with Alcohols

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

Nelson, Nicholas C.; Manzano, J. Sebastián; Slowing, Igor I.

The stability of palladium supported on ceria (Pd/CeO 2) was studied during liquid flow transfer hydrogenation using primary and secondary alcohols as hydrogen donors. For primary alcohols, the ceria support was reduced to cerium hydroxy carbonate within 14 h and was a contributing factor toward catalyst deactivation. For secondary alcohols, cerium hydroxy carbonate was not observed during the same time period and the catalyst was stable upon prolonged reaction. Regeneration through oxidation/reduction does not restore initial activity likely due to irreversible catalyst restructuring. Lastly, a deactivation mechanism involving C–C scission of acyl and carboxylate intermediates is proposed.

Continuous Precipitation of Ceria Nanoparticles from a Continuous Flow Micromixer

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

Tseng, Chih Heng; Paul, Brian; Chang, Chih-hung

2013-01-01

Cerium oxide nanoparticles were continuously precipitated from a solution of cerium(III) nitrate and ammonium hydroxide using a micro-scale T-mixer. Findings show that the method of mixing is important in the ceria precipitation process. In batch mixing and deposition, disintegration and agglomeration dominates the deposited film. In T-mixing and deposition, more uniform nanorod particles are attainable. In addition, it was found that the micromixing approach reduced the exposure of the Ce(OH)3 precipates to oxygen, yielding hydroxide precipates in place of CeO2 precipitates. Advantages of the micro-scale T-mixing approach include shorter mixing times, better control of nanoparticle shape and less agglomeration.

Deactivation of Ceria Supported Palladium through C–C Scission during Transfer Hydrogenation of Phenol with Alcohols

DOE PAGES

Nelson, Nicholas C.; Manzano, J. Sebastián; Slowing, Igor I.

2016-11-21

The stability of palladium supported on ceria (Pd/CeO 2) was studied during liquid flow transfer hydrogenation using primary and secondary alcohols as hydrogen donors. For primary alcohols, the ceria support was reduced to cerium hydroxy carbonate within 14 h and was a contributing factor toward catalyst deactivation. For secondary alcohols, cerium hydroxy carbonate was not observed during the same time period and the catalyst was stable upon prolonged reaction. Regeneration through oxidation/reduction does not restore initial activity likely due to irreversible catalyst restructuring. Lastly, a deactivation mechanism involving C–C scission of acyl and carboxylate intermediates is proposed.

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.

Selective Aerobic Oxidation of 5-(Hydroxymethyl)furfural to 5-Formyl-2-furancarboxylic Acid in Water.

PubMed

Ventura, Maria; Aresta, Michele; Dibenedetto, Angela

2016-05-23

A simple, cheap, and selective catalyst based on copper/cerium oxides is described for the oxidation of 5-(hydroxymethyl)furfural (5-HMF) in water. An almost quantitative conversion (99 %) with excellent (90 %) selectivity towards the formation of 5-formyl-2-furancarboxylic acid, a platform molecule for other high value chemicals, is observed. The catalyst does not require any pretreatment or additives, such as bases, to obtain high yield and selectivity in water as solvent and using oxygen as oxidant. When a physical mixture of the oxides is used, low conversion and selectivity are observed. Air can be used instead of oxygen, but a lower conversion rate is observed if the same overall pressure is used, and the selectivity remains high. The catalyst can be recovered almost quantitatively and reused. Deactivation of the catalyst, observed in repeated runs, is due to the deposition of humins on its surface. Upon calcination the catalyst almost completely recovers its activity and selectivity, proving that the catalyst is robust. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

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.

Influence of sealing post-treatments on the corrosion resistance of PEO coated AZ91 magnesium alloy

NASA Astrophysics Data System (ADS)

Mingo, B.; Arrabal, R.; Mohedano, M.; Llamazares, Y.; Matykina, E.; Yerokhin, A.; Pardo, A.

2018-03-01

The effect of three different post-treatments carried out on Plasma Electrolytic Oxidation (PEO) coated magnesium alloys are evaluated in terms of characterisation and corrosion resistance. Special interest is given to the role of a common additive (NaF) to the coating properties. The post-treatments are based on immersion sealing processes in aqueous solutions of inorganic salts (cerium and stannate based salts) and alcoholic solution of an organic acid (octodecylphosphate acid, ODP). Sealing mechanisms for each post-treatment are proposed. Cerium and stannate sealings are based on filling of the pores with the products of dissolution/precipitation reactions, while the ODP acid sealing is based on the formation of a thin layer of ODP over the coating through specific interactions between the polar part of the organic acid and the coating surface. All coatings are evaluated by salt fog test and analysed by electrochemical impedance spectroscopy. All sealings show a slight increase in the corrosion resistance of the coatings formed in the NaF-free electrolyte, but their positive influence is boosted in case of the coatings obtained in the NaF-containing electrolyte. This is related to the chemical and morphological changes at the coating surface induced by the presence of NaF in the electrolyte.

Novel borothermal route for the synthesis of lanthanum cerium hexaborides and their field emission properties

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

Menaka; Patra, Rajkumar; Ghosh, Santanu

2012-10-15

The present study describes the development of a simple approach to stabilize polycrystalline lanthanum cerium hexaborides without using any flux and at ambient pressure. The nanostructured lanthanum-cerium borides were synthesized using hydroxide precursors. These precursors (La{sub 1-x}Ce{sub x}(OH){sub 3}, x=0.1, 0.2, 0.3 and 0.5) were synthesized via hydrothermal route in the presence of Tergitol (surfactant, nonylphenol ethoxylate) as a capping agent. The precursors on heating with boron at 1300 Degree-Sign C lead to the formation of nanostructures (cubes, rods and pyramids) of lanthanum cerium hexaboride. We have investigated the field emission behaviour of the hexaboride films fabricated by spin coating.more » It was observed that the pyramidal shaped nanostructures of La{sub 0.5}Ce{sub 0.5}B{sub 6} shows excellent field emission characteristics with high field enhancement factor of 4502. - Graphical abstract: Nanostructured lanthanum cerium hexaboride with efficient field emission have fabricated by low temperature hydroxide precursor mediated route. Highlights: Black-Right-Pointing-Pointer New methodology to prepare lanthanum cerium hexaboride at 1300 Degree-Sign C via borothermal route. Black-Right-Pointing-Pointer Nanostructured lanthanum cerium hexaboride film by spin coating process. Black-Right-Pointing-Pointer Nanopyramids based lanthanum cerium hexaboride shows excellent field emission.« less

The impact of thermal treatment conditions on the formation of crystalline structure of Ce-Zr-oxide composite obtained by a modified sol-gel technique

NASA Astrophysics Data System (ADS)

Trusova, E. A.; Khrushcheva, A. A.; Shvorneva, L. I.

2012-02-01

We present the results of the modified sol-gel synthesis of ultrafine ceria-doped zirconia powder for medical ceramics (implants) and catalytic purposes (environmental catalysis and petrochemistry). Special attention has been paid to study the influence of thermal treatment on crystallite size and crystal lattice parameters of zirconia doped by ceria. Zirconyl chloride and cerium nitrate were used as metal sources, and tetraethylammonium hydroxide (TEAH) was used as a sol stabilizer at molar ratio TEAH/Σ (Ce + Zr) equal to 0.5. It was proved that zirconium and cerium practically completely were included in the obtained solid solutions, since their phase compositions fully correspond to initial quantities of cerium and zirconium in reaction mixture. It was shown that average crystallite size of the obtained powders did not exceed 75Å, and the powders were resistant to thermal treatment. It was established that stabilization of the crystal lattice of ZrO2 occurs through formation of a cubic ceria sublattice.

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...

Production of Monodisperse Cerium Oxide Microspheres with Diameters near 100 µm by Internal-Gelation Sol-Gel Methods

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

Katalenich, Jeffrey A.; Kitchen, Brian B.; Pierson, Bruce

Cerium dioxide microspheres with uniform diameters between 65 – 211 µm were fabricated using internal gelation sol-gel methods. Although uniform microspheres are produced for nuclear fuel applications with diameters above 300 µm, sol-gel microspheres with diameters of 50 - 200 µm have historically been made by emulsion techniques and had poor size uniformity [1, 2]. An internal gelation, sol-gel apparatus was designed and constructed to accommodate the production of small, uniform microspheres whereby cerium-containing solutions were dispersed into flowing silicone oil and heated in a gelation column to initiate solidification [3, 4]. Problems with premature feed gelation and microsphere coalescencemore » were overcome by equipment modifications unique among known internal gelation setups. Microspheres were fabricated and sized in batches as a function of dispersing needle diameter and silicone oil flow rate in the two-fluid nozzle in order to determine the range of sizes possible and corresponding degree of monodispersity. Initial experiments with poor size uniformity were linked to microsphere coalescence in the gelation column prior to solidification as well as excessive flow rates for the cerium feed solution. Average diameter standard deviations as low as 2.23% were observed after optimization of flow rates and minimization of coalescence reactions.« less

Production of monodisperse cerium oxide microspheres with diameters near 100 µm by internal-gelation sol–gel methods

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

Katalenich, Jeffrey A.; Kitchen, Brian B.; Pierson, Bruce D.

Cerium dioxide microspheres with uniform diameters between 65 – 211 µm were fabricated using internal gelation sol-gel methods. Although uniform microspheres are produced for nuclear fuel applications with diameters above 300 µm, sol-gel microspheres with diameters of 50 - 200 µm have historically been made by emulsion techniques and had poor size uniformity [1, 2]. An internal gelation, sol-gel apparatus was designed and constructed to accommodate the production of small, uniform microspheres whereby cerium-containing solutions were dispersed into flowing silicone oil and heated in a gelation column to initiate solidification [3, 4]. Problems with premature feed gelation and microsphere coalescencemore » were overcome by equipment modifications unique among known internal gelation setups. Microspheres were fabricated and sized in batches as a function of dispersing needle diameter and silicone oil flow rate in the two-fluid nozzle in order to determine the range of sizes possible and corresponding degree of monodispersity. Initial experiments with poor size uniformity were linked to microsphere coalescence in the gelation column prior to solidification as well as excessive flow rates for the cerium feed solution. Average diameter standard deviations as low as 2.23% were observed after optimization of flow rates and minimization of coalescence reactions.« less

Predicting the effects of nanoscale cerium additives in diesel fuel on regional-scale air quality.

PubMed

Erdakos, Garnet B; Bhave, Prakash V; Pouliot, George A; Simon, Heather; Mathur, Rohit

2014-11-04

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) emissions and alter the emissions of carbon monoxide (CO), nitrogen oxides (NOx), and hydrocarbon (HC) species, including several hazardous air pollutants (HAPs). To predict their net effect on regional air quality, we review the emissions literature and develop a multipollutant inventory for a hypothetical scenario in which nCe additives are used in all on-road and nonroad diesel vehicles. We apply the Community Multiscale Air Quality (CMAQ) model to a domain covering the eastern U.S. for a summer and a winter period. Model calculations suggest modest decreases of average PM2.5 concentrations and relatively larger decreases in particulate elemental carbon. The nCe additives also have an effect on 8 h maximum ozone in summer. Variable effects on HAPs are predicted. The total U.S. emissions of fine-particulate cerium are estimated to increase 25-fold and result in elevated levels of airborne cerium (up to 22 ng/m3), which might adversely impact human health and the environment.

E-beam and UV induced fabrication of CeO2, Eu2O3 and their mixed oxides with UO2

NASA Astrophysics Data System (ADS)

Pavelková, Tereza; Vaněček, Vojtěch; Jakubec, Ivo; Čuba, Václav

2016-07-01

CeO2, Eu2O3 and mixed oxides of CeO2-UO2, Eu2O3-UO2 were fabricated. The preparative method was based on the irradiation of aqueous solutions containing cerium/europium (and uranyl) nitrates and ammonium formate. In the course of irradiation, the solid phase (precursor) was precipitated. The composition of irradiated solutions significantly affected the properties of precursor formed in the course of the irradiation. However, subsequent heat treatment of (amorphous) precursors at temperatures ≤650 °C invariably resulted in the formation of powder oxides with well-developed nanocrystals with linear crystallite size 13-27 nm and specific surface area 10-46 m2 g-1. The applicability of both ionizing (e-beam) and non-ionizing (UV) radiation was studied.

Superconductive articles including cerium oxide layer

DOEpatents

Wu, X.D.; Muenchausen, R.E.

1993-11-16

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. 7 figures.

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.

Titanium dioxide nanoparticles cause genotoxicity in human lung epithelial cells

EPA Science Inventory

The use of engineered nanoparticles in consumer products is steadily increasing. However, the health effects of exposure to these nanoparticles are not thoroughly understood. This study investigated the genotoxicity of six titanium dioxide and two cerium oxide nanoparticles of va...

USE OF COMBUSTION SYNTHESIS IN PREPARING CERAMIC-MATRIX AND METAL-MATRIX COMPOSITE POWDERS

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

Weil, K. Scott; Hardy, John S.

A standard combustion-based approach typically used to synthesize nanosize oxide powders has been modified to prepare composite oxide-metal powders for subsequent densification via sintering or hot-pressing into ceramic- or metal-matrix composites. Copper and cerium nitrate salts were dissolved in the appropriate ratio in water and combined with glycine, then heated to cause autoignition. The ratio of glycine-to-total nitrate concentration was found to have the largest effect on the composition, agglomerate size, crystallite size, and dispersivity of phases in the powder product. After consolidation and sintering under reducing conditions, the resulting composite compact consists of a well-dispersed mixture of sub-micron sizemore » reinforcement particles in a fine-grained matrix.« less

Evaluation of the effect of valence state on cerium oxide nanoparticle toxicity following intratracheal instillation in rats

PubMed Central

Dunnick, Katherine M.; Morris, Anna M.; Badding, Melissa A.; Barger, Mark; Stefaniak, Aleksandr B.; Sabolsky, Edward M.; Leonard, Stephen S.

2016-01-01

Cerium (Ce) is becoming a popular metal for use in electrochemical applications. When in the form of cerium oxide (CeO2), Ce can exist in both 3 + and 4 + valence states, acting as an ideal catalyst. Previous in vitro and in vivo evidence have demonstrated that CeO2 has either anti- or pro-oxidant properties, possibly due to the ability of the nanoparticles to transition between valence states. Therefore, we chose to chemically modify the nanoparticles to shift the valence state toward 3+. During the hydrothermal synthesis process, 10 mol% gadolinium (Gd) and 20 mol% Gd, were substituted into the lattice of the CeO2 nanoparticles forming a perfect solid solution with various A-site valence states. These two Gd-doped CeO2 nanoparticles were compared to pure CeO2 nanoparticles. Preliminary characteristics indicated that doping results in minimal size and zeta potential changes but alters valence state. Following characterization, male Sprague-Dawley rats were exposed to 0.5 or 1.0 mg/kg nanoparticles via a single intratracheal instillation. Animals were sacrificed and bronchoalveolar lavage fluid and various tissues were collected to determine the effect of valence state and oxygen vacancies on toxicity 1-, 7-, or 84-day post-exposure. Results indicate that damage, as measured by elevations in lactate dehydrogenase, occurred within 1-day post-exposure and was sustained 7-day post-exposure, but subsided to control levels 84-day post-exposure. Furthermore, no inflammatory signaling or lipid peroxidation occurred following exposure with any of the nanoparticles. Our results implicate that valence state has a minimal effect on CeO2 nanoparticle toxicity in vivo. PMID:26898289

Brain suppression of AP-1 by inhaled diesel exhaust and reversal by cerium oxide nanoparticles.

PubMed

Lung, Shyang; Cassee, Flemming R; Gosens, Ilse; Campbell, Arezoo

2014-08-01

One of the uses of cerium oxide nanoparticles (nanoceria, CeO2) is as a diesel fuel additive to improve fuel efficiency. Gene/environment interactions are important determinants in the etiology of age-related disorders. Thus, it is possible that individuals on high-fat diet and genetic predisposition to vascular disease may be more vulnerable to the adverse health effects of particle exposure. The aim of this pilot study was to test the hypothesis that inhalation of diesel exhaust (DE) or diesel exhaust-containing cerium oxide nanoparticles (DCeE) induces stress in the brain of a susceptible animal model. Atherosclerotic prone, apolipoprotein E knockout (ApoE(-/-)) mice fed a high-fat diet, were exposed by inhalation to purified air (control), DE or DCeE. The stress-responsive transcription factor, activator protein-1 (AP-1), was significantly decreased in the cortical and subcortical fraction of the brain after DE exposure. The addition of nanoceria to the diesel fuel reversed this effect. The activation of another stress-related transcription factor (NF-κB) was not inhibited. AP-1 is composed of complexes of the Jun and/or Fos family of proteins. Exposure to DCeE caused c-Jun activation and this may be a mechanism by which addition of nanoceria to the fuel reversed the effect of DE exposure on AP-1 activation. This pilot study demonstrates that exposure to DE does impact the brain and addition of nanoceria may be protective. However, more extensive studies are necessary to determine how DE induced reduction of AP-1 activity and compensation by nanoceria impacts normal function of the brain.

In situ flow cell for combined X-ray absorption spectroscopy, X-ray diffraction, and mass spectrometry at high photon energies under solar thermochemical looping conditions

NASA Astrophysics Data System (ADS)

Rothensteiner, Matthäus; Jenni, Joel; Emerich, Hermann; Bonk, Alexander; Vogt, Ulrich F.; van Bokhoven, Jeroen A.

2017-08-01

An in situ/operando flow cell for transmission mode X-ray absorption spectroscopy (XAS), X-ray diffraction (XRD), and combined XAS/XRD measurements in a single experiment under the extreme conditions of two-step solar thermochemical looping for the dissociation of water and/or carbon dioxide was developed. The apparatus exposes materials to relevant conditions of both the auto-reduction and the oxidation sub-steps of the thermochemical cycle at ambient temperature up to 1773 K and enables determination of the composition of the effluent gases by online quadrupole mass spectrometry. The cell is based on a tube-in-tube design and is heated by means of a focusing infrared furnace. It was tested successfully for carbon dioxide splitting. In combined XAS/XRD experiments with an unfocused beam, XAS measurements were performed at the Ce K edge (40.4 keV) and XRD measurements at 64.8 keV and 55.9 keV. Furthermore, XRD measurements with a focused beam at 41.5 keV were carried out. Equimolar ceria-hafnia was auto-reduced in a flow of argon and chemically reduced in a flow of hydrogen/helium. Under reducing conditions, all cerium(iv) was converted to cerium(iii) and a cation-ordered pyrochlore-type structure was formed, which was not stable upon oxidation in a flow of carbon dioxide.

In situ flow cell for combined X-ray absorption spectroscopy, X-ray diffraction, and mass spectrometry at high photon energies under solar thermochemical looping conditions.

PubMed

Rothensteiner, Matthäus; Jenni, Joel; Emerich, Hermann; Bonk, Alexander; Vogt, Ulrich F; van Bokhoven, Jeroen A

2017-08-01

An in situ/operando flow cell for transmission mode X-ray absorption spectroscopy (XAS), X-ray diffraction (XRD), and combined XAS/XRD measurements in a single experiment under the extreme conditions of two-step solar thermochemical looping for the dissociation of water and/or carbon dioxide was developed. The apparatus exposes materials to relevant conditions of both the auto-reduction and the oxidation sub-steps of the thermochemical cycle at ambient temperature up to 1773 K and enables determination of the composition of the effluent gases by online quadrupole mass spectrometry. The cell is based on a tube-in-tube design and is heated by means of a focusing infrared furnace. It was tested successfully for carbon dioxide splitting. In combined XAS/XRD experiments with an unfocused beam, XAS measurements were performed at the Ce K edge (40.4 keV) and XRD measurements at 64.8 keV and 55.9 keV. Furthermore, XRD measurements with a focused beam at 41.5 keV were carried out. Equimolar ceria-hafnia was auto-reduced in a flow of argon and chemically reduced in a flow of hydrogen/helium. Under reducing conditions, all cerium(iv) was converted to cerium(iii) and a cation-ordered pyrochlore-type structure was formed, which was not stable upon oxidation in a flow of carbon dioxide.

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.

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.

Nanoceria as Antioxidant: Synthesis and Biomedical Applications

USDA-ARS?s Scientific Manuscript database

The therapeutic application of nanomaterials has been a focus of numerous studies in the past decade. Due to its unique redox properties, cerium oxide (ceria) is finding widespread use in the treatment of medical disorders caused by the reactive oxygen intermediates (ROI). The radical-scavenging rol...

Investigations of nano-particle toxicity and uptake of Cerium oxide and Titanium dioxide in Arabidopsis thaliana (L.)

EPA Science Inventory

The emergence of nanotechnology and incorporation of nanoparticles in consumer products necessitates risk assessment from an environmental and health safety standpoint. To date, very few studies have examined nanoparticle effects on terrestrial species, especially plants. In ...

Effects of the Physical Characteristics of Cerium Oxide on Plasma-Enhanced Tetraethylorthosiliate Removal Rate of Chemical Mechanical Polishing for Shallow Trench Isolation

NASA Astrophysics Data System (ADS)

Kim, Sang-Kyun; Paik, Ungyu; Oh, Seong-Geun; Park, Yong-Kook; Katoh, Takeo; Park, Jea-Gun

2003-03-01

Ceria powders were synthesized by two different methods, solid-state displacement reaction and wet chemical precipitation, and the influence of the physical characteristics of cerium oxide on the removal rate of plasma-enhanced tetraethylorthosilicate (PETEOS) and chemical vapor deposition (CVD) nitride films in chemical mechanical planarization (CMP) was investigated. The fundamental physicochemical property and electrokinetic behavior of ceria particles in aqueous suspending media were investigated to identify the correlation between the colloidal property of ceria and the CMP performance. The surface potentials of two different ceria particles are found to have different isoelectric point (pHiep) values and differences in physical properties of ceria particles such as porosity and density were found to be the key parameters in CMP of PETEOS films. Ceria powders synthesized by the solid-state displacement reaction method yielded a higher removal rate of PETEOS and higher selectivity than powders synthesized by the wet chemical precipitation method.

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. © 2011 American Chemical Society

Synthesis of nanocrystalline CeO{sub 2} particles by different emulsion methods

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

Supakanapitak, Sunisa; Boonamnuayvitaya, Virote; Jarudilokkul, Somnuk, E-mail: somnuk.jar@kmutt.ac.th

2012-05-15

Cerium oxide nanoparticles were synthesized using three different methods of emulsion: (1) reversed micelle (RM); (2) emulsion liquid membrane (ELM); and (3) colloidal emulsion aphrons (CEAs). Ammonium cerium nitrate and polyoxyethylene-4-lauryl ether (PE4LE) were used as cerium and surfactant sources in this study. The powder was calcined at 500 Degree-Sign C to obtain CeO{sub 2}. The effect of the preparation procedure on the particle size, surface area, and the morphology of the prepared powders were investigated. The obtained powders are highly crystalline, and nearly spherical in shape. The average particle size and the specific surface area of the powders frommore » the three methods were in the range of 4-10 nm and 5.32-145.73 m{sup 2}/g, respectively. The CeO{sub 2} powders synthesized by the CEAs are the smallest average particle size, and the highest surface area. Finally, the CeO{sub 2} prepared by the CEAs using different cerium sources and surfactant types were studied. It was found that the surface tensions of cerium solution and the type of surfactant affect the particle size of CeO{sub 2}. - Graphical Abstract: The emulsion droplet size distribution and the TEM images of CeO{sub 2} prepared by different methods: reversed micelle (RM), emulsion liquid membrane (ELM) and colloidal emulsion aphrons (CEAs). Highlights: Black-Right-Pointing-Pointer Nano-sized CeO{sub 2} was successfully prepared by three different emulsion methods. Black-Right-Pointing-Pointer The colloidal emulsion aphrons method producing CeO{sub 2} with the highest surface area. Black-Right-Pointing-Pointer The surface tensions of a cerium solution have slightly effect on the particle size. Black-Right-Pointing-Pointer The size control could be interpreted in terms of the adsorption of the surfactant.« less

In situ supported MnOx-CeOx on carbon nanotubes for the low-temperature selective catalytic reduction of NO with NH3

NASA Astrophysics Data System (ADS)

Zhang, Dengsong; Zhang, Lei; Shi, Liyi; Fang, Cheng; Li, Hongrui; Gao, Ruihua; Huang, Lei; Zhang, Jianping

2013-01-01

The MnOx and CeOx were in situ supported on carbon nanotubes (CNTs) by a poly(sodium 4-styrenesulfonate) assisted reflux route for the low-temperature selective catalytic reduction (SCR) of NO with NH3. X-Ray diffraction (XRD), transmission electron microscopy (TEM), high-resolution TEM (HRTEM), X-ray photoelectron spectroscopy (XPS), H2 temperature-programmed reduction (H2-TPR) and NH3 temperature-programmed desorption (NH3-TPD) have been used to elucidate the structure and surface properties of the obtained catalysts. It was found that the in situ prepared catalyst exhibited the highest activity and the most extensive operating-temperature window, compared to the catalysts prepared by impregnation or mechanically mixed methods. The XRD and TEM results indicated that the manganese oxide and cerium oxide species had a good dispersion on the CNT surface. The XPS results demonstrated that the higher atomic concentration of Mn existed on the surface of CNTs and the more chemisorbed oxygen species exist. The H2-TPR results suggested that there was a strong interaction between the manganese oxide and cerium oxide on the surface of CNTs. The NH3-TPD results demonstrated that the catalysts presented a larger acid amount and stronger acid strength. In addition, the obtained catalysts exhibited much higher SO2-tolerance and improved the water-resistance as compared to that prepared by impregnation or mechanically mixed methods.The MnOx and CeOx were in situ supported on carbon nanotubes (CNTs) by a poly(sodium 4-styrenesulfonate) assisted reflux route for the low-temperature selective catalytic reduction (SCR) of NO with NH3. X-Ray diffraction (XRD), transmission electron microscopy (TEM), high-resolution TEM (HRTEM), X-ray photoelectron spectroscopy (XPS), H2 temperature-programmed reduction (H2-TPR) and NH3 temperature-programmed desorption (NH3-TPD) have been used to elucidate the structure and surface properties of the obtained catalysts. It was found that the in situ prepared catalyst exhibited the highest activity and the most extensive operating-temperature window, compared to the catalysts prepared by impregnation or mechanically mixed methods. The XRD and TEM results indicated that the manganese oxide and cerium oxide species had a good dispersion on the CNT surface. The XPS results demonstrated that the higher atomic concentration of Mn existed on the surface of CNTs and the more chemisorbed oxygen species exist. The H2-TPR results suggested that there was a strong interaction between the manganese oxide and cerium oxide on the surface of CNTs. The NH3-TPD results demonstrated that the catalysts presented a larger acid amount and stronger acid strength. In addition, the obtained catalysts exhibited much higher SO2-tolerance and improved the water-resistance as compared to that prepared by impregnation or mechanically mixed methods. Electronic supplementary information (ESI) available: SEM images and EDS analysis, TEM images, and XPS spectrum of samples. See DOI: 10.1039/c2nr33006g

Effects of Dopant Ionic Radius on Cerium Reduction in Epitaxial Cerium Oxide Thin Films

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

Yang, Nan; Orgiani, Pasquale; Di Bartolomeo, Elisabetta

The role of trivalent rare-earth dopants in ceria epitaxial films on surface ion exchange reactivity and ion conductivity has been systematically studied. Single-crystal epitaxial films with unique crystal orientation and micro-structure nature have allowed us to rule out the influence of structural defects on both transport and surface ion exchange properties. The films conductivities were larger than those reported in literature for both polycrystalline ceramic pellets and crystalline films. An increase in oxygen vacancies and Ce 3+ concentration while decreasing the dopant ionic radius from La 3+ to Yb 3+ was observed, thus explaining the measured increased activation energy andmore » enhanced surface reactivity. The more significant ability of smaller dopant ionic radius in releasing the stress strength induced by the larger Ce 3+ ionic radius allows promoting the formation of oxygen vacancies and Ce 3+, which are two precious species in determining the efficiency of ion transport and surface ion exchange processes. This can open new perspectives in designing ceria-based materials in tailoring functional properties, either ion migration or surface reactivity, by rational cation substitutions.« less

Effects of Dopant Ionic Radius on Cerium Reduction in Epitaxial Cerium Oxide Thin Films

DOE PAGES

Yang, Nan; Orgiani, Pasquale; Di Bartolomeo, Elisabetta; ...

2017-04-17

The role of trivalent rare-earth dopants in ceria epitaxial films on surface ion exchange reactivity and ion conductivity has been systematically studied. Single-crystal epitaxial films with unique crystal orientation and micro-structure nature have allowed us to rule out the influence of structural defects on both transport and surface ion exchange properties. The films conductivities were larger than those reported in literature for both polycrystalline ceramic pellets and crystalline films. An increase in oxygen vacancies and Ce 3+ concentration while decreasing the dopant ionic radius from La 3+ to Yb 3+ was observed, thus explaining the measured increased activation energy andmore » enhanced surface reactivity. The more significant ability of smaller dopant ionic radius in releasing the stress strength induced by the larger Ce 3+ ionic radius allows promoting the formation of oxygen vacancies and Ce 3+, which are two precious species in determining the efficiency of ion transport and surface ion exchange processes. This can open new perspectives in designing ceria-based materials in tailoring functional properties, either ion migration or surface reactivity, by rational cation substitutions.« less

Cardioprotective effect of cerium oxide nanoparticles in monocrotaline rat model of pulmonary hypertension: A possible implication of endothelin-1.

PubMed

Nassar, Seham Zakaria; Hassaan, Passainte S; Abdelmonsif, Doaa A; ElAchy, Samar Nabil

2018-05-15

Cerium oxide nanoparticles (CeO 2 NPs) have been recently introduced into the medical field for their antioxidant properties. The ability of CeO 2 NPs alone or in combination with spironolactone (SP) to attenuate monocrotaline (MCT)-induced pulmonary hypertension and associated right ventricular hypertrophy was studied in rats. A special emphasis was given to endothelin-1 pathway. Pulmonary hypertension was induced in albino rats by a single subcutaneous injection of MCT (60 mg/kg). Rats received either single CeO 2 NPs therapy or combined therapy with SP for 2 weeks. CeO 2 NPs improved pulmonary function tests with concomitant decrease in serum endothelin-1 and pulmonary expression of endothelin-1 and its receptor ETAR. Besides, CeO 2 NPs diminished MCT-induced right ventricular hypertrophy and reduced cardiac oxidative stress and apoptosis. CeO 2 NPs could improve pulmonary hypertension and associated right ventricular hypertrophy with no additive value for SP. Besides being an antioxidant, CeO 2 NPs work through endothelin-1 pathway to improve pulmonary hypertension. Copyright © 2018 Elsevier Inc. All rights reserved.

Accessing the genomic effects of naked nanoceria in murine neuronal cells.

PubMed

Lee, Tin-Lap; Raitano, Joan M; Rennert, Owen M; Chan, Siu-Wai; Chan, Wai-Yee

2012-07-01

Cerium oxide nanoparticles (nanoceria) are engineered nanoparticles whose versatility is due to their unique redox properties. We and others have demonstrated that naked nanoceria can act as antioxidants to protect cells against oxidative damage. Although the redox properties may be beneficial, the genome-wide effects of nanoceria on gene transcription and associated biological processes remain elusive. Here we applied a functional genomic approach to examine the genome-wide effects of nanoceria on global gene transcription and cellular functions in mouse neuronal cells. Importantly, we demonstrated that nanoceria induced chemical- and size-specific changes in the murine neuronal cell transcriptome. The nanoceria contributed more than 83% of the population of uniquely altered genes and were associated with a unique spectrum of genes related to neurological disease, cell cycle control, and growth. These observations suggest that an in-depth assessment of potential health effects of naked nanoceria and other naked nanoparticles is both necessary and imminent. Cerium oxide nanoparticles are important antioxidants, with potential applications in neurodegenerative conditions. This team of investigators demonstrated the genomic effects of nanoceria, showing that it induced chemical- and size-specific changes in the murine neuronal cell transcriptome. Published by Elsevier Inc.

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

Evaluation of in vitro cytotoxicity, biocompatibility, and changes in the expression of apoptosis regulatory proteins induced by cerium oxide nanocrystals

NASA Astrophysics Data System (ADS)

Khan, Shahanavaj; Ansari, Anees A.; Rolfo, Christian; Coelho, Andreia; Abdulla, Maha; Al-Khayal, Khayal; Ahmad, Rehan

2017-12-01

Cerium oxide nanocrystals (CeO2-NCs) exhibit superoxide dismutase and catalase mimetic activities. Based on these catalytic activities, CeO2-NCs have been suggested to have the potential to treat various diseases. The crystalline size of these materials is an important factor that influences the performance of CeO2-NCs. Previous reports have shown that several metal-based nanocrystals, including CeO2-NCs, can induce cytotoxicity in cancer cells. However, the underlying mechanisms have remained unclear. To characterize the anticancer activities of CeO2-NCs, several assays related to the mechanism of cytotoxicity and induction of apoptosis has been performed. Here, we have carried out a systematic study to characterize CeO2-NCs phase purity (X-ray diffraction), morphology (electron microscopy), and optical features (optical absorption, Raman scattering, and photoluminescence) to better establish their potential as anticancer drugs. Our study revealed anticancer effects of CeO2-NCs in HT29 and SW620 colorectal cancer cell lines with half-maximal inhibitory concentration (IC50) values of 2.26 and 121.18 μg ml-1, respectively. Reductions in cell viability indicated the cytotoxic potential of CeO2-NCs in HT29 cells based on inverted and florescence microscopy assessments. The mechanism of cytotoxicity confirmed by estimating possible changes in the expression levels of Bcl2, BclxL, Bax, PARP, cytochrome c, and β-actin (control) proteins in HT29 cells. Down-regulation of Bcl2 and BclxL and up-regulation of Bax, PARP, and cytochrome c proteins suggested the significant involvement of CeO2-NCs exposure in the induction of apoptosis. Furthermore, biocompatibility assay showed minimum effect of CeO2-NCs on human red blood cells.

Structure and corrosion behavior of sputter deposited cerium oxide based coatings with various thickness on Al 2024-T3 alloy substrates

NASA Astrophysics Data System (ADS)

Liu, Yuanyuan; Huang, Jiamu; Claypool, James B.; Castano, Carlos E.; O'Keefe, Matthew J.

2015-11-01

Cerium oxide based coatings from ∼100 to ∼1400 nm in thickness were deposited onto Al 2024-T3 alloy substrates by magnetron sputtering of a 99.99% pure CeO2 target. The crystallite size of CeO2 coatings increased from 15 nm to 46 nm as the coating thickness increased from ∼100 nm to ∼1400 nm. The inhomogeneous lattice strain increased from 0.36% to 0.91% for the ∼100 nm to ∼900 nm thick coatings and slightly decreased to 0.89% for the ∼1400 nm thick coating. The highest adhesion strength to Al alloy substrates was for the ∼210 nm thick coating, due to a continuous film coverage and low internal stress. Electrochemical measurements indicated that sputter deposited crystalline CeO2 coatings acted as physical barriers that provide good cathodic inhibition for Al alloys in saline solution. The ∼900 nm thick CeO2 coated sample had the best corrosion performance that increased the corrosion resistance by two orders magnitude and lowered the cathodic current density 30 times compared to bare Al 2024-T3 substrates. The reduced defects and exposed surface, along with suppressed charge mobility, likely accounts for the improved corrosion performance as coating thickness increased from ∼100 nm to ∼900 nm. The corrosion performance decreased for ∼1400 nm thick coatings due in part to an increase in coating defects and porosity along with a decrease in adhesion strength.

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

Cassee, Flemming R., E-mail: flemming.cassee@rivm.nl; Campbell, Arezoo, E-mail: acampbell@westernu.edu; Boere, A. John F., E-mail: john.boere@rivm.nl

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} tomore » 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.« less

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. Published by Oxford University Press on behalf of the Society of Toxicology 2014. This work is written by US Government employees and is in the public domain in the US.

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...

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...

Manipulating the Rate-Limiting Step in Water Oxidation Catalysis by Ruthenium Bipyridine–Dicarboxylate Complexes

DOE PAGES

Shaffer, David W.; Xie, Yan; Szalda, David J.; ...

2016-11-01

In order to gain a deeper mechanistic understanding of water oxidation by [(bda)Ru(L) 2] catalysts (bdaH 2 = [2,2'-bipyridine]-6,6'-dicarboxylic acid; L = pyridine-type ligand), a series of modified catalysts with one and two trifluoromethyl groups in the 4 position of the bda 2– ligand was synthesized and studied using stopped-flow kinetics. The additional $-$CF 3 groups increased the oxidation potentials for the catalysts and enhanced the rate of electrocatalytic water oxidation at low pH. Stopped-flow measurements of cerium(IV)-driven water oxidation at pH 1 revealed two distinct kinetic regimes depending on catalyst concentration. At relatively high catalyst concentration (ca. ≥10 –4more » M), the rate-determining step (RDS) was a proton-coupled oxidation of the catalyst by cerium(IV) with direct kinetic isotope effects (KIE > 1). At low catalyst concentration (ca. ≤10 –6 M), the RDS was a bimolecular step with k H/k D ≈ 0.8. The results support a catalytic mechanism involving coupling of two catalyst molecules. The rate constants for both RDSs were determined for all six catalysts studied. The presence of $-$CF 3 groups had inverse effects on the two steps, with the oxidation step being fastest for the unsubstituted complexes and the bimolecular step being faster for the most electron-deficient complexes. Finally, though the axial ligands studied here did not significantly affect the oxidation potentials of the catalysts, the nature of the ligand was found to be important not only in the bimolecular step but also in facilitating electron transfer from the metal center to the sacrificial oxidant.« less

Antioxidant and antigenotoxic properties of CeO2 NPs and cerium sulphate: Studies with Drosophila melanogaster as a promising in vivo model.

PubMed

Alaraby, Mohamed; Hernández, Alba; Annangi, Balasubramanyam; Demir, Esref; Bach, Jordi; Rubio, Laura; Creus, Amadeu; Marcos, Ricard

2015-01-01

Although in vitro approaches are the most used for testing the potential harmful effects of nanomaterials, in vivo studies produce relevant information complementing in vitro data. In this context, we promote the use of Drosophila melanogaster as a suitable in vivo model to characterise the potential risks associated to nanomaterials exposure. The main aim of this study was to evaluate different biological effects associated to cerium oxide nanoparticles (Ce-NPs) and cerium (IV) sulphate exposure. The end-points evaluated were egg-to-adult viability, particles uptake through the intestinal barrier, gene expression and intracellular reactive oxygen species (ROS) production by haemocytes, genotoxicity and antigenotoxicity. Transmission electron microscopy images showed internalisation of Ce-NPs by the intestinal barrier and haemocytes, and significant expression of Hsp genes was detected. In spite of these findings, neither toxicity nor genotoxicity related to both forms of cerium were observed. Interestingly, Ce-NPs significantly reduced the genotoxic effect of potassium dichromate and the intracellular ROS production. No morphological malformations were detected after larvae treatment. This study highlights the importance of D. melanogaster as animal model in the study of the different biological effects caused by nanoparticulated materials, at the time that shows its usefulness to study the role of the intestinal barrier in the transposition of nanomaterials entering via ingestion.

Solubility of Nanocrystalline Cerium Dioxide: Experimental Data and Thermodynamic Modeling

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

Plakhova, Tatiana V.; Romanchuk, Anna Yu.; Yakunin, Sergey N.

For this study, ultrafine 5 nm ceria isotropic nanoparticles were prepared using the rapid chemical precipitation approach from cerium(III) nitrate and ammonium hydroxide aqueous solutions. The as-prepared nanoparticles were shown to contain predominantly Ce(IV) species. The solubility of nanocrystalline CeO 2 at several pH values was determined using ICP-MS and radioactive tracer methods. Phase composition of the ceria samples remained unchanged upon partial dissolution, while the shape of the particles changed dramatically, yielding nanorods under neutral pH conditions. According to X-ray absorption spectroscopy investigation of the supernatant, Ce(III) was the main cerium species in solution at pH < 4. Basedmore » on the results obtained, a reductive dissolution model was used for data interpretation. According to this model, the solubility product for ceria nanoparticles was determined to be log K sp = -59.3 ± 0.3 in 0.01 M NaClO 4. Taken together, our results show that the pH dependence of ceria anti- and pro-oxidant activity can be related to the dissolution of CeO 2 in aqueous media.« less

Solubility of Nanocrystalline Cerium Dioxide: Experimental Data and Thermodynamic Modeling

DOE PAGES

Plakhova, Tatiana V.; Romanchuk, Anna Yu.; Yakunin, Sergey N.; ...

2016-09-12

For this study, ultrafine 5 nm ceria isotropic nanoparticles were prepared using the rapid chemical precipitation approach from cerium(III) nitrate and ammonium hydroxide aqueous solutions. The as-prepared nanoparticles were shown to contain predominantly Ce(IV) species. The solubility of nanocrystalline CeO 2 at several pH values was determined using ICP-MS and radioactive tracer methods. Phase composition of the ceria samples remained unchanged upon partial dissolution, while the shape of the particles changed dramatically, yielding nanorods under neutral pH conditions. According to X-ray absorption spectroscopy investigation of the supernatant, Ce(III) was the main cerium species in solution at pH < 4. Basedmore » on the results obtained, a reductive dissolution model was used for data interpretation. According to this model, the solubility product for ceria nanoparticles was determined to be log K sp = -59.3 ± 0.3 in 0.01 M NaClO 4. Taken together, our results show that the pH dependence of ceria anti- and pro-oxidant activity can be related to the dissolution of CeO 2 in aqueous media.« less

Comparative DNA damage and transcriptomic effects of engineered nanoparticles in human lung cells in vitro

EPA Science Inventory

A series of six titanium dioxide and two cerium oxide engineered nanomaterials were assessed for their ability to induce cytotoxicity, reactive oxygen species (ROS), various types of DNA damage, and transcriptional changes in human respiratory BEAS-2B cells exposed in vitro at se...

Health Effects Associated with Inhalation Exposure to Diesel Emission Generated with and without CeO2 Nano Fuel Additive

EPA Science Inventory

Diesel exhaust (DE) exposure induces adverse cardiopulmonary effects. Addition of nano cerium (Ce) oxide additive to diesel fuel (DECe) increases fuel burning efficiency resulting in altered emission characteristics and potentially altered health effects. We hypothesized that inh...

Cerium Oxide Nanoparticle Nose-Only Inhalation Exposures Using a Low-Sample-Consumption String Generator

EPA Science Inventory

There is a critical need to assess the health effects associated with exposure of commercially produced NPs across the size ranges reflective of that detected in the industrial sectors that are generating, as well as incorporating, NPs into products. Generation of stable and low ...

Near-Road Modeling and Measurement of Particles Generated by Nanoparticle Diesel Fuel Additive Use

EPA Science Inventory

Cerium oxide (ceria) nanoparticles (n-Ce) are used as a fuel-borne catalyst in diesel engines to reduce particulate emissions, yet the environmental and human health impacts of the ceria-doped diesel exhaust aerosols are not well understood. To bridge the gap between emission mea...

Superconducting composite with multilayer patterns and multiple buffer layers

DOEpatents

Wu, X.D.; Muenchausen, R.E.

1993-10-12

An article of manufacture is described including a substrate, a patterned interlayer of a material selected from the group consisting of magnesium oxide, barium-titanium oxide or barium-zirconium oxide, the patterned interlayer material overcoated with a secondary interlayer material of yttria-stabilized zirconia or magnesium-aluminum oxide, upon the surface of the substrate whereby an intermediate article with an exposed surface of both the overcoated patterned interlayer and the substrate is formed, a coating of a buffer layer selected from the group consisting of cerium oxide, yttrium oxide, curium oxide, dysprosium oxide, erbium oxide, europium oxide, iron oxide, gadolinium oxide, holmium oxide, indium oxide, lanthanum oxide, manganese oxide, lutetium oxide, neodymium oxide, praseodymium oxide, plutonium oxide, samarium oxide, terbium oxide, thallium oxide, thulium oxide, yttrium oxide and ytterbium oxide over the entire exposed surface of the intermediate article, and, a ceramic superconductor. 5 figures.

An investigation of the use of cerium and polyhedral oligomeric silsesquioxanes for the protection of polymeric epoxy compounds in the low Earth orbit environment

NASA Astrophysics Data System (ADS)

Piness, Jessica Miriam

Low Earth orbit presents many hazards for composites including atomic oxygen, UV radiation, thermal cycling, micrometeoroids, and high energy protons. Atomic oxygen and vacuum ultraviolet radiation are of concern for space-bound polymeric materials as they degrade the polymers used as matrices for carbon fiber composites, which are used in satellites and space vehicles due to their high strength to weight ratios. Epoxy-amine thermosets comprise a common class of matrix due to processability and good thermal attributes. Polyhedral oligomeric silsesquioxanes (POSS) have shown the ability to reduce erosion in polyimides, polyurethanes, and other polymers when exposed to atomic oxygen. The POSS particle is composed of a SiO1.5 cage from which up to eight organic pendant groups are attached at the silicon corners of the cage. POSS reduced atomic oxygen impact on polymers by a process known as glassification wherein the organic pendants are removed from the cage upon atomic oxygen exposure and then the cage rearranges to a passive silica network. In addition, POSS shows good UV absorbance in the UVb and UVc ranges and POSS can aid dispersion of titanium dioxide in a nanocomposite. In this work, Chapter I focuses on hazards in low Earth orbit, strategies for protecting organic material in orbit, and the capabilities of POSS. Chapter II details the experimental practices used in this work. Chapter III focuses on work to induce POSS phase separation and layering at the surface of an epoxy-amine thermoset. Generally, POSS is dispersed throughout a nanocomposite, and in the process of erosion by atomic oxygen, some polymer mass loss is lost before enough POSS is exposed to begin glassification. Locating POSS at a surface of composite could possibly reduce this mass loss and the objective of this research was to investigate the formation of POSS-rich surfaces. Three POSS derivatives with different pendant groups were chosen. The POSS derivatives had a range of miscibilities with the epoxy-amine matrix. A sedimented layer of the most incompatible POSS moiety was observed at the bottom of bars at the highest loading level of 5 wt% POSS. It was concluded that POSS could form a sedimented layer in this epoxy during cure. Epoxy amine materials containing POSS derivatives were tested by exposure to atomic oxygen at NASA Glenn Research Center with each POSS derivative present in separate samples at 2.5 wt% loading levels. Mass loss did not decrease against an unfilled control and glassification was not observed, leading to the conclusion that POSS could not be effectively concentrated at a surface to reduce degradation given the methods used. Taking this into account, the study transitioned into seeking ways to integrate highly UV absorbent cerium compounds with POSS. This part of the study is reported in Chapter IV. It was anticipated that POSS with a polar pendant group would interact through intermolecular forces with cerium (IV) oxide and produce a suspension that could be cured at the surface of polymers. However, in every experiment, the cerium (IV) oxide was not dispersed. However, a homogeneous dispersion of a cerium-containing compound was achieved by combining trisilanol phenyl POSS with cerium (III) nitrate hexahydrate. NMR and mass spectrometry showed that the mixture of Cerium nitrate and trisilanol phenyl POSS did not result in the formation of a chemical compound but FTIR studies indicated the presence of hydrogen bonding between the POSS silanols and cerium-associated water. The resulting material was termed "CePOSS". CePOSS was more UV absorbent in the UVc region than POSS or other cerium compounds as measured by solution UV-vis spectroscopy. In addition, CePOSS could be mixed into a POSS-epoxy coating, after pre-blending with poly(ethylene glycol) POSS, to produce films that were essentially opaque in the UV region below a wavelength of about 300 nm, and transparent in the visible region above 300 nm. The discovery of a 'window of transparency' in the visible region is significant in view of the fact that the epoxy-amine polymers, sans the POSS and cerium additives, were opaque across the entire UV/ visible range. The investigation of the UV transmittance and glassification response of these CePOSS-POSS-epoxy films is described in Chapter V. UV transmittance of the POSS-epoxy coating was predicted to decrease below 275 nm with the presence of CePOSS given the solution UV-vis spectroscopy results. However, there was no difference seen in transmittance between coatings with and without CePOSS below 275 nm. The transparent region above 300 nm was seen in all samples with any type of POSS. In addition, UV/ozone exposure was completed on epoxy, POSS-epoxy, and CePOSS-POSS-epoxy coatings to examine the effect of cerium on POSS glassification. Oxidation was achieved even in the presence of CePOSS as verified by x-ray photoelectron spectroscopy, scanning electron microscopy, and contact angle. Finally, UV transmittance was done on pre and post exposed materials.

International strategic minerals inventory summary report; rare-earth oxides

USGS Publications Warehouse

Jackson, W.D.; Christiansen, Grey

1993-01-01

Bastnaesite, monazite, and xenotime are currently the most important rare-earth minerals. Bastnaesite occurs as a primary mineral in carbonatites. Monazite and xenotime also can be found in primary deposits but are recovered principally from heavy-mineral placers that are mined for titanium or tin. Each of these minerals has a different composition of the 15 rare-earth elements. World resources of economically exploitable rare-earth oxides (REO) are estimated at 93.4 million metric tons in place, composed of 93 percent in primary deposits and 7 percent in placers. The average mineral composition is 83 percent bastnaesite, 13 percent monazite, and 4 percent of 10 other minerals. Annual global production is about 67,000 metric tons of which 41 percent is from placers and 59 percent is from primary deposits; mining methods consist of open pits (94 percent) and dredging (6 percent). This output could be doubled if the operations that do not currently recover rare earths would do so. Resources are more than sufficient to meet the demand for the predictable future. About 52 percent of the world's REO resources are located in China. Ranking of other countries is as follows: Namibia (22 percent), the United States (15 percent), Australia (6 percent), and India (3 percent); the remainder is in several other countries. Conversely, 38 percent of the production is in China, 33 percent in the United States, 12 percent in Australia, and 5 percent each in Malaysia and India. Several other countries, including Brazil, Canada, South Africa, Sri Lanka, and Thailand, make up the remainder. Markets for rare earths are mainly in the metallurgical, magnet, ceramic, electronic, chemical, and optical industries. Rare earths improve the physical and rolling properties of iron and steel and add corrosion resistance and strength to structural members at high temperatures. Samarium and neodymium are used in lightweight, powerful magnets for electric motors. Cerium and yttrium increase the density and heat resistance of sintered ceramics. Yttrium and gadolinium contribute to the efficiency of electronic switches and sensors. Cerium improves the effectiveness of catalysts in the petroleum and automotive industries. Cerium oxides speed glass melting and are used to polish glass by chemical, rather than mechanical, means. Cerium, europium, terbium, and yttrium, as phosphoric compounds, promote the vivid colors of television screens. Consumption of rare earths is expected to grow by about 2.6 percent per year.

A fully spray-coated fuel cell membrane electrode assembly using Aquivion ionomer with a graphene oxide/cerium oxide interlayer

NASA Astrophysics Data System (ADS)

Breitwieser, Matthias; Bayer, Thomas; Büchler, Andreas; Zengerle, Roland; Lyth, Stephen M.; Thiele, Simon

2017-05-01

A novel multilayer membrane electrode assembly (MEA) for polymer electrolyte membrane fuel cells (PEMFCs) is fabricated in this work, within a single spray-coating device. For the first time, direct membrane deposition is used to fabricate a PEMFC by spraying the short-side-chain ionomer Aquivion directly onto the gas diffusion electrodes. The fully sprayed MEA, with an Aquivion membrane 10 μm in thickness, achieved a high power density of 1.6 W/cm2 for H2/air operation at 300 kPaabs. This is one of the highest reported values for thin composite membranes operated in H2/air atmosphere. By the means of confocal laser scanning microscopy, individual carbon fibers from the gas diffusion layer are identified to penetrate through the micro porous layer (MPL), likely causing a low electrical cell resistance in the range of 150 Ω cm2 through the thin sprayed membranes. By spraying a 200 nm graphene oxide/cerium oxide (GO/CeO2) interlayer between two layers of Aquivion ionomer, the impact of the electrical short is eliminated and the hydrogen crossover current density is reduced to about 1 mA/cm2. The peak power density of the interlayer-containing MEA drops only by 10% compared to a pure Aquivion membrane of similar thickness.

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

On the Use of Thermal NF3 as the Fluorination and Oxidation Agent in Treatment of Used Nuclear Fuels

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

Scheele, Randall D.; McNamara, Bruce K.; Casella, Andrew M.

2012-05-01

This paper presents results of our investigation on the use of nitrogen trifluoride as the fluorination or fluorination/oxidation agent for use in a process for separating valuable constituents from used nuclear fuels by employing the volatility of many transition metal and actinide fluorides. Nitrogen trifluoride is less chemically and reactively hazardous than the hazardous and aggressive fluorinating agents used to prepare uranium hexafluoride and considered for fluoride volatility based nuclear fuels reprocessing. In addition, nitrogen trifluoride’s less aggressive character may be used to separate the volatile fluorides from used fuel and from themselves based on the fluorination reaction’s temperature sensitivitymore » (thermal tunability) rather than relying on differences in sublimation/boiling temperature and sorbents. Our thermodynamic calculations found that nitrogen trifluoride has the potential to produce volatile fission product and actinide fluorides from candidate oxides and metals. Our simultaneous thermogravimetric and differential thermal analyses found that the oxides of lanthanum, cerium, rhodium, and plutonium fluorinated but did not form volatile fluorides and that depending on temperature volatile fluorides formed from the oxides of niobium, molybdenum, ruthenium, tellurium, uranium, and neptunium. We also demonstrated near-quantitative removal of uranium from plutonium in a mixed oxide.« less

Negative cerium anomalies in manganese (hydr)oxide precipitates due to cerium oxidation in the presence of dissolved siderophores

NASA Astrophysics Data System (ADS)

Kraemer, Dennis; Tepe, Nathalie; Pourret, Olivier; Bau, Michael

2017-01-01

We present experimental results on the sorption behavior of rare earth elements and yttrium (REY) on precipitating manganese (hydr)oxide in the presence of the biogenic siderophore desferrioxamine B (DFOB). In marked contrast to inorganic systems, where preferential adsorption of HREY and depletion of LREY is commonly observed in manganese (hydr)oxide precipitates, sorption of REY in presence of the DFOB siderophore leads to HREY-depleted and LREY-enriched patterns in the precipitates. Moreover, our data indicate that surface oxidation of Ce(III) to Ce(IV) during sorption onto manganese (hydr)oxides and the resulting development of a positive Ce anomaly, which are commonly observed in inorganic experiments, are prevented in the presence of DFOB. Instead, Ce(III) is oxidized to Ce(IV) but associated with the dissolved desferrioxamine B which forms complexes with Ce(IV), that are at least twenty orders of magnitude more stable than those with Ce(III) and REY(III). The overall result is the formation of a positive Ce anomaly in the solution and a negative Ce anomaly in the Mn (hydr)oxides. The distribution of the strictly trivalent REY and Eu(III) between the manganese (hydr)oxide phase and the remaining ambient solution mimics the distribution of published stability constants for complexes of REY(III) with DFOB, i.e. the heavy REY form more stable complexes with the ligand and hence are better shielded from sorption than the LREY. Surface complexation modeling corroborates our experimental results. Negative Ce anomalies in Mn precipitates have been described from biogenic Mn oxides. Our results provide experimental evidence for the development of negative Ce anomalies in abiogenic Mn (hydr)oxide precipitates and show that the presence of the widespread siderophore desferrioxamine B during mineral precipitation results in HREY-depleted Mn (hydr)oxides with negative Ce anomalies.

Nano-sized Mn3O4 and β-MnOOH from the decomposition of β-cyclodextrin-Mn: 2. The water-oxidizing activities.

PubMed

Najafpour, Mohammad Mahdi; Mostafalu, Ramin; Hołyńska, Małgorzata; Ebrahimi, Foad; Kaboudin, Babak

2015-11-01

Nano-sized Mn oxides contain Mn3O4, β-MnOOH and Mn2O3 have been prepared by a previously reported method using thermal decomposition of β-cyclodextrin-Mn complexes. In the next step, the water-oxidizing activities of these Mn oxides using cerium(IV) ammonium nitrate as a chemical oxidant are studied. The turnover frequencies for β-MnO(OH) and Mn3O4 are 0.24 and 0.01-0.17 (mmol O2/mol Mns), respectively. Subsequently, water-oxidizing activities of these compounds are compared to the other previously reported Mn oxides. Important factors affecting water oxidation by these Mn oxides are also discussed. Copyright © 2015 Elsevier B.V. All rights reserved.

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%.

New Scintillator Materials (K2CeBr5) and (Cs2CeBr5)

NASA Technical Reports Server (NTRS)

Hawrami, R.; Volz, M. P.; Batra, A. K.; Aggarwal, M. D.; Roy, U. N.; Groza, M.; Burger, A.; Cherepy, Nerine; Niedermayr, Thomas; Payne, Stephen A.

2008-01-01

Cesium cerium bromide (Cs2CeBr5) and potassium cerium bromide (K2CeBr5) are new scintillator materials for X-ray and gamma ray detector applications. Recently halide scintillator materials, such as Ce doped lanthanum bromide has been proved to be very important material for the same purpose. These materials are highly hygroscopic; a search for high light yield non-hygroscopic materials was highly desirable to advance the scintillator technology. In this paper, we are reporting the crystal growth of novel scintillator materials, cesium cerium bromide (Cs2CeBr5) and potassium cerium bromide (K2CeBr5). Crystals were successfully grown from the melt using the vertical Bridgman-Stockbarger technique, in a comparison with the high performance LaBr3 or LaCl3 crystals, cerium based alkali halides crystals, (Cs2CeBr5) and (K2CeBr5) have similar scintillation properties, while being much less hygroscopic. Furthermore, cesium based compounds will not suffer from the self-activity present in potassium and lanthanum compounds. However the Cs2CeBr5 crystals did not grow properly probably due to non-congruent melting or to some phase transition during cooling. Keywords." Scintillator materials; Ce3+; Energy resolution; Light yield; K2CeBr5

Transcriptome Changes in Douglas-fir (Pseudotsuga menziesii) Induced by Exposure to Diesel Emissions Generated with CeO2 Nanoparticle Fuel Additive

EPA Science Inventory

When cerium oxide nanoparticles are added to diesel fuel, fuel burning efficiency increases, producing emissions (DECe) with characteristics that differ from conventional diesel exhaust (DE). It has previously been shown that DECe induces more adverse pulmonary effects in rats on...

Catalytic Oxidative Dehydration of Butanol Isomers: 1-Butanol, 2-Butanol, and Isobutanol

DTIC Science & Technology

2011-09-01

butanol, 2-butanol, and isobutanol using a millisecond contact time reactor. Both alumina foam and rhodium -alumina foam catalysts convert these four...such as n-octane, into mixtures of olefins (10). A rhodium /cerium catalyst has been proposed in the past to convert biodiesel into olefins (11). The

Preparation, Characterization, and Preliminary In Vitro Testing of Nanoceria-Loaded Liposomes

PubMed Central

Grillone, Agostina; Li, Tianshu; Battaglini, Matteo; Scarpellini, Alice; Takeoka, Shinji

2017-01-01

Cerium oxide nanoparticles (nanoceria), well known for their pro- and antioxidant features, have been recently proposed for the treatment of several pathologies, including cancer and neurodegenerative diseases. However, interaction between nanoceria and biological molecules such as proteins and lipids, short blood circulation time, and the need of a targeted delivery to desired sites are some aspects that require strong attention for further progresses in the clinical application of these nanoparticles. The aim of this work is the encapsulation of nanoceria into a liposomal formulation in order to improve their therapeutic potentialities. After the preparation through a reverse-phase evaporation method, size, Z-potential, morphology, and loading efficiency of nanoceria-loaded liposomes were investigated. Finally, preliminary in vitro studies were performed to test cell uptake efficiency and preserved antioxidant activity. Nanoceria-loaded liposomes showed a good colloidal stability, an excellent biocompatibility, and strong antioxidant properties due to the unaltered activity of the entrapped nanoceria. With these results, the possibility of exploiting liposomes as carriers for cerium oxide nanoparticles is demonstrated here for the first time, thus opening exciting new opportunities for in vivo applications. PMID:28926967

Beneficial Effects of Cerium Oxide Nanoparticles in Development of Chondrocyte-Seeded Hydrogel Constructs and Cellular Response to Interleukin Insults

PubMed Central

Ponnurangam, Sathish; O'Connell, Grace D.; Chernyshova, Irina V.; Wood, Katherine; Hung, Clark Tung-Hui

2014-01-01

The harsh inflammatory environment associated with injured and arthritic joints represents a major challenge to articular cartilage repair. In this study, we report the effect of cerium oxide nanoparticles, or nanoceria, in modulating development of engineered cartilage and in combating the deleterious effects of interleukin-1α. Nanoceria was found to be biocompatible with bovine chondrocytes up to a concentration of 1000 μg/mL (60,000 cells/μg of nanoceria), and its presence significantly improved compressive mechanical properties and biochemical composition (i.e., glycosaminoglycans) of engineered cartilage. Raman microspectroscopy revealed that individual chondrocytes with internalized nanoceria have increased concentrations of proline, procollagen, and glycogen as compared with cells without the nanoparticles in their vicinity. The inflammatory response due to physiologically relevant quantities of interluekin-1α (0.5 ng/mL) is partially inhibited by nanoceria. To the best of the authors' knowledge, these results are the first to demonstrate a high potential for nanoceria to improve articular cartilage tissue properties and for their long-term treatment against an inflammatory reaction. PMID:24762195

Beneficial effects of cerium oxide nanoparticles in development of chondrocyte-seeded hydrogel constructs and cellular response to interleukin insults.

PubMed

Ponnurangam, Sathish; O'Connell, Grace D; Chernyshova, Irina V; Wood, Katherine; Hung, Clark Tung-Hui; Somasundaran, Ponisseril

2014-11-01

The harsh inflammatory environment associated with injured and arthritic joints represents a major challenge to articular cartilage repair. In this study, we report the effect of cerium oxide nanoparticles, or nanoceria, in modulating development of engineered cartilage and in combating the deleterious effects of interleukin-1α. Nanoceria was found to be biocompatible with bovine chondrocytes up to a concentration of 1000 μg/mL (60,000 cells/μg of nanoceria), and its presence significantly improved compressive mechanical properties and biochemical composition (i.e., glycosaminoglycans) of engineered cartilage. Raman microspectroscopy revealed that individual chondrocytes with internalized nanoceria have increased concentrations of proline, procollagen, and glycogen as compared with cells without the nanoparticles in their vicinity. The inflammatory response due to physiologically relevant quantities of interluekin-1α (0.5 ng/mL) is partially inhibited by nanoceria. To the best of the authors' knowledge, these results are the first to demonstrate a high potential for nanoceria to improve articular cartilage tissue properties and for their long-term treatment against an inflammatory reaction.

[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.

[Na5(THF)10Ce(mnt)4]infinity: a honeycomb network polymer that yields homoleptic cerium(III) tetrakis(dithiolene) complexes in donor solvents.

PubMed

Weis, Eric M; Barnes, Charles L; Duval, Paul B

2006-12-11

The first example of a lanthanide tetrakis(dithiolene) complex, [Na5(THF)10Ce(mnt)4] (1) (mnt = 1,2-maleonitrile-1,2-dithiolate), has been synthesized and characterized by X-ray crystallography and spectroscopic methods. In the solid state, 1 exists as a 2-D corrugated honeycomb network polymer in which the monomeric units comprising the trigonal nodes are knitted together by interlocking dative Na-N bonds extended from nitrile groups of bifunctional mnt ligands coordinated through the sulfur atoms to adjacent cerium centers. Individual honeycomb sheets are separated by 14.8 A. Compound 1 dissolves in donor solvents such as THF and acetonitrile to give soluble [Ce(mnt)4]5- units that exhibit spectroscopic features (i.e., NMR, luminescence, UV-vis) that are consistent with the 4f1 Ce(III) ion. In the first examination of the redox chemistry of a lanthanide dithiolene complex, cyclic voltammetry measurements conducted on 1 reveal a single irreversible oxidation wave that is likely attributable to ligand-centered oxidation.

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

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. PMID:27818836

Influence of synthesis conditions on the crystal structure of the powder formed in the “HfO2 - CeO2/Ce2O3” system

NASA Astrophysics Data System (ADS)

Popov, V. V.; Menushenkov, A. P.; Khubbutdinov, R. M.; Yastrebtsev, A. A.; Svetogorov, R. D.; Zubavichus, Ya V.; Trigub, A. L.; Sharapov, A. S.; Pisarev, A. A.; Kurilkin, V. V.; Tsarenko, N. A.; Arzhatkina, L. A.

2017-12-01

Influence of synthesis conditions (type of atmosphere: reduction or oxidation, annealing temperature) on the chemical composition and structure of the compounds formed in the “HfO2 - CeO2/Ce2O3” system has been investigated by X-ray absorption fine structure spectroscopy combined with Raman spectroscopy, X-ray diffraction and thermogravimetric analysis. It was revealed that isothermal annealing of precursor at temperatures less than 1000°C in air leads to formation of Ce0.5Hf0.5O2 powders with cubic fluorite-type structure (space group Fm-3m). Further increase of annealing temperatures above 1000°C causes decomposition of formed crystal structure into two phases: cubic and monoclinic. Annealing in reduction hydrogen atmosphere causes formation of Ce4+ 2x Ce3+ 2-2x Hf2O7+x compounds with intermediate oxidation state of cerium, where value of x depends on the reducing conditions and treatment parameters. Annealing in vacuum at 1400°C strongly reduces the content of Ce4+ in a powder samples and leads to formation of pyrochlore structure (space group Fd-3m) with predominant +3 oxidation state of cerium.

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

Supported catalyst systems and method of making biodiesel products using such catalysts

DOEpatents

Kim, Manhoe; Yan, Shuli; Salley, Steven O.; Ng, K. Y. Simon

2015-10-20

A heterogeneous catalyst system, a method of preparing the catalyst system and a method of forming a biodiesel product via transesterification reactions using the catalyst system is disclosed. The catalyst system according to one aspect of the present disclosure represents a class of supported mixed metal oxides that include at least calcium oxide and another metal oxide deposited on a lanthanum oxide or cerium oxide support. Preferably, the catalysts include CaO--CeO.sub.2ZLa.sub.2O.sub.3 or CaO--La.sub.2O.sub.3/CeO.sub.2. Optionally, the catalyst may further include additional metal oxides, such as CaO--La.sub.2O.sub.3--GdOxZLa.sub.2O.sub.3.

[Ion chromatography of L-ascorbic acid, sulfite and thiosulfate using their postcolumn reactions with cerium (IV) and fluorescence detection of cerium (III)].

PubMed

Chen, Q; Hu, K; Miura, Y

1999-09-01

An ion chromatographic method was used to separate the species of L-ascorbic acid, sulfite and thiosulfate in their mixtures. This method is based on the separation of each anion in their mixtures by using a separation column, and then on the fluorimetric measurement of cerium (III) formed by a postcolumn reaction of cerium (IV) with the species of L-ascorbic acid, sulfite and thiosulfate in the effluent. The optimal conditions for separating and determining the above three species have been established. By using a 3 mmol/L carbonate eluent, the species of L-ascorbic acid, sulfite and thiosulfate could be eluted at the proper retention times of 1.7, 2.6 and 5.0 min, respectively, and these three anions could be separated completely. The effects of the concentrations of cerium (IV) and sulfuric acid in the postcolumn reaction solution on the chromatographic peak-height were tested in order to obtain the optimal peak-height. It was found that the peak-height at first increases rapidly with an increase in the concentration of cerium (IV) and sulfuric acid respectively up to a certain concertation, then increases slowly. These critical concentrations of cerium (IV) and sulfuric acid also depend on the amount of the analyte injected. Meanwhile the baseline signals of the sepectra increase with an increase in the concentration of cerium (IV). Some concentrations above the critical concentration of sulfuric acid could be selected as the optimal concentration of sulfuric acid, but the concentration of cerium (IV) should be optimized by establishing a compromise between the higher peak-height and the lower baseline signal. The detection limit of this method was found to be 1 mumol/L for thiosulfate when an amount of 100 microL analyte was injected.

Fuel electrode containing pre-sintered nickel/zirconia for a solid oxide fuel cell

DOEpatents

Ruka, Roswell J.; Vora, Shailesh D.

2001-01-01

A fuel cell structure (2) is provided, having a pre-sintered nickel-zirconia fuel electrode (6) and an air electrode (4), with a ceramic electrolyte (5) disposed between the electrodes, where the pre-sintered fuel electrode (6) contains particles selected from the group consisting of nickel oxide, cobalt and cerium dioxide particles and mixtures thereof, and titanium dioxide particles, within a matrix of yttria-stabilized zirconia and spaced-apart filamentary nickel strings having a chain structure, and where the fuel electrode can be sintered to provide an active solid oxide fuel cell.

Advanced materials and design for low temperature SOFCs

DOEpatents

Wachsman, Eric D.; Yoon, Heesung; Lee, Kang Taek; Camaratta, Matthew; Ahn, Jin Soo

2016-05-17

Embodiments of the invention are directed to SOFC with a multilayer structure comprising a porous ceramic cathode, optionally a cathodic triple phase boundary layer, a bilayer electrolyte comprising a cerium oxide comprising layer and a bismuth oxide comprising layer, an anion functional layer, and a porous ceramic anode with electrical interconnects, wherein the SOFC displays a very high power density at temperatures below 700.degree. C. with hydrogen or hydrocarbon fuels. The low temperature conversion of chemical energy to electrical energy allows the fabrication of the fuel cells using stainless steel or other metal alloys rather than ceramic conductive oxides as the interconnects.

Radioactive rare-earth deposit at Scrub Oaks mine, Morris County, New Jersey

USGS Publications Warehouse

Klemic, Harry; Heyl, A.V.; Taylor, Audrey R.; Stone, Jerome

1959-01-01

A deposit of rare-earth minerals in the Scrub Oaks iron mine, Morris County, N. J., was mapped and sampled in 1955. The rare-earth minerals are mainly in coarse-grained magnetite ore and in pegmatite adjacent to it. Discrete bodies of rare-earth-bearing magnetite ore apparently follow the plunge of the main magnetite ore body at the north end of the mine. Radioactivity of the ore containing rare earths is about 0.2 to 0.6 mllliroentgens per hour. The principal minerals of the deposit are quartz, magnetite, hematite, albiteoligoclase, perthite and antiperthite. Xenotime and doverite aggregates and bastnaesite with intermixed leucoxene are the most abundant rare-earth minerals, and zircon, sphene, chevkinite, apatite, and monazite are of minor abundance in the ore. The rare-earth elements are partly differentiated into cerium-rich bastnaesite, chevkinite, and monazite, and yttrium-rich xenotime and doverite. Apatite, zircon, and sphene contain both cerium and yttrium group earths. Eleven samples of radioactive ore and rock average 0.009 percent uranium, 0.062 percent thorium, 1.51 percent combined rare-earth oxides including yttrium oxide and 24.8 percent iron. Scatter diagrams of sample data show a direct correlation between equivalent uranium, uranium, thorium, and combined rare^ earth oxides. Both cerium- and yttrium-group earths are abundant in the rare-earth minerals. Radioactive magnetite ore containing rare-earth minerals probably formed as a variant of the magnetite mineralization that produced the main iron ore of the Scrub Oaks deposit. The rare-earth minerals and the iron ore were deposited contemporaneously. Zircon crystals, probably deposited at the same time, have been determined by the Larsen method to be about 550 to 600 million years old (late Precambrian age). Uranium, thorium, and rare-earth elements are potential byproducts of iron in the coarse-grained magnetite ore.

Predictive tests to evaluate oxidative potential of engineered nanomaterials

NASA Astrophysics Data System (ADS)

Ghiazza, Mara; Carella, Emanuele; Oliaro-Bosso, Simonetta; Corazzari, Ingrid; Viola, Franca; Fenoglio, Ivana

2013-04-01

Oxidative stress constitutes one of the principal injury mechanisms through which particulate toxicants (asbestos, crystalline silica, hard metals) and engineered nanomaterials can induce adverse health effects. ROS may be generated indirectly by activated cells and/or directly at the surface of the material. The occurrence of these processes depends upon the type of material. Many authors have recently demonstrated that metal oxides and carbon-based nanoparticles may influence (increasing or decreasing) the generation of oxygen radicals in a cell environment. Metal oxide, such as iron oxides, crystalline silica, and titanium dioxide are able to generate free radicals via different mechanisms causing an imbalance within oxidant species. The increase of ROS species may lead to inflammatory responses and in some cases to the development of cancer. On the other hand carbon-based nanomaterials, such as fullerene, carbon nanotubes, carbon black as well as cerium dioxide are able to scavenge the free radicals generated acting as antioxidant. The high numbers of new-engineered nanomaterials, which are introduced in the market, are exponentially increasing. Therefore the definition of toxicological strategies is urgently needed. The development of acellular screening tests will make possible the reduction of the number of in vitro and in vivo tests to be performed. An integrated protocol that may be used to predict the oxidant/antioxidant potential of engineered nanoparticles will be here presented.

Casting Characteristics of High Cerium Content Aluminum Alloys

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

Weiss, D; Rios, O R; Sims, Z C

This paper compares the castability of the near eutectic aluminum-cerium alloy system to the aluminum-silicon and aluminum-copper systems. The alloys are compared based on die filling capability, feeding characteristics and tendency to hot tear in both sand cast and permanent mold applications. The castability ranking of the binary Al–Ce systems is as good as the aluminum-silicon system with some deterioration as additional alloying elements are added. In alloy systems that use cerium in combination with common aluminum alloying elements such as silicon, magnesium and/or copper, the casting characteristics are generally better than the aluminum-copper system. In general, production systems formore » melting, de-gassing and other processing of aluminum-silicon or aluminum-copper alloys can be used without modification for conventional casting of aluminum-cerium alloys.« less

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%.

Mediated electrochemical oxidation (MEO) process: a study on nonylphenol ethoxylates (NPE) oxidation in batch mode using cerium (IV) oxidant

NASA Astrophysics Data System (ADS)

Setiyanto, H.; Adyatmika, I. M.; Syaifullah, M. M.; Zulfikar, M. A.; Buchari

2018-05-01

Nonylphenol ethoxylate (NPE-10) is one type of non-ionic surfactants from the class of alkylphenol ethoxylate (APE). This compound is already tightened their use in European Union countries. However, these surfactants are still used widely in Indonesia because the price is relatively cheap. Consequently, these compounds can accumulate in aquatic environments. NPE-10 can disrupt aquatic ecosystems. This study aimed to describe the electro-oxidation process of NPE-10 based on the parameters of a potential difference, concentration of NPE-10, concentration of Ce (III), and oxidation time. The result of oxidation NPE-10 was measured by the amount of current generated from voltammetry technique. Studies of cyclic voltammetry using carbon paste electrodes illustrates the potential value of the oxidation of Ce (III) / Ce (IV) of 1.25 V and the reduction potential value of Ce (IV) / Ce (III) of 1.192 V. NPE-10 are electroactive irreversible because it only provides the potential value of oxidation at 1.44 V. Percent of total degradation of 84.96% was obtained at electro-oxidation of 500 ppm NPE-10 by the addition of 0.015 M Ce (III) for 90 minutes at 0.2 M H2SO4and the use of potential of 6 V.

Antimicrobial potential of green synthesized CeO2 nanoparticles from Olea europaea leaf extract.

PubMed

Maqbool, Qaisar; Nazar, Mudassar; Naz, Sania; Hussain, Talib; Jabeen, Nyla; Kausar, Rizwan; Anwaar, Sadaf; Abbas, Fazal; Jan, Tariq

This article reports the green fabrication of cerium oxide nanoparticles (CeO 2 NPs) using Olea europaea leaf extract and their applications as effective antimicrobial agents. O. europaea leaf extract functions as a chelating agent for reduction of cerium nitrate. The resulting CeO 2 NPs exhibit pure single-face cubic structure, which is examined by X-ray diffraction, with a uniform spherical shape and a mean size 24 nm observed through scanning electron microscopy and transmission electron microscopy. Ultraviolet-visible spectroscopy confirms the characteristic absorption peak of CeO 2 NPs at 315 nm. Fourier transform infrared spectroscopy reflects stretching frequencies at 459 cm -1 , showing utilization of natural components for the production of NPs. Thermal gravimetric analysis predicts the successful capping of CeO 2 NPs by bioactive molecules present in the plant extract. The antimicrobial studies show significant zone of inhibition against bacterial and fungal strains. The higher activities shown by the green synthesized NPs than the plant extract lead to the conclusion that they can be effectively used in biomedical application. Furthermore, reduction of cerium salt by plant extract will reduce environmental impact over chemical synthesis.

Antimicrobial potential of green synthesized CeO2 nanoparticles from Olea europaea leaf extract

PubMed Central

Maqbool, Qaisar; Nazar, Mudassar; Naz, Sania; Hussain, Talib; Jabeen, Nyla; Kausar, Rizwan; Anwaar, Sadaf; Abbas, Fazal; Jan, Tariq

2016-01-01

This article reports the green fabrication of cerium oxide nanoparticles (CeO2 NPs) using Olea europaea leaf extract and their applications as effective antimicrobial agents. O. europaea leaf extract functions as a chelating agent for reduction of cerium nitrate. The resulting CeO2 NPs exhibit pure single-face cubic structure, which is examined by X-ray diffraction, with a uniform spherical shape and a mean size 24 nm observed through scanning electron microscopy and transmission electron microscopy. Ultraviolet-visible spectroscopy confirms the characteristic absorption peak of CeO2 NPs at 315 nm. Fourier transform infrared spectroscopy reflects stretching frequencies at 459 cm−1, showing utilization of natural components for the production of NPs. Thermal gravimetric analysis predicts the successful capping of CeO2 NPs by bioactive molecules present in the plant extract. The antimicrobial studies show significant zone of inhibition against bacterial and fungal strains. The higher activities shown by the green synthesized NPs than the plant extract lead to the conclusion that they can be effectively used in biomedical application. Furthermore, reduction of cerium salt by plant extract will reduce environmental impact over chemical synthesis. PMID:27785011

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

Luňáček, J., E-mail: jiri.lunacek@vsb.cz

The present paper is devoted to detailed study of the magnetically separable sorbents based on a cerium dioxide/iron oxide composite annealed at temperatures T{sub a} = 773 K, 873 K, and 973 K. The X-ray diffraction and high resolution transmission electron microscopy are used to determine the phase composition and microstructure morphology. Mössbauer spectroscopy at room (300 K) and low (5 K) temperatures has contributed to more exact identification of iron oxides and their transformations Fe{sub 3}O{sub 4} → γ-Fe{sub 2}O{sub 3} (ε-Fe{sub 2}O{sub 3}) → α-Fe{sub 2}O{sub 3} in dependence on calcination temperature. Different iron oxide phase compositions andmore » grain size distributions influence the magnetic characteristics determined from the room- and low-temperature hysteresis loop measurements. The results are supported by zero-field-cooled and field-cooled magnetization measurements allowing a quantitative estimation of the grain size distribution and its effect on the iron oxide transformations. - Highlights: •Magnetically separable sorbents based on a CeO{sub 2}/Fe{sub 2}O{sub 3} composite were investigated. •Microstructure of sorbents was determined by XRD, TEM and Mössbauer spectroscopy. •Magnetic properties were studied by hysteresis loops at room- and low-temperatures. •Phase transitions of iron oxides with increasing annealing temperature are observed.« less

Tribological study on rapeseed oil with nano-additives in close contact sliding situation

NASA Astrophysics Data System (ADS)

Gupta, Rajeev Nayan; Harsha, A. P.; Singh, Sagar

2018-02-01

The present work deals with the tribological evaluation of three types of nano-additives, i.e., copper oxide (CuO; ≈ 151.2 nm), cerium oxide (CeO2; ≈ 80 nm) and polytetrafluoroethylene (PTFE; ≈ 90.4 nm) with rapeseed oil under steel-steel sliding contacts. The nano-additives concentrations in the base oil were 0.1, 0.25 and 0.5% w/v for the lubricant formulation. Further, the rapeseed oil was also epoxidized by a chemical method and the tribological behavior was compared with the base oil (unmodified oil) at similar nano-additives concentrations. The ASTM standards were followed for the study of wear preventive and extreme-pressure analysis of nanolubricants, and it was carried out using four-ball tester. In the antiwear test, CeO2 and PTFE nano-additives have shown the significant reduction in the wear scar diameter at the concentration of 0.1% w/v. In the extreme-pressure test, 0.5% w/v concentration was optimum for oxide nanoparticles; however, PTFE nanoparticles did not show positive effect with both the base oils. Different characterization techniques were employed to confirm the oil modification and for the study of the worn surfaces.

Cerium oxide nanoparticle elicits oxidative stress, endocrine imbalance and lowers sperm characteristics in testes of balb/c mice.

PubMed

Adebayo, O A; Akinloye, O; Adaramoye, O A

2018-04-01

The toxicity of metallic nanoparticles is a growing concern due to its application in industries and homes. We investigated the toxicity of cerium oxide nanoparticles (CeO 2 NPs) on reproductive system in male balb/c mice. Twenty mice were divided into four groups of five animals each and treated thus: normal saline (control), 100, 200 and 300 μg/kg CeO 2 NPs (i.p.,) thrice in a week for five consecutive weeks. Results showed that CeO 2 NPs significantly reduced the levels of haemoglobin, PCV and RBC count relative to controls. In addition, luteinising and follicle-stimulating hormones (FSH and LH) and prolactin were significantly reduced in the mice. Specifically, CeO 2 NPs at 100 μg/kg decreased testosterone by 23%, while CeO 2 NPs at 200 μg/kg decreased FSH, LH and prolactin by 25%, 26% and 13%, respectively. Testicular malondialdehyde was increased by 103%, 106% and 135% in mice treated with 100, 200 and 300 μg/kg CeO 2 NPs, respectively. CeO 2 NPs caused a significant reduction in activities of antioxidant enzymes and levels of reduced glutathione and total nitric oxide. Moreso, CeO 2 NPs decreased sperm motility and count and increased total sperm abnormality in mice. Histology revealed congestion and degeneration of seminiferous tubules. Overall, CeO 2 NPs induces testicular dysfunction via disruption of antioxidant/oxidant balance and endocrine suppression. © 2017 Blackwell Verlag GmbH.

Cerium migration during PEM fuel cell accelerated stress testing

DOE PAGES

Baker, Andrew M.; Mukundan, Rangachary; Borup, Rodney L.; ...

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

Low-temperature carbon monoxide oxidation over zirconia-supported CuO-CeO2 catalysts: Effect of zirconia support properties

NASA Astrophysics Data System (ADS)

Moretti, Elisa; Molina, Antonia Infantes; Sponchia, Gabriele; Talon, Aldo; Frattini, Romana; Rodriguez-Castellon, Enrique; Storaro, Loretta

2017-05-01

A study was conducted to investigate the effect of the preparation route of ZrO2 in CuO-CeO2/ZrO2 catalysts for the oxidation of carbon monoxide at low temperature (COX). Four ZrO2 supports were synthetized via either type sol-gel methodology or precipitation. The final Cu-Ce-Zr oxide catalysts were prepared by incipient wetness co-impregnation with copper and cerium solutions (with a loading of 6 wt% of CuO and 20 wt% of CeO2). The catalyst crystalline phases, texture and active species reducibility were determined by XRD, N2 physisorption at -196 °C and H2-TPR, respectively; meanwhile the surface composition and copper-cerium electronic states were studied by XPS. The catalytic activity was evaluated in the oxidation of CO to CO2, in the 40-215 °C temperature range. Catalytic results evidenced that the samples prepared by a sol-gel methodology showed, after the impregnation, a severe decrease of specific surface area and pore volume attributable to a wide degree of pore blockage caused by the presence of metal oxide particles and a collapse of the structure partially burying the active sites. A simple co-impregnation of a zirconia support, obtained through facile and fast precipitation, provided instead a catalyst with very good redox properties and high dispersion of the active phases, which completely oxidizes CO in the range 115-215 °C with T50 of 65 °C. This higher observed activity was ascribed to the formation of a larger fraction of highly dispersed and easily reducible Cu species and ceria nanocrystallites, mainly present as Ce(IV), with an average size of 5 nm.

XPS studies of Mg doped GDC (Ce0.8Gd0.2O2-δ) for IT-SOFC

NASA Astrophysics Data System (ADS)

Tyagi, Deepak; Rao, P. Koteswara; Wani, B. N.

2018-04-01

Fuel Cells have gained much attention as efficient and environment friendly device for both stationary as well as mobile applications. For intermediate temperature SOFC (IT-SOFC), ceria based electrolytes are the most promising one, due to their higher ionic conductivity at relatively lower temperatures. Gd doped ceria is reported to be having the highest ionic conductivity. In the present work, Mg is codoped along with Gd and the electronic structure of the constituents is studied by XPS. XPS confirm that the Cerium is present in +4 oxidation state only which indicates that electronic conduction can be completely avoided.

Induction of molecular endpoints by reactive oxygen species in human lung cells predicted by physical chemical properties of engineered nanoparticles

EPA Science Inventory

A series of six titanium dioxide and two cerium oxide engineered nanomaterials were assessed for their ability to induce cytotoxicity, reactive oxygen species (ROS), and various types of DNA and protein damage in human respiratory BEAS-2B cells exposed in vitro for 72 hours at se...

An Evaluation of the Potential Phototoxicity of CeO2 Nanoparticles in Retinal Pigment Epithelial Cells in-vitro

EPA Science Inventory

Cerium dioxide (CeO2) engineered nanoparticles (NP) are used as fuel-borne catalysts in off-road diesel engines, which can lead to exhaust emissions of respirable CeO2 NP. Other metal oxides may act as photo-catalysts which induce the generation of free radicals upon exposure to ...

Antioxidative study of Cerium Oxide nanoparticle functionalised PCL-Gelatin electrospun fibers for wound healing application.

PubMed

Rather, Hilal Ahmad; Thakore, Ria; Singh, Ragini; Jhala, Dhwani; Singh, Sanjay; Vasita, Rajesh

2018-06-01

Skin wound healing involves a coordinated cellular response to achieve complete reepithelialisation. Elevated levels of reactive oxygen species (ROS) in the wound environment often pose a hindrance in wound healing resulting in impaired wound healing process. Cerium oxide nanoparticles (CeNPs) have the ability to protect the cells from oxidative damage by actively scavenging the ROS. Furthermore, matrices like nanofibers have also been explored for enhancing wound healing. In the current study CeNP functionalised polycaprolactone (PCL)-gelatin nanofiber (PGNPNF) mesh was fabricated by electrospinning and evaluated for its antioxidative potential. Wide angle XRD analysis of randomly oriented nanofibers revealed ∼2.6 times reduced crystallinity than pristine PCL which aided in rapid degradation of nanofibers and release of CeNP. However, bioactive composite made between nanoparticles and PCL-gelatin maintained the fibrous morphology of PGNPNF upto 14 days. The PGNPNF mesh exhibited a superoxide dismutase (SOD) mimetic activity due to the incorporated CeNPs. The PGNPNF mesh enhanced proliferation of 3T3-L1 cells by ∼48% as confirmed by alamar blue assay and SEM micrographs of cells grown on the nanofibrous mesh. Furthermore, the PGNPNF mesh scavenged ROS, which was measured by relative DCF intensity and fluorescence microscopy; and subsequently increased the viability and proliferation of cells by three folds as it alleviated the oxidative stress. Overall, the results of this study suggest the potential of CeNP functionalised PCL-gelatin nanofibrous mesh for wound healing applications.

Sulfation of ceria-zirconia model automotive emissions control catalysts

NASA Astrophysics Data System (ADS)

Nelson, Alan Edwin

Cerium-zirconium mixed metal oxides are used in automotive emissions control catalysts to regulate the partial pressure of oxygen near the catalyst surface. The near surface oxygen partial pressure is regulated through transfer of atomic oxygen from the ceria-zirconia solid matrix to the platinum group metals to form metal oxides capable of oxidizing carbon monoxide and unburned hydrocarbons. Although the addition of zirconium in the cubic lattice of ceria increases the oxygen storage capacity and thermal stability of the ceria matrix, the cerium-zirconium oxide system remains particularly susceptible to deactivation from sulfur compounds. While the overall effect of sulfur on these systems is understood (partially irreversible deactivation), the fundamental and molecular interaction of sulfur with ceria-zirconia remains a challenging problem. Ceria-zirconia metal oxide solid solutions have been prepared through co-precipitation with nitrate precursors. The prepared powders were calcined and subsequently formed into planer wafers and characterized for chemical and physical attributes. The prepared samples were subsequently exposed to a sulfur dioxide based environment and characterized with spectroscopic techniques to characterize the extent of sulfation and the nature of surface sulfur species. The extent of sulfation of the model ceria-zirconia systems was characterized with Auger electron spectroscopy (AES) prior to and after treatment in a microreactor. Strong dependencies were observed between the atomic ratio of ceria to zirconia and the extent of sulfation. In addition, the partial pressure of sulfur dioxide during treatments also correlated to the extent of sulfation, while temperature only slightly effected the extent of sulfation. The AES data suggests the gas phase sulfur dioxide preferentially chemisorbs on surface ceria atoms and the extent of sulfation is heavily dependent on sulfur dioxide concentrations and only slightly dependent on catalyst temperatures, as confirmed by thermal programmed desorption (TPD). While hydrogen exposure indicated slight sulfur removal, exposure to a redox environment or atmosphere nearly eliminated the quantity of chemisorbed surface sulfur. The nature of sulfur removal is attributed to the inherent redox properties of ceria-zirconia systems. The complete analysis provides mechanistic insight into sulfation dependencies and fundamental information regarding sulfur adsorption on ceria-zirconia model automotive emissions control systems.

Redox conditions in the Late Cretaceous Chalk Sea: the possible use of cerium anomalies as palaeoredox indicators in the Cenomanian and Turonian Chalk of England

NASA Astrophysics Data System (ADS)

Jeans, Christopher V.; Wray, David S.; Williams, C. Terry

2015-09-01

The cerium anomalies preserved in the Chalk have been investigated as possible palaeoredox indicators of the Late Cretaceous Sea and its sediment. This has been based upon over a hundred new rare earth element analyses of selected samples and grain size fractions from the Chalk. Particular attention has been given to the methodology of differentiating between the cerium anomalies preserved in the bioclastic calcite and those in carbonate-fluorapatite preserved in the acetic acid insoluble residues of chalks. Variations in the cerium anomaly of different particle size fractions of uncemented chalks suggest that fractionation of rare earth elements between the Chalk's seawater and the various organisms that contributed skeletal material to the bioclastic calcite of the Chalk may have occurred. Post-depositional processes of calcite cementation and late diagenetic sulphidisation have had no apparent effect on the cerium anomaly of the acetic acid insoluble residues. The cerium anomalies associated with the acetic acid insoluble residues from (1) an alternating sequence of chalks and marls from Ballard Cliff (Dorset, UK) typical of Milankovitch cyclicity show a marked diagenetic pattern, whereas those from (2) non-volcanic and volcanic marls display a pattern that is best explained by the variations in the availability of phosphorus and the timing of argillisation of volcanic glass during diagenesis. The general conclusion is drawn that the cerium anomalies preserved in the Chalk can provide an insight into the changing palaeoredox conditions in the Late Cretaceous Sea as well as in the pore fluids of its sediments.

Using Biomolecules to Separate Plutonium

NASA Astrophysics Data System (ADS)

Gogolski, Jarrod

Used nuclear fuel has traditionally been treated through chemical separations of the radionuclides for recycle or disposal. This research considers a biological approach to such separations based on a series of complex and interdependent interactions that occur naturally in the human body with plutonium. These biological interactions are mediated by the proteins serum transferrin and the transferrin receptor. Transferrin to plutonium in vivo and can deposit plutonium into cells after interacting with the transferrin receptor protein at the cell surface. Using cerium as a non-radioactive surrogate for plutonium, it was found that cerium(IV) required multiple synergistic anions to bind in the N-lobe of the bilobal transferrin protein, creating a conformation of the cerium-loaded protein that would be unable to interact with the transferrin receptor protein to achieve a separation. The behavior of cerium binding to transferrin has contributed to understanding how plutonium(IV)-transferrin interacts in vivo and in biological separations.

Polypropylene oil as fuel for solid oxide fuel cell with samarium doped-ceria (SDC)-carbonate as electrolyte

NASA Astrophysics Data System (ADS)

Syahputra, R. J. E.; Rahmawati, F.; Prameswari, A. P.; Saktian, R.

2017-03-01

The research focusses on converting polypropylene oil as pyrolysis product of polypropylene plastic into an electricity. The converter was a direct liquid fuel-solid oxide fuel cell (SOFC) with cerium oxide based material as electrolyte. The polypropylene vapor flowed into fuel cell, in the anode side and undergo oxidation reaction, meanwhile, the Oxygen in atmosphere reduced into oxygen ion at cathode. The fuel cell test was conducted at 400 - 600 °C. According to GC-MS analysis, the polypropylene oil consist of C8 to C27 hydrocarbon chain. The XRD analysis result shows that Na2CO3 did not change the crystal structure of SDC even increases the electrical conductivity. The maximum power density is 0.079 mW.cm-2 at 773 K. The open circuite voltage is 0.77 volt. Chemical stability test by analysing the single cell at before and after fuel cell test found that ionic migration occured during fuel cell operation. It is supported by the change of elemental composition in the point position of electrolyte and at the electrolyte-electrode interface

Catalytic ozonation of dimethyl phthalate over cerium supported on activated carbon.

PubMed

Li, Laisheng; Ye, Weiying; Zhang, Qiuyun; Sun, Fengqiang; Lu, Ping; Li, Xukai

2009-10-15

Cerium supported on activated carbon (Ce/AC), which was prepared by dipping method, was employed to degrade dimethyl phthalate (DMP) in water. The mineral matter present in the activated carbon positively contributes to its activity to enhance DMP ozonation process. A higher dipping Ce(NO(3))(3) concentration and calcination process increase its microporous volume and surface area, and decreases its exterior surface area. The catalytic activity reaches optimal when 0.2% (w/w) cerium is deposited on activated carbon. Ce/AC catalyst was characterized by XRD, SEM and BET. The presence of either activated carbon or Ce/AC catalyst considerably improves their degradation and mineralization in the ozonation of DMP. During the ozonation (50mg/h ozone flow rate) of a 30 mg/L DMP (initial pH 5.0) with the presence of Ce/AC catalyst, TOC removal rate reaches 68% at 60 min oxidation time, 48% using activated carbon as catalyst, only 22% with ozonation alone. The presence of tert-butanol (a well known OH radical scavenger) strongly inhibits DMP degradation by activated carbon or Ce/AC catalytic ozonation. TOC removal rate follows the second-order kinetics model well. In the ozonation of DMP with 50mg/h ozone flow rate, its mineralization rate constant with the presence of Ce/AC catalyst is 2.5 times higher than that of activated carbon, 7.5 times higher than that of O(3) alone. Ce/AC catalyst shows the better catalytic activity and stability based on 780 min sequential reaction in the ozonation of DMP. Ce/AC was a promising catalyst for ozonizing organic pollutants in the aqueous solution.

Dispersion characteristic of photoluminescence decay times of phosphor YAG: Ce, Gd

NASA Astrophysics Data System (ADS)

Lisitsyn, V. M.; Ju, Yangyang; Stepanov, S. A.; Soschin, N. M.

2017-05-01

The dispersion of the characteristic decay times of gadolinium co-doped yttrium aluminum garnet doped with cerium phosphors were studied. In the present work, an ultraviolet semiconductor laser (λem=375 nm, τ = 1 ns) was used as excitation source for measuring kinetics characteristics of phosphor groups based on YAG with different content of cerium.

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.

Influence of collector surface composition and water chemistry on the deposition of cerium dioxide nanoparticles: QCM-D and column experiment approaches.

PubMed

Liu, Xuyang; Chen, Gexin; Su, Chunming

2012-06-19

The deposition behavior of cerium dioxide (CeO(2)) 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 in quartz crystal microbalance with dissipation (QCM-D) to examine the effect of these mineral phases on CeO(2) deposition in NaCl solution (1-200 mM). Frequency and dissipation shift followed the order: silica > iron oxide > alumina in 10 mM NaCl at pH 4.0. No significant deposition was observed at pH 6.0 and 8.5 on any of the tested sensors. However, ≥ 94.3% of CeO(2) NPs deposited onto Ottawa sand in columns in 10 mM NaCl at pH 6.0 and 8.5. The inconsistency in the different experimental approaches can be mainly attributed to NP aggregation, surface heterogeneity of Ottawa sand, and flow geometry. In QCM-D experiments, the deposition kinetics was found to be qualitatively consistent with the predictions based on the classical colloidal stability theory. The presence of low levels (1-6 mg/L) of Suwannee River humic acid, fulvic acid, alginate, citric acid, and carboxymethyl cellulose greatly enhanced the stability and mobility of CeO(2) NPs in 1 mM NaCl at pH 6.5. The poor correlation between the transport behavior and electrophoretic mobility of CeO(2) NPs implies that the electrosteric effect of OM was involved.

Two-stage epitaxial growth of vertically-aligned SnO 2 nano-rods on(001) ceria

DOE PAGES

Solovyov, Vyacheslav F.; Wu, Li-jun; Rupich, Martin W.; ...

2014-09-20

Growth of high-aspect ratio oriented tin oxide, SnO 2, nano-rods is complicated by a limited choice of matching substrates. We show that a (001) cerium oxide, CeO 2, surface uniquely enables epitaxial growth of tin-oxide nano-rods via a two-stage process. First, (100) oriented nano-wires coat the ceria surface by lateral growth, forming a uniaxially-textured SnO 2 deposit. Second, vertical SnO 2nano-rods nucleate on the deposit by homoepitaxy. We demonstrate growth of vertically oriented 1-2 μm long nano-rods with an average diameter of ≈20 nm.

Modulation of surface structure and catalytic properties of cerium oxide nanoparticles by thermal and microwave synthesis techniques

NASA Astrophysics Data System (ADS)

He, Jian; Zhou, Lan; Liu, Jie; Yang, Lu; Zou, Ling; Xiang, Junyu; Dong, Shiwu; Yang, Xiaochao

2017-04-01

Cerium oxide nanoparticles (CNPs) have been intensively explored for biomedical applications in recent few years due to the versatile enzyme mimetic activities of the nanoparticles. However, the control of CNPs quality through the optimization of synthesis conditions remains largely unexplored as most of the previous studies only focus on utilizing the catalytic activities of the nanoparticles. In the present study, CNPs with size about 5 nm were synthesized by thermal decomposition method using traditional convective heating and recently developed microwave irradiation as heating source. The quality of CNPs synthesized by the two heating manner was evaluated. The CNPs synthesized by convective heating were slightly smaller than that synthesized by microwave irradiation heating. The cores of the CNPs synthesized by the two heating manner have similar crystal structure. While the surface subtle structures of the CNPs synthesized by two heating manner were different. The CNPs synthesized by microwave irradiation have more surface reactive hot spot than that synthesized by convective heating as the nanoparticles responded more actively to the redox environment variation. This difference resulted in the higher superoxide dismutase (SOD) mimetic activity of CNPs synthesized by microwave irradiation heating than that of the convective heating. Preliminary experiments indicated that the CNPs synthesized by microwave irradiation heating could better protect cells from oxidative stress due to the higher SOD mimetic activity of the nanoparticles.

PEO of pre-anodized Al-Si alloys: Corrosion properties and influence of sealings

NASA Astrophysics Data System (ADS)

Mohedano, M.; Matykina, E.; Arrabal, R.; Mingo, B.; Pardo, A.

2015-08-01

Voltage-controlled PEO coatings were developed on A356 aluminum alloys (gravity-cast and rheocast) with a pre-anodized layer. The influence of the alloy manufacturing process and the effect of Si-rich phase on the structure and composition of the oxide layers were evaluated using SEM, EDS and XRD. The pre-anodized oxide layer preserves the microstructure of the substrate due to the presence of secondary phases that have a different behavior relative to the matrix during anodizing. PEO coatings consisted of a mixture of α-Al2O3, γ-Al2O3 and mullite. The corrosion behavior and the effectiveness of different sealing techniques based on salts of nickel, cobalt, cerium and phosphonic acid were also studied. Post-treatments improved the hydrophobic properties of the coatings and showed a beneficial effect, significantly increasing the coating impedance and thereby reducing the susceptibility to corrosion.

Stability and Transport of Cerium Oxide Nanoparticles in Aqueous Environment: Effect of pH, Ionic Strength, and Organic Matter.

EPA Science Inventory

This study investigated the stability and transport of CeO2 NPs under the influence of pH, natural/manmade organic matter, and electrolyte (NaCl) concentrations. In column test, effluent concentration of CeO2 NPs was close to the influent at pH 10, while most NPs deposited on san...

In Situ Characterization of Mesoporous Co/CeO 2 Catalysts for the High-Temperature Water-Gas Shift

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

Vovchok, Dimitriy; Guild, Curtis J.; Dissanayake, Shanka

Here, mesoporous Co/CeO 2 catalysts were found to exhibit significant activity for the high-temperature water-gas shift (WGS) reaction with cobalt loadings as low as 1 wt %. The catalysts feature a uniform dispersion of cobalt within the CeO 2 fluorite type lattice with no evidence of discrete cobalt phase segregation. In situ XANES and ambient pressure XPS experiments were used to elucidate the active state of the catalysts as partially reduced cerium oxide doped with oxidized cobalt atoms. In situ XRD and DRIFTS experiments suggest facile cerium reduction and oxygen vacancy formation, particularly with lower cobalt loadings. In situ DRIFTSmore » analysis also revealed the presence of surface carbonate and bidentate formate species under reaction conditions, which may be associated with additional mechanistic pathways for the WGS reaction. Deactivation behavior was observed with higher cobalt loadings. XANES data suggest the formation of small metallic cobalt clusters at temperatures above 400 °C may be responsible. Notably, this deactivation was not observed for the 1% cobalt loaded catalyst, which exhibited the highest activity per unit of cobalt.« less

Enhanced Colloidal Stability of CeO2 Nanoparticles by Ferrous Ions: Adsorption, Redox Reaction, and Surface Precipitation.

PubMed

Liu, Xuyang; Ray, Jessica R; Neil, Chelsea W; Li, Qingyun; Jun, Young-Shin

2015-05-05

Due to the toxicity of cerium oxide (CeO2) nanoparticles (NPs), a better understanding of the redox reaction-induced surface property changes of CeO2 NPs and their transport in natural and engineered aqueous systems is needed. This study investigates the impact of redox reactions with ferrous ions (Fe2+) on the colloidal stability of CeO2 NPs. We demonstrated that under anaerobic conditions, suspended CeO2 NPs in a 3 mM FeCl2 solution at pH 4.8 were much more stable against sedimentation than those in the absence of Fe2+. Redox reactions between CeO2 NPs and Fe2+ lead to the formation of 6-line ferrihydrite on the CeO2 surfaces, which enhanced the colloidal stability by increasing the zeta potential and hydrophilicity of CeO2 NPs. These redox reactions can affect the toxicity of CeO2 NPs by increasing cerium dissolution, and by creating new Fe(III) (hydr)oxide reactive surface layers. Thus, these findings have significant implications for elucidating the phase transformation and transport of redox reactive NPs in the environment.

Post-GOE redox insights from Mo isotopes, Ce anomalies, and Mn from the 2.24 Ga Kazput Formation

NASA Astrophysics Data System (ADS)

Thoby, M.; Konhauser, K.; Philippot, P.; Killingsworth, B.; Warchola, T.; Lalonde, S.

2017-12-01

Following the Great Oxidation event (GOE) defined from 2.45 to 2.2 Ga, an event marking the first appearance of widespread atmospheric oxygen, a combination of decreased Mn(II) supply from land and increased Mn(IV)-precipitation in the oceans should have resulted in lower concentrations of Mn in seawater. Nevertheless, it appears that some early Proterozoic marine sediments record high seawater Mn concentrations hundreds of millions of years after the GOE. Here we investigate a Mn excursion associated with marine carbonates and shales of the 2.31 Ga Kazput Formation. Samples were recovered from drill core collected during the Turee Creek Drilling Project (TCDP). Using molybdenum (Mo) isotope data coupled with cerium (Ce) anomalies, we define the redox condition of the Kazput depositional environment. Initial results show no Mo fractionation and few cerium anomalies in carbonates, pointing to an anoxic basin without Mn oxide precipitates. Additionally, XRF data on the shales indicates an association of Mn with calcium (Ca) suggesting an anoxic environment at the time of their deposition. Our results provide new insights into the nature and environment of the Turee Creek basin and the extent of oxygenation of surface waters after the GOE.

Effect of Cerium Oxide on Morphologies and Electrochemical Properties of Ni-W-P Coating on AZ91D Magnesium

NASA Astrophysics Data System (ADS)

Sun, Wan-chang; Xu, Jia-Min; Wang, Yuan; Guo, Fang; Jia, Zong-Wei

2017-12-01

AZ91D magnesium alloy substrate was first pretreated in a phosphoric acid to obtain a phosphate coating, and then, the electroless ternary Ni-W-P coating was deposited using a sulfate nickel bath. The morphologies of the Ni-W-P coating were observed by using scanning electron microscope, the deposition rate of the coating was examined with the method of gravimetric analysis, and the phase analysis was identified by x-ray diffractometer. Electrochemical property was tested by means of an electrochemical analyzer. The results indicated that the addition of an optimum concentration of CeO2 (cerium oxide) particles could evidently improve the deposition rate and the stability of the plating bath. However, it acted as an inhibiting effect as the concentration of CeO2 particles exceeded to 8 mg/L in the sulfate nickel bath. The results also revealed that the morphology of Ni-W-P coating became more smooth, compact and uniform with the increase in the concentrations of CeO2 particles in the bath, but the corrosion resistance decreased due to the precipitation of crystal phases (Ni3P, Ni4W, etc.) after heat treatment.

In Situ Characterization of Mesoporous Co/CeO 2 Catalysts for the High-Temperature Water-Gas Shift

DOE PAGES

Vovchok, Dimitriy; Guild, Curtis J.; Dissanayake, Shanka; ...

2018-04-04

Here, mesoporous Co/CeO 2 catalysts were found to exhibit significant activity for the high-temperature water-gas shift (WGS) reaction with cobalt loadings as low as 1 wt %. The catalysts feature a uniform dispersion of cobalt within the CeO 2 fluorite type lattice with no evidence of discrete cobalt phase segregation. In situ XANES and ambient pressure XPS experiments were used to elucidate the active state of the catalysts as partially reduced cerium oxide doped with oxidized cobalt atoms. In situ XRD and DRIFTS experiments suggest facile cerium reduction and oxygen vacancy formation, particularly with lower cobalt loadings. In situ DRIFTSmore » analysis also revealed the presence of surface carbonate and bidentate formate species under reaction conditions, which may be associated with additional mechanistic pathways for the WGS reaction. Deactivation behavior was observed with higher cobalt loadings. XANES data suggest the formation of small metallic cobalt clusters at temperatures above 400 °C may be responsible. Notably, this deactivation was not observed for the 1% cobalt loaded catalyst, which exhibited the highest activity per unit of cobalt.« less

Thermoelectric properties of cerium monopnictides

NASA Technical Reports Server (NTRS)

Danielson, L. R.; Alexander, M. N.; Wood, C.; Lockwood, R. A.; Vandersande, J. W.

1987-01-01

Several cerium pnictides have been synthesized from the pure elements and hot pressed into test samples. Measurements of Seebeck coefficients and electrical resistivities were performed on these samples from room temperature to 1000 C. Cerium arsenide and cerium antimonide are n-type; cerium nitride changes from p-type to n-type conduction at 800 C. The materials are semimetals with resistivities below 1 mohm/cm. Cerium arsenide is the most favorable of the pnictides studied for high-temperature thermoelectric energy conversion, with an average power factor of 15 microW/cm K sq from 500 to 1000 C.

Redox-Sensitive Cerium Oxide Nanoparticles Protect Human Keratinocytes from Oxidative Stress Induced by Glutathione Depletion.

PubMed

Singh, Ragini; Karakoti, Ajay S; Self, William; Seal, Sudipta; Singh, Sanjay

2016-11-22

Cerium oxide nanoparticles (CeNPs) have gathered much attention in the biomedical field due to its unique antioxidant property. It can protect cells and tissues from oxidative stress induced damage due to its autoregenerative redox cycle. Our study explores the antioxidant and antigenotoxic behavior of PEGylated CeNPs toward oxidative insult produced by buthionine sulfoximine (BSO) in human keratinocytes (HaCaT cells). BSO inhibits the γ-glutamylcysteinesynthetase (γ-GCS) enzyme and thus acts as a glutathione (GSH) depleting agent to modulate the cellular redox potential. GSH is a natural ROS scavenger present in the mammalian cells, and its depletion causes generation of reactive oxygen species (ROS). In this study, we challenged HaCaT cells (keratinocytes) with BSO to alter the redox potential within the cell and monitored toxicity, ROS generation, and nuclear fragmentation. We also followed changes in expressions of related proteins and genes. We found that PEGylated CeNPs can protect HaCaT cells from BSO-induced oxidative damage. BSO-exposed cells, preincubated with PEGylated CeNPs, showed better cell survival and significant decrease in the intracellular levels of ROS. We also observed decrease in lactate dehydrogenase (LDH) release and nuclear fragmentation in CeNP-treated cells that were challenged with BSO as compared to treatment with BSO alone. Exposure of HaCaT cells with BSO leads to altered expression of antioxidant genes and proteins, i.e., thioredoxin reductase (TrxR) and peroxiredoxin 6 (Prx6) whereas, in our study, pretreatment of PEGylated CeNPs reduces the need for induction of genes that produce enzymes involved in the defense against oxidative stress. Since, growing evidence argued the involvement of ROS in mediating death of mammalian cells in several ailments, our finding reinforces the use of PEGylated CeNPs as a potent pharmacological agent under the lower cellular GSH/GSSG ratios for the treatment of diseases mediated by free radicals.

Oriented conductive oxide electrodes on SiO2/Si and glass

DOEpatents

Jia, Quanxi; Arendt, Paul N.

2001-01-01

A thin film structure is provided including a silicon substrate with a layer of silicon dioxide on a surface thereof, and a layer of cubic oxide material deposited upon the layer of silicon dioxide by ion-beam-assisted-deposition, said layer of cubic oxide material characterized as biaxially oriented. Preferably, the cubic oxide material is yttria-stabilized zirconia. Additional thin layers of biaxially oriented ruthenium oxide or lanthanum strontium cobalt oxide are deposited upon the layer of yttria-stabilized zirconia. An intermediate layer of cerium oxide is employed between the yttria-stabilized zirconia layer and the lanthanum strontium cobalt oxide layer. Also, a layer of barium strontium titanium oxide can be upon the layer of biaxially oriented ruthenium oxide or lanthanum strontium cobalt oxide. Also, a method of forming such thin film structures, including a low temperature deposition of a layer of a biaxially oriented cubic oxide material upon the silicon dioxide surface of a silicon dioxide/silicon substrate is provided.

Structural, optical and dielectric properties of Sn0.97Ce0.03O2 nanostructures

NASA Astrophysics Data System (ADS)

Ahmed, Ateeq; Siddique, M. Naseem; Ali, Tinku; Tripathi, P.

2018-05-01

In present work, 3% cerium doped SnO2 (Sn0.97Ce0.03O2) nanoparticles (NPs) have been synthesized by sol-gel method. The prepared sample has been characterized by using various techniques such as XRD, UV-visible absorption spectroscopy and LCR meter measurements. Structural Rietveld refinement of XRD data reveals that (Sn0.97Ce0.03O2) sample has a pure single phase tetragonal structure with space group (P42/mnm) without creating any impurity phase such as cerium oxide. UV-visible spectroscopy determines band gap value 3.47 eV for (Sn0.97Ce0.03O2) NPs using Tauc's relation. Dielectric constant and loss decreased with increase in frequency while ac conductivity was found to increase with increase in frequency. The observed dielectric results has been explained in the light of Maxwell-Wagner model.

Direct Neutron Spectroscopy Observation of Cerium Hydride Species on a Cerium Oxide Catalyst

DOE PAGES

Wu, Zili; Cheng, Yongqiang; Tao, Franklin; ...

2017-06-27

Ceria has recently shown intriguing hydrogenation reactivity in catalyzing alkyne selectively to alkenes. However, the mechanism of the hydrogenation reaction, especially the activation of H 2, remains experimentally elusive. In this paper, we report the first direct spectroscopy evidence for the presence of both surface and bulk Ce–H species upon H 2 dissociation over ceria via in situ inelastic neutron scattering spectroscopy. Combined with in situ ambient-pressure X-ray photoelectron spectroscopy, IR, and Raman spectroscopic studies, the results together point to a heterolytic dissociation mechanism of H 2 over ceria, leading to either homolytic products (surface OHs) on a close-to-stoichiometric ceriamore » surface or heterolytic products (Ce–H and OH) with the presence of induced oxygen vacancies in ceria. Finally, the finding of this work has significant implications for understanding catalysis by ceria in both hydrogenation and redox reactions where hydrogen is involved.« less

Direct Neutron Spectroscopy Observation of Cerium Hydride Species on a Cerium Oxide Catalyst

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

Wu, Zili; Cheng, Yongqiang; Tao, Franklin

Ceria has recently shown intriguing hydrogenation reactivity in catalyzing alkyne selectively to alkenes. However, the mechanism of the hydrogenation reaction, especially the activation of H 2, remains experimentally elusive. In this paper, we report the first direct spectroscopy evidence for the presence of both surface and bulk Ce–H species upon H 2 dissociation over ceria via in situ inelastic neutron scattering spectroscopy. Combined with in situ ambient-pressure X-ray photoelectron spectroscopy, IR, and Raman spectroscopic studies, the results together point to a heterolytic dissociation mechanism of H 2 over ceria, leading to either homolytic products (surface OHs) on a close-to-stoichiometric ceriamore » surface or heterolytic products (Ce–H and OH) with the presence of induced oxygen vacancies in ceria. Finally, the finding of this work has significant implications for understanding catalysis by ceria in both hydrogenation and redox reactions where hydrogen is involved.« less

Mixed cerium-platinum oxides: Electronic structure of [CeO]Pt{sub n} (n = 1, 2) and [CeO{sub 2}]Pt complex anions and neutrals

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

Ray, Manisha; Kafader, Jared O.; Topolski, Josey E.

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 Pt{sub 2} 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]Pt{sub 2} complexes are therefore ionic, with electronic structures described qualitatively as [CeO{sup +2}]Pt{sup −2} and [CeO{sup +}]Pt{sub 2}{sup −}, respectively. The associated anions are described qualitatively as [CeO{sup +}]Pt{sup −2} and [CeO{sup +}]Pt{sub 2}{sup −2}, respectively. In both neutrals and anions, the most stable molecularmore » structures determined by calculations feature a distinct CeO moiety, with the positively charged Ce center pointing toward the electron rich Pt or Pt{sub 2} 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 CeO{sub 2}, which has no Ce-localized electrons that can readily be donated to Pt, the anion is described as [CeO{sub 2}]Pt{sup −}. The molecular structure predicted computationally suggests that it is governed by charge-dipole interactions. The neutral [CeO{sub 2}]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{sup −} daughter ion formation. The electronic structures of these complexes are related to local interactions in Pt-ceria catalyst-support systems.« less

Facile synthesis of heterostructured cerium oxide/yttrium oxide nanocomposite in UV light induced photocatalytic degradation and catalytic reduction: Synergistic effect of antimicrobial studies.

PubMed

Maria Magdalane, C; Kaviyarasu, K; Judith Vijaya, J; Siddhardha, B; Jeyaraj, B

2017-08-01

Ceria (CeO 2 ) is an exciting alternative noble metal catalyst, because it has ability to release and absorb oxygen in the redox system, and function as an oxygen buffer. In this study, heterostructured catalysts consisting of CeO 2 /Y 2 O 3 nanocomposites were successfully synthesized by hydrothermal method in the presence of sodium hydroxide as a reducing agent from cerium nitrate and yttrium nitrate as a precursor which was then evaluated for its photocatalytic activity in the degradation of Rhodamine B (RhB) synthetic dye. Scanning electron microscopy (SEM) imparts the surface morphology and size of the prepared sample. Elemental compositions and the purity of the nanoparticles are proved by energy dispersive X-ray Spectroscopy (EDX). CeO 2 /Y 2 O 3 nanoparticles were made up of CeO and YO bonds which are confirmed by Fourier transform infrared spectroscopy (FTIR). Synthesis temperature and pressure, during hydrothermal reactions, plays a critical role in controlling the shape, size, oxygen vacancy concentration, and low temperature reducibility in CeO 2 based nanocomposites. The lattice constants and oxygen vacancy concentrations of ceria nanoparticles also depend upon the concentration of hydroxide ion which leads to better morphology at low temperature and pressure. Hydrogenation of p-nitrophenol to p-aminophenol with a reducing agent is conveniently carried out in aqueous medium by using this binary metal oxide catalyst. Further, the photocatalytic performance of the synthesized nanoparticles was monitored by photocatalytic degradation of Rhodamine B synthetic dye under UV light irradiation. To get maximum photocatalytic degradation (PCD) efficiency, we have used H 2 O 2 for the generation of excess reactive oxygen species (ROS). In addition, the antibacterial activity of nanoparticles against bacteria was also examined. The observed antibacterial activity results are comparable with the results obtained using the standard antibiotic. Copyright © 2017 Elsevier B.V. All rights reserved.

Elemental sulfur recovery process

DOEpatents

Flytzani-Stephanopoulos, M.; Zhicheng Hu.

1993-09-07

An improved catalytic reduction process for the direct recovery of elemental sulfur from various SO[sub 2]-containing industrial gas streams. The catalytic process provides combined high activity and selectivity for the reduction of SO[sub 2] to elemental sulfur product with carbon monoxide or other reducing gases. The reaction of sulfur dioxide and reducing gas takes place over certain catalyst formulations based on cerium oxide. The process is a single-stage, catalytic sulfur recovery process in conjunction with regenerators, such as those used in dry, regenerative flue gas desulfurization or other processes, involving direct reduction of the SO[sub 2] in the regenerator off gas stream to elemental sulfur in the presence of a catalyst. 4 figures.

Elemental sulfur recovery process

DOEpatents

Flytzani-Stephanopoulos, Maria; Hu, Zhicheng

1993-01-01

An improved catalytic reduction process for the direct recovery of elemental sulfur from various SO.sub.2 -containing industrial gas streams. The catalytic process provides combined high activity and selectivity for the reduction of SO.sub.2 to elemental sulfur product with carbon monoxide or other reducing gases. The reaction of sulfur dioxide and reducing gas takes place over certain catalyst formulations based on cerium oxide. The process is a single-stage, catalytic sulfur recovery process in conjunction with regenerators, such as those used in dry, regenerative flue gas desulfurization or other processes, involving direct reduction of the SO.sub.2 in the regenerator off gas stream to elemental sulfur in the presence of a catalyst.

Ceramification: A plutonium immobilization process

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

Rask, W.C.; Phillips, A.G.

1996-05-01

This paper describes a low temperature technique for stabilizing and immobilizing actinide compounds using a combination process/storage vessel of stainless steel, in which measured amounts of actinide nitrate solutions and actinide oxides (and/or residues) are systematically treated to yield a solid article. The chemical ceramic process is based on a coating technology that produces rare earth oxide coatings for defense applications involving plutonium. The final product of this application is a solid, coherent actinide oxide with process-generated encapsulation that has long-term environmental stability. Actinide compounds can be stabilized as pure materials for ease of re-use or as intimate mixtures withmore » additives such as rare earth oxides to increase their degree of proliferation resistance. Starting materials for the process can include nitrate solutions, powders, aggregates, sludges, incinerator ashes, and others. Agents such as cerium oxide or zirconium oxide may be added as powders or precursors to enhance the properties of the resulting solid product. Additives may be included to produce a final product suitable for use in nuclear fuel pellet production. The process is simple and reduces the time and expense for stabilizing plutonium compounds. It requires a very low equipment expenditure and can be readily implemented into existing gloveboxes. The process is easily conducted with less associated risk than proposed alternative technologies.« less

High energy resolution with transparent ceramic garnet scintillators

NASA Astrophysics Data System (ADS)

Cherepy, N. J.; Seeley, Z. M.; Payne, S. A.; Beck, P. R.; Swanberg, E. L.; Hunter, S.; Ahle, L.; Fisher, S. E.; Melcher, C.; Wei, H.; Stefanik, T.; Chung, Y.-S.; Kindem, J.

2014-09-01

Breakthrough energy resolution, R(662keV) < 4%, has been achieved with an oxide scintillator, Cerium-doped Gadolinium Yttrium Gallium Aluminum Garnet, or GYGAG(Ce). Transparent ceramic GYGAG(Ce), has a peak emission wavelength of 550 nm that is better matched to Silicon photodetectors than to standard PMTs. We are therefore developing a spectrometer based on pixelated GYGAG(Ce) on a Silicon photodiode array that can provide R(662 keV) = 3.6%. In comparison, with large 1-2 in3 size GYGAG(Ce) ceramics we obtain R(662 keV) = 4.6% with PMT readout. We find that ceramic GYGAG(Ce) of a given stoichiometric chemical composition can exhibit very different scintillation properties, depending on sintering conditions and post-anneal treatments. Among the characteristics of transparent ceramic garnet scintillators that can be controlled by fabrication conditions are: scintillation decay components and their amplitudes, intensity and duration of afterglow, thermoluminescence glow curve peak positions and amplitudes, integrated light yield, light yield non-proportionality - as measured in the Scintillator Light Yield Non-Proportionality Characterization Instrument (SLYNCI), and energy resolution for gamma spectroscopy. Garnet samples exhibiting a significant fraction of Cerium dopant in the tetravalent valence also exhibit: faster overall scintillation decay, very low afterglow, high light yield, but poor light yield proportionality and degraded energy resolution.

[Coloration of mica glass ceramic for use in dental CAD/CAM system].

PubMed

Sun, Ying; Wang, Zhong-yi; Tian, Jie-mo; Cao, Xiao-gang

2003-03-01

An intrinsically colored machinable glass-ceramic containing tetrasilicic fluormica as the predominant crystal phase was studied, which was used in molar crown in dental CAD/CAM system. Orthogonal design analysis was used to select appropriate base formula, coloration and heat treatment process. Factors influencing the color appearance of mica glass ceramic were nucleation agent and the ratio of Mg(2+) to K(+) in base formula; Cerium oxide (CeO(2)) was used as the main coloration; The preferred heat treatment was 650 degrees C for 1 h and 1,000 degrees C or 1,050 degrees C for 3 h - 4 h. This mica glass-ceramic could provide 4 to 5 color appearance for dental use, it showed excellent machinability which was eminently suitable for use in dental CAD/CAM system.

Two-stage epitaxial growth of vertically-aligned SnO2 nano-rods on (001) ceria

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

Solovyov, VF; Wu, LJ; Rupich, MW

2014-12-15

Growth of high-aspect ratio oriented tin oxide, SnO2, nano-rods is complicated by a limited choice of matching substrates. We show that a (001) cerium oxide, CeO2, surface uniquely enables epitaxial growth of tin-oxide nano-rods via a two-stage process. First, (100) oriented nano-wires coat the ceria surface by lateral growth, forming a uniaxially-textured SnO2 deposit. Second, vertical SnO2 nano-rods nucleate on the deposit by homoepitaxy. We demonstrate growth of vertically oriented 1-2 mu m long nano-rods with an average diameter of approximate to 20 nm. 2014 Elsevier B.V. All rights reserved.

Nanocrystal assembly for tandem catalysis

DOEpatents

Yang, Peidong; Somorjai, Gabor; Yamada, Yusuke; Tsung, Chia-Kuang; Huang, Wenyu

2014-10-14

The present invention provides a nanocrystal tandem catalyst comprising at least two metal-metal oxide interfaces for the catalysis of sequential reactions. One embodiment utilizes a nanocrystal bilayer structure formed by assembling sub-10 nm platinum and cerium oxide nanocube monolayers on a silica substrate. The two distinct metal-metal oxide interfaces, CeO.sub.2--Pt and Pt--SiO.sub.2, can be used to catalyze two distinct sequential reactions. The CeO.sub.2--Pt interface catalyzed methanol decomposition to produce CO and H.sub.2, which were then subsequently used for ethylene hydroformylation catalyzed by the nearby Pt--SiO.sub.2 interface. Consequently, propanal was selectively produced on this nanocrystal bilayer tandem catalyst.

NON-CORROSIVE PLUTONIUM FUEL SYSTEMS

DOEpatents

Coffinberry, A.S.; Waber, J.T.

1962-10-23

An improved plutonium reactor liquid fuel is described for utilization in a nuclear reactor having a tantalum fuel containment vessel. The fuel consists of plutonium and a diluent such as iron, cobalt, nickel, cerium, cerium-- iron, cerium--cobalt, cerium--nickel, and cerium--copper, and an additive of carbon and silicon. The carbon and silicon react with the tantalum container surface to form a coating that is self-healing and prevents the corrosive action of liquid plutonium on the said tantalum container. (AEC)

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

Yan, Yushan

In this work, multiple polymer backbones were screened for oxidation resistance and multiple chemistries were explored for tethering tris(2,4,6-trimethylphenyl)phosphonium (9MeTTP +) to the selected polymer backbones. A new tethering strategy through brominated 9MeTTP+ cation was developed and used to obtain the desired 9MeTTP +-functionalized polysulfone (PSf) and hexafluoro polybenzimidazole (F 6PBI) polymer. The crosslinked 9MeTTP+-functionalized hexafluoro polybenzimidazole (9MeTTP-F 6PBI) polymer demonstrated excellent oxidation stability that met the go-no-go milestone of the first year. However, large-scale bromination inevitably involved multi-bromination products, which led to polymer crosslinking in the next tethering. A new synthesis strategy with diiodobutane as linker was developed tomore » overcome the crosslinking problem. The prepared 9MeTTP +-F 6PBI membrane without crosslinking showed only 3.58% water uptake and less than 1 mS/cm OH - conductivity in water at 20°C, possibly due to the hydrophobic 9MeTTP + cation. In order to improve the conductivity, hydrophilic tris(2,4,6-trimethoxylphenyl)phosphonium (9MeOTTP+) cation was tethered to an F 6PBI backbone, and a 9MeOTTP +-F 6PBI PTFE reinforced membrane was prepared with 17.4% water uptake to increase the mechanical strength and durability in cerium (IV) solution. A 9MeOTTP+-F 6PBI PTFE reinforced membrane had less than 20% conductivity loss during an accelerated stability test in 0.5 M cerium (IV) and 1.3 M HClO 4 at 55°C for 100 hours. Moreover, a 9MeOTTP +-F 6PBI PTFE reinforced membrane had more than double the lifetime of commercial FAS-30 and FAB-PK-130 AEMs during an accelerated stability test in 0.5 M cerium (IV) and 1.3 M HClO 4 at 55°C. Low area specific resistance (ASR) of a 9MeOTTP +-F 6PBI PTFE reinforced membrane in the sulfuric acid system was also achieved due to the high acid doping ability of the polymer structure. The cationic 9MeOTTP +-F 6PBI PTFE reinforced membrane shows a cerium (IV) permeability that is 27-fold lower than that of Nafion 212. Excellent voltage and energy efficiencies with a 9MeOTTP +-F 6PBI PTFE reinforced membrane were demonstrated in an all-vanadium redox flow battery (VRFB).« less

TU-H-CAMPUS-TeP2-05: Selective Protection of Normal Tissue by Cerium Oxide Nanoparticles During Radiation Therapy

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

Ouyang, Z; Ngwa, W; Brigham and Women’s Hospital, Dana-Farber Cancer Institute and Harvard Medical School, Boston, MA

2016-06-15

Purpose: Cerium oxide nanoparticles (CONPs) have unique pH dependent properties such that they act as a radical modulator. These properties may be used in radiation therapy (RT) to protect normal tissue. This work investigates the selective radioprotection of CONPs in-vitro and potential for in-situ delivery of CONPs in prostate cancer RT. Methods: i) Normal human umbilical vein endothelial cells (HUVEC) and human prostate cancer cells (PC-3) were treated with 0 or 2 ng/mL CONPs (NP size: 5 nm). 2 Gy of 100 kVp radiation was delivered to the cells 4 hours after the CONP treatment. Cell viability was checked 48more » hours later using MTS assays. ii) A prostate tumor was modeled as a 2-cm diameter sphere. CONPs were proposed to be loaded in a hollow radiotherapy fiducial marker. The concentration profile for the CONPs within the tumor was modeled with a previously validated diffusion equation employed in other studies for nanoparticles 10 nm or less. Results: i) Without radiation, cell viability was above 90% when treated with 2 ng/mL CONPs for both HUVEC and PC-3. After irradiation, a slightly higher viability was observed in HUVEC with CONPs than the ones without CONPs, and this effect was not observed in PC-3. ii) Based on the calculations, 2 ng/mL of CONPs could be delivered to normal cells by diffusion with a 1 µg/mL initial concentration within two weeks. Conclusion: We conclude that CONPs can provide selective radioprotection. The delivery of needed concentrations of CONPs is feasible via in-situ release from radiotherapy biomaterials (e.g. fiducials) loaded with the CONPs.« less

A facile synthesis for cauliflower like CeO2 catalysts from Ce-BTC precursor and their catalytic performance for CO oxidation

NASA Astrophysics Data System (ADS)

Zhang, Xiaodong; Hou, Fulin; Yang, Yang; Wang, Yuxin; Liu, Ning; Chen, Dan; Yang, Yiqiong

2017-11-01

The paper presents a novel and facile method for preparing cauliflowerlike CeO2 through direct decomposition of cerium based metal-organic framework (MOF) Ce-BTC (BTC = 1,3,5-benzenetricarboxylic acid) straw in air. Several analytical tools such as Scanning electron microscopy (SEM), X-ray diffraction (XRD), Thermogravimetric (TG), N2 adsorption-desorption, Temperature programmed reduction (TPR), Raman, X-ray photoelectron spectroscopic (XPS) and Photoluminescence (PL) have been used to characterize Ce-BTC and CeO2. The Ce-BTC calcined at 500 °C (CeO2-500) maintains the morphology of its template ;Ce-BTC; and forms a special cauliflower-like structure. XRD patterns showed that the catalyst has a perfect CeO2 crystal structure and has a smaller particle size. The prepared CeO2 cauliflowers exhibit excellent catalytic activities, long-term stability, and cycling stability for CO oxidation. The improved catalytic activities could be attributed to porous nanorods of CeO2 cauliflowers, which provide more active sites and oxygen vacancy for CO oxidation.

Application of 3-methylbenzothiazolin-2-one hydrazone for the quantitative spectrophotometric determination of oxcarbazepine in pharmaceuticals with cerium(IV) and periodate

NASA Astrophysics Data System (ADS)

Rajendraprasad, N.; Basavaiah, K.; Vinay, K. B.

2012-09-01

Two simple, sensitive, selective, accurate, and cost-effective spectrophotometric methods are described for the assay of oxcarbazepine (OXC) in bulk drug and in tablets. The methods are based on an oxidative coupling reaction involving OXC, 3-methylbenzothiazolin-2-one hydrazone (MBTH), and cerium(IV) sulfate at pH 4.28 ± 0.07 (method A) or sodium periodate at pH > 4.0 (method B) to form an orange colored product with an absorption maximum at 450 nm. Under optimized experimental conditions, the calibration graphs are linear over the ranges of 4-80 and 2-32 μg/ml for methods A and B, respectively, with correlation coefficient (r) values of 0.9984 and 0.9976. The apparent molar absorptivity values are 3.13ṡ103 and 9.13ṡ103 l/molṡcm for methods A and B, respectively. The other optical characteristics such as Sandell's sensitivity, limits of detection (LOD) and quantification (LOQ) values are also reported. The accuracy and precision of the methods were evaluated based on intra-day and inter-day variations. The proposed methods were successfully applied to the determination of OXC in tablets: the results were comparable with the published data obtained using the reference method. The reaction stoichiometry of OXC with MBTH (1:1 in method A and 1:2 in method B) was also evaluated using the limiting logarithmic method, and a possible reaction pathway is presented for the both methods.

Cerium oxide nanoparticles protect rodent lungs from hypobaric hypoxia-induced oxidative stress and inflammation.

PubMed

Arya, Aditya; Sethy, Niroj Kumar; Singh, Sushil Kumar; Das, Mainak; Bhargava, Kalpana

2013-01-01

Cerium oxide nanoparticles (nanoceria) are effective at quenching reactive oxygen species (ROS) in cell culture and animal models. Although nanoceria reportedly deposit in lungs, their efficacy in conferring lung protection during oxidative stress remains unexplored. Thus, the study evaluated the protective efficacy of nanoceria in rat lung tissue during hypobaric hypoxia. A total of 48 animals were randomly divided into four equal groups (control [C], nanoceria treated [T], hypoxia [H], and nanoceria treated plus hypoxia [T+H]). Animals were injected intraperitoneally with either a dose of 0.5 μg/kg body weight/week of nanoceria (T and T+H groups) or vehicle (C and H groups) for 5 weeks. After the final dose, H and T+H animals were challenged with hypobaric hypoxia, while C and T animals were maintained at normoxia. Lungs were isolated and homogenate was obtained for analysis of ROS, lipid peroxidation, glutathione, protein carbonylation, and 4-hydroxynonenal-adduct formation. Plasma was used for estimating major inflammatory cytokines using enzyme-linked immunosorbent assay. Intact lung tissues were fixed and both transmission electron microscopy and histopathological examinations were carried out separately for detecting internalization of nanoparticles as well as altered lung morphology. Spherical nanoceria of 7-10 nm diameter were synthesized using a microemulsion method, and the lung protective efficacy of the nanoceria evaluated during hypobaric hypoxia. With repeated intraperitoneal injections of low micromole concentration, we successfully localized the nanoceria in rodent lung without any inflammatory response. The lung-deposited nanoceria limited ROS formation, lipid peroxidation, and glutathione oxidation, and prevented oxidative protein modifications like nitration and carbonyl formation during hypobaric hypoxia. We also observed reduced lung inflammation in the nanoceria-injected lungs, supporting the anti-inflammatory properties of nanoceria. Cumulatively, these results suggest nanoceria deposit in lungs, confer protection by quenching noxious free radicals during hypobaric hypoxia, and do not evoke any inflammatory response.

On the use of thermal NF3 as the fluorination and oxidation agent in treatment of used nuclear fuels

NASA Astrophysics Data System (ADS)

Scheele, Randall; McNamara, Bruce; Casella, Andrew M.; Kozelisky, Anne

2012-05-01

This paper presents results of our investigation on the use of nitrogen trifluoride as a fluorination or fluorination/oxidation agent for separating valuable constituents from used nuclear fuels by exploiting the different volatilities of the constituent fission product and actinide fluorides. Our thermodynamic calculations show that nitrogen trifluoride has the potential to produce volatile fission product and actinide fluorides from oxides and metals that can form volatile fluorides. Simultaneous thermogravimetric and differential thermal analyses show that the oxides of lanthanum, cerium, rhodium, and plutonium are fluorinated but do not form volatile fluorides when treated with nitrogen trifluoride at temperatures up to 550 °C. However, depending on temperature, volatile fluorides or oxyfluorides can form from nitrogen trifluoride treatment of the oxides of niobium, molybdenum, ruthenium, tellurium, uranium, and neptunium. Thermoanalytical studies demonstrate near-quantitative separation of uranium from plutonium in a mixed 80% uranium and 20% plutonium oxide. Our studies of neat oxides and metals suggest that the reactivity of nitrogen trifluoride may be adjusted by temperature to selectively separate the major volatile fuel constituent uranium from minor volatile constituents, such as Mo, Tc, Ru and from the non-volatile fuel constituents based on differences in their reaction temperatures and kinetic behaviors. This reactivity is novel with respect to that reported for other fluorinating reagents F2, BrF5, ClF3.

Structural and magnetic conformation of a cerocene [Ce(COT'')2]- exhibiting a uniconfigurational f1 ground state and slow-magnetic relaxation.

PubMed

Le Roy, Jennifer J; Korobkov, Ilia; Kim, Jee Eon; Schelter, Eric J; Murugesu, Muralee

2014-02-21

Magnet-like behaviour, in the form of slow relaxation of the magnetization, was observed for a monometallic cerium(III) sandwich complex. The use of trimethylsilyl substituted COT ligands (COT'') led to the formation of a staggered COT'' arrangement in the cerocene-type sandwich complex with a well-defined oxidation state of +3 for the Ce ion.

Design and Synthesis of Novel Isoxazole Tethered Quinone-Amino Acid Hybrids

PubMed Central

Ravi Kumar, P.; Sambaiah, M.; Kandula, Venu; Payili, Nagaraju; Jaya Shree, A.; Yennam, Satyanarayana

2014-01-01

A new series of isoxazole tethered quinone-amino acid hybrids has been designed and synthesized involving 1,3-dipolar cycloaddition reaction followed by an oxidation reaction using cerium ammonium nitrate (CAN). Using this method, for the first time various isoxazole tethered quinone-phenyl alanine and quinone-alanine hybrids were synthesized from simple commercially available 4-bromobenzyl bromide, propargyl bromide, and 2,5-dimethoxybenzaldehyde in good yield. PMID:25709839

Design and synthesis of novel isoxazole tethered quinone-amino Acid hybrids.

PubMed

Ravi Kumar, P; Behera, Manoranjan; Sambaiah, M; Kandula, Venu; Payili, Nagaraju; Jaya Shree, A; Yennam, Satyanarayana

2014-01-01

A new series of isoxazole tethered quinone-amino acid hybrids has been designed and synthesized involving 1,3-dipolar cycloaddition reaction followed by an oxidation reaction using cerium ammonium nitrate (CAN). Using this method, for the first time various isoxazole tethered quinone-phenyl alanine and quinone-alanine hybrids were synthesized from simple commercially available 4-bromobenzyl bromide, propargyl bromide, and 2,5-dimethoxybenzaldehyde in good yield.

Cerium and zinc: Dual-doped LiMn 2O 4 spinels as cathode material for use in lithium rechargeable batteries

NASA Astrophysics Data System (ADS)

Thirunakaran, R.; Sivashanmugam, A.; Gopukumar, S.; Rajalakshmi, R.

Pristine spinel lithium manganese oxide (LiMn 2O 4) and zinc- and cerium-doped lithium manganese oxide [LiZn xCe yMn 2- x- yO 4 (x = 0.01-0.10; y = 0.10-0.01)] are synthesized for the first time via the sol-gel route using p-amino benzoic acid as a chelating agent to obtain micron-sized particles and enhanced electrochemical performance. The sol-gel route offers shorter heating time, better homogeneity and control over stoichiometry. The resulting spinel product is characterized through various methods such as thermogravimetic and differential thermal analysis (TG/DTA), Fourier-transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDAX) and electrochemical galvanostatic cycling studies. Charge-discharge studies of LiMn 2O 4 samples heated at 850 °C exhibit a discharge capacity of 122 mAh g -1 and a corresponding 99% coulombic efficiency in the 1st cycle. The discharge capacity and cycling performance of LiZn 0.01Ce 0.01Mn 1.98O 4 is found to be superior (124 mAh g -1), with a low capacity fade (0.1 mAh g -1 cycle -1) over the investigated 10 cycles.

Porous nano-cerium oxide wood chip biochar composites for aqueous levofloxacin removal and sorption mechanism insights.

PubMed

Yi, Shengze; Sun, Yuanyuan; Hu, Xin; Xu, Hongxia; Gao, Bin; Wu, Jichun

2017-01-14

The adsorption removal of levofloxacin (LEV), a widely used fluoroquinolone antibiotic, by using the biochars derived from the pyrolysis of pine wood chip pretreated with cerium trichloride was investigated through batch sorption experiments and multiple characterization techniques. The differences in the basic physicochemical properties between Ce-impregnated biochars and the pristine biochars were confirmed by the analysis of elemental compositions, specific surface areas, energy dispersive spectrometry, X-ray diffraction, and thermo-gravimetry. FT-IR spectra of the pre- and post-sorption biochars confirmed the chemical adsorption for LEV sorption onto the biochars. Large shifts in the binding energy of Ce 3d , O 1s , C 1s , and N 1s regions on the pre- and post-sorption biochars indicated the surface complexation of LEV molecule onto the biochars. The binding species of Ce 4+ and Ce 3+ identified by X-ray photoelectron spectroscopy reflect the role of Ce oxides during sorption. Batch adsorption showed the significant enhancement of adsorption capacity for LEV after the Ce modification. Batch adsorption kinetic data fitted well with the pseudo-second-order model. Both the Langmuir and the Freundlich models reproduced the isotherm data well. Findings from this work indicated that Ce-impregnated biochars can be effective for the removal of aqueous LEV.

Chemoselective phototransformation of C-H bonds on a polymer surface through a photoinduced cerium recycling redox reaction.

PubMed

Huang, Zhenhua; Wu, Zhengfang; Yang, Peng; Yang, Wantai

2014-09-01

It is generally accepted that Ce(4+) is unable to directly oxidize unreactive alkyl C-H bonds without the assistance of adjacent polar groups. Herein, we demonstrate in our newly developed confined photochemical reaction system that this recognized issue may be challenged. As we found, when a thin layer of a CeCl(3)/HCl aqueous solution was applied to a polymeric substrate and the substrate subjected to UV irradiation, Ce(3+) was first photooxidized to form Ce(4+) in the presence of H(+), and the in situ formed Ce(4+) then performs an oxidation reaction on the C-H bonds of the polymer surface to form surface-carbon radicals for radical graft polymerization reactions and functional-group transformations, while reducing to Ce(3+) and releasing H(+) in the process. This photoinduced cerium recycling redox (PCRR) reaction behaved as a biomimetic system in an artificial recycling reaction, leading to a sustainable chemical modification strategy for directly transforming alkyl C-H bonds on polymer surfaces into small-molecule groups and polymer brushes. This method is expected to provide a green and economical tool for industrial applications of polymer-surface modification. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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. Copyright © 2014 Elsevier Ltd. All rights reserved.

Photovoltaic performance and stability of fullerene/cerium oxide double electron transport layer superior to single one in p-i-n perovskite solar cells

NASA Astrophysics Data System (ADS)

Xing, Zhou; Li, Shu-Hui; Wu, Bao-Shan; Wang, Xin; Wang, Lu-Yao; Wang, Tan; Liu, Hao-Ran; Zhang, Mei-Lin; Yun, Da-Qin; Deng, Lin-Long; Xie, Su-Yuan; Huang, Rong-Bin; Zheng, Lan-Sun

2018-06-01

Interface engineering that involves in the metal cathodes and the electron transport layers (ETLs) facilitates the simultaneous improvement of device performances and stability in perovskite solar cells (PSCs). Herein, low-temperature solution-processed cerium oxide (CeOx) films are prepared by a facile sol-gel method and employed as the interface layers between [6,6]-phenyl-C61-butyric acid methyl ester (PC61BM) and an Ag back contact to form PC61BM/CeOx double ETLs. The introduction of CeOx enables electron extraction to the Ag electrode and protects the underlying perovskite layer and thus improves the device performance and stability of the p-i-n PSCs. The p-i-n PSCs with double PC61BM/CeOx ETLs demonstrate a maximum power conversion efficiency (PCE) of 17.35%, which is superior to those of the devices with either PC61BM or CeOx single ETLs. Moreover, PC61BM/CeOx devices exhibit excellent stability in light soaking, which is mainly due to the chemically stable CeOx interlayer. The results indicate that CeOx is a promising interface modification layer for stable high-efficiency PSCs.

Protection and Sensitization of Human Cells to Proton Radiation by Cerium Oxide Nanoparticles

NASA Astrophysics Data System (ADS)

Carlson, Nathan B.

In radiation therapy for the treatment of cancer, there is demand for novel approaches that will improve tumor cell killing while protecting healthy tissue. One such approach that has shown considerable promise is the application of nanoparticles as radiation sensitizers for tumor cells and as radiation protectants for healthy tissue. In this investigation, cerium oxide nanoparticles (CNPs) obtained from the University of Central Florida's NanoScience Technology Center were studied for their protective effect to charged particle radiation in non-malignant breast cells, and for their sensitizing effect in breast and prostate cancer cell lines. These experiments were conducted at East Carolina University, where human cells were grown in the cell culture facility in the Department of Biology and then irradiated with energetic protons in the Accelerator Laboratory in the Department of Physics. Prior to irradiation, the cells were treated with distinct CNP preparations ranging in concentrations from 10 nanomolar to 10 micromolar, and cell viability was assessed using multiple assays post-irradiation. Radioprotection and radiosensitization were observed for several of the CNP treatments tested. Ultimately, the goal is to find a specific nanoparticle treatment that holds the synergistic effect of enhancing the rate of killing in tumor cells while simultaneously improving the survival of normal cells.

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.

Ultrastructural Interactions and Genotoxicity Assay of Cerium Dioxide Nanoparticles on Mouse Oocytes

PubMed Central

Courbiere, Blandine; Auffan, Mélanie; Rollais, Raphaël; Tassistro, Virginie; Bonnefoy, Aurélie; Botta, Alain; Rose, Jérôme; Orsière, Thierry; Perrin, Jeanne

2013-01-01

Cerium dioxide nanoparticles (CeO2 ENPs) are on the priority list of nanomaterials requiring evaluation. We performed in vitro assays on mature mouse oocytes incubated with CeO2 ENPs to study (1) physicochemical biotransformation of ENPs in culture medium; (2) ultrastructural interactions with follicular cells and oocytes using Transmission Electron Microscopy (TEM); (3) genotoxicity of CeO2 ENPs on follicular cells and oocytes using a comet assay. DNA damage was quantified as Olive Tail Moment. We show that ENPs aggregated, but their crystal structure remained stable in culture medium. TEM showed endocytosis of CeO2 ENP aggregates in follicular cells. In oocytes, CeO2 ENP aggregates were only observed around the zona pellucida (ZP). The comet assay revealed significant DNA damage in follicular cells. In oocytes, the comet assay showed a dose-related increase in DNA damage and a significant increase only at the highest concentrations. DNA damage decreased significantly both in follicular cells and in oocytes when an anti-oxidant agent was added in the culture medium. We hypothesise that at low concentrations of CeO2 ENPs oocytes could be protected against indirect oxidative stress due to a double defence system composed of follicular cells and ZP. PMID:24185910

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.

Method for decontamination of radioactive metal surfaces

DOEpatents

Bray, L.A.

1996-08-13

Disclosed is a method for removing radioactive contaminants from metal surfaces by applying steam containing an inorganic acid and cerium IV. Cerium IV is applied to contaminated metal surfaces by introducing cerium IV in solution into a steam spray directed at contaminated metal surfaces. Cerium IV solution is converted to an essentially atomized or vapor phase by the steam.

Synthesis of cerium and nickel doped titanium nanofibers for hydrolysis of sodium borohydride.

PubMed

Tamboli, Ashif H; Gosavi, S W; Terashima, Chiaki; Fujishima, Akira; Pawar, Atul A; Kim, Hern

2018-07-01

A recyclable titanium nanofibers, doped with cerium and nickel doped was successfully synthesized by using sol-gel and electrospinning method for hydrogen generation from alkali free hydrolysis of NaBH 4 . The resultant nanocomposite was characterized to find out the structural and physical-chemical properties by a series of analytical techniques such as FT-IR (Fourier transform infrared spectroscopy), XRD (X-ray diffraction), SEM (scanning electron microscope), EDX (energy-dispersive X-ray spectroscopy),N 2 adsorption-desorption and BET (Brunauer-Emmett-Teller), etc. The results revealed that cerium and nickel nanoparticles were homogeneously distributed on the surface of the TiO 2 nanofibers due to having similar oxidation state and atomic radium of TiO 2 nanofibers with CeO 2 and NiO for the effective immobilization of metal ions. The NiO doped catalyst showed superior catalytic performance towards the hydrolysis reaction of NaBH 4 at room temperature. These catalysts have ability to produce 305 mL of H 2 within the time of 160 min at room temperature. Additionally, reusability test revealed that the catalyst is active even after five runs of hydrolytic reaction, implying the as-prepared NiO doped TiO 2 nanofibers could be considered as a potential candidate catalyst for portable hydrogen fuel system such as PEMFC (proton exchange membrane fuel cells). Copyright © 2018 Elsevier Ltd. All rights reserved.

Superconducting composite with multilayer patterns and multiple buffer layers

DOEpatents

Wu, Xin D.; Muenchausen, Ross E.

1993-01-01

An article of manufacture including a substrate, a patterned interlayer of a material selected from the group consisting of magnesium oxide, barium-titanium oxide or barium-zirconium oxide, the patterned interlayer material overcoated with a secondary interlayer material of yttria-stabilized zirconia or magnesium-aluminum oxide, upon the surface of the substrate whereby an intermediate article with an exposed surface of both the overcoated patterned interlayer and the substrate is formed, a coating of a buffer layer selected from the group consisting of cerium oxide, yttrium oxide, curium oxide, dysprosium oxide, erbium oxide, europium oxide, iron oxide, gadolinium oxide, holmium oxide, indium oxide, lanthanum oxide, manganese oxide, lutetium oxide, neodymium oxide, praseodymium oxide, plutonium oxide, samarium oxide, terbium oxide, thallium oxide, thulium oxide, yttrium oxide and ytterbium oxide over the entire exposed surface of the intermediate article, and, a ceramic superco n FIELD OF THE INVENTION The present invention relates to the field of superconducting articles having two distinct regions of superconductive material with differing in-plane orientations whereby the conductivity across the boundary between the two regions can be tailored. This invention is the result of a contract with the Department of Energy (Contract No. W-7405-ENG-36).

Anionic Cerium Oxide Nanoparticles Protect Plant Photosynthesis from Abiotic Stress by Scavenging Reactive Oxygen Species.

PubMed

Wu, Honghong; Tito, Nicholas; Giraldo, Juan P

2017-11-28

Plant abiotic stress leads to accumulation of reactive oxygen species (ROS) and a consequent decrease in photosynthetic performance. We demonstrate that a plant nanobionics approach of localizing negatively charged, sub-11 nm, spherical cerium oxide nanoparticles (nanoceria) inside chloroplasts in vivo augments ROS scavenging and photosynthesis of Arabidopsis thaliana plants under excess light (2000 μmol m -2 s -1 , 1.5 h), heat (35 °C, 2.5 h), and dark chilling (4 °C, 5 days). Poly(acrylic acid) nanoceria (PNC) with a hydrodynamic diameter (10.3 nm)-lower than the maximum plant cell wall porosity-and negative ζ-potential (-16.9 mV) exhibit significantly higher colocalization (46%) with chloroplasts in leaf mesophyll cells than aminated nanoceria (ANC) (27%) of similar size (12.6 nm) but positive charge (9.7 mV). Nanoceria are transported into chloroplasts via nonendocytic pathways, influenced by the electrochemical gradient of the plasma membrane potential. PNC with a low Ce 3+ /Ce 4+ ratio (35.0%) reduce leaf ROS levels by 52%, including hydrogen peroxide, superoxide anion, and hydroxyl radicals. For the latter ROS, there is no known plant enzyme scavenger. Plants embedded with these PNC that were exposed to abiotic stress exhibit an increase up to 19% in quantum yield of photosystem II, 67% in carbon assimilation rates, and 61% in Rubisco carboxylation rates relative to plants without nanoparticles. In contrast, PNC with high Ce 3+ /Ce 4+ ratio (60.8%) increase overall leaf ROS levels and do not protect photosynthesis from oxidative damage during abiotic stress. This study demonstrates that anionic, spherical, sub-11 nm PNC with low Ce 3+ /Ce 4+ ratio can act as a tool to study the impact of oxidative stress on plant photosynthesis and to protect plants from abiotic stress.

Chemical analysis of extracting transition metal oxides from polymetallic ore by sulphate process

NASA Astrophysics Data System (ADS)

Enkh-Uyanga, Otgon-Uul; Munkhtsetseg, Baatar; Urangoo, Urtnasan; Tserendulam, Enkhtur; Agiimaa, Davaadorj

2017-06-01

In this research work we attempt to improve the purity of polymetallic ores in Mongolia whilst developing practical applications of its refinement processes and this paper presents the results of chemical research of extracting transition metal titanium oxides, ferrous oxide and rare earth oxides from polymetallic ore. Thereby, chemical and mineral analysis of polymetallic ore is carried out basis of responses to the support process at various degrees of water whereas transition metal sulphates solubility differ. As a result of sulphate and resulphurization process we have extracted anatase with 62.5 percent titanium dioxide and brookite mineral with 89.6 percent of titanium dioxide as well as mineral with 83.8 percent of ferrous oxide hematite and rare earth oxides with 57.6 percent of cerium oxide. These oxides are identified under various conditions in the thermal processing. The morphology structure and chemical content compound of the mineral has been verified as a result of the XRF, XRD, SEM-EDX analysis.

A simple thermometric technique for reaction-rate determination of inorganic species, based on the iodide-catalysed cerium(IV)-arsenic(III) reaction.

PubMed

Grases, F; Forteza, R; March, J G; Cerda, V

1985-02-01

A very simple reaction-rate thermometric technique is used for determination of iodide (5-20 ng ml ), based on its catalytic action on the cerium(IV)-arsenic(III) reaction, and for determination of mercury(II) (1.5-10 ng ml ) and silver(I) (2-10 ng ml ), based on their inhibitory effect on this reaction. The reaction is followed by measuring the rate of temperature increase. The method suffers from very few interferences and is applied to determination of iodide in biological and inorganic samples, and Hg(II) and Ag(I) in pharmaceutical products.

High performance Aurivillius phase sodium-potassium bismuth titanate lead-free piezoelectric ceramics with lithium and cerium modification

NASA Astrophysics Data System (ADS)

Wang, Chun-Ming; Wang, Jin-Feng

2006-11-01

The piezoelectric properties of the lithium and cerium modified A-site vacancies sodium-potassium bismuth titanate (NKBT) lead-free piezoceramics are investigated. The piezoelectric activity of NKBT ceramics is significantly improved by the modification of lithium and cerium. The Curie temperature TC, piezoelectric coefficient d33, and mechanical quality factor Qm for the NKBT ceramics modified with 0.10mol% (LiCe) are found to be 660°C, 25pC/N, and 3135, respectively. The Curie temperature gradually decreases from 675to650°C with the increase of (LiCe) modification. The dielectric spectroscopy shows that all the samples possess stable piezoelectric properties, demonstrating that the (LiCe) modified NKBT-based ceramics are the promising candidates for high temperature applications.

Specific Features of the Response of Cerium to Pulsed Actions

NASA Astrophysics Data System (ADS)

Atroshenko, S. A.; Zubareva, A. N.; Morozov, V. A.; Savenkov, G. G.; Utkin, A. V.

2018-02-01

Experimental studies of cerium at high rates and nanosecond durations of action have been performed. The isomorphic phase transition was studied upon shock compression. The spall strength of cerium has been determined. Cerium demonstrates anomalous compressibility upon dynamic loading. Stress waves dampen under action of a high-current electron beam due to the energy dissipation during fragmentation and twinning.

Pyrochlore-rich titanate ceramics for the immobilization of plutonium: redox effects on phase equilibria in cerium- and thorium- substituted analogs

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

Ryerson, F J; Ebbinghaus, B

2000-05-25

Three compositions representing plutonium-free analogs of a proposed Ca-Ti-Gd-Hf-U-PU oxide ceramic for the immobilization of plutonium were equilibrated at 1 atm, 1350 C over a range of oxygen fugacities between air and that equivalent to the iron-wuestite buffer. The cerium analog replaces Pu on a mole-per-mole basic with Ce; the thorium analog replaces Pu with Th. A third material has 10 wt% Al{sub 2}O{sub 3} added to the cerium analog to encourage the formation of a Hf-analog of, CaHfTi{sub 2}O{sub 7}, zirconolite, which is referred to as hafnolite. The predominant phase produced in each formulation under all conditions is pyrochlore,more » A{sub 2}T{sub 2}O{sub 7}, where the T site is filled by Ti, and Ca, the lanthanides, Hf, U and Pu are accommodated on the A-site. Other lanthanide and uranium-bearing phases encountered include brannerite (UTi{sub 2}O{sub 6}), hafnolite (CaHfTi{sub 2}O{sub 7}), perovskite (CaTiO{sub 3}) and a calcium-lanthanide aluminotitanate with nominal stoichiometry (Ca,Ln)Ti{sub 2}Al{sub 9}O{sub 19}, where Ln is a lanthanide. The phase compositions show progressive shifts with decreasing oxygen fugacity. All of the phases observed have previously been identified in titanate-based high-level radioactive waste ceramics and demonstrate the flexibility of these ceramics to variations in processing parameters. The main variation is an increase in the uranium concentrations of pyrochlore and brannerite which must be accommodated by variations in modal abundance. Pyrochlore compositions are consistent with existing spectroscopic data suggesting that uranium is predominantly pentavalent in samples synthesized in air. A simple model based on ideal stoichiometry suggests the U{sup +4}/{Sigma}U varies linearly with log fO{sub 2} and that all of the uranium is quadravalent at the iron-wuestite buffer.« less

Green chemical approach towards the synthesis of CeO2 doped with seashell and its bacterial applications intermediated with fruit extracts.

PubMed

Arasu, Mariadas Valan; Thirumamagal, R; Srinivasan, M P; Al-Dhabi, Naif Abdullah; Ayeshamariam, A; Saravana Kumar, D; Punithavelan, N; Jayachandran, M

2017-08-01

Nanomaterials of CeO 2 with A. vera were synthesized by using simple chemical method. Grapes drops are used as an oxidizing agent. Structural and morphological studies of nanomaterials of cerium oxide (CeO 2 ), were studied for combustion method of preparation. The precursor solution was initialized by a hydrothermal reaction. Cerium hydroxyl carbonate precursors which involves cerium (III) nitrate Ce(NO 3 ) 3 . 6 H 2 O with (1.0M) of seashell powder, 3% A. vera, extracts, grapes and pomegranate drops and this complex solution was used to produce the CeO 2 powder particles. We have prepared another sample with 5% of Aloe vera extract and found that 3% Aloe vera extract has lesser grain size and enhanced band gap values, so the article explained the sample analysis of combination with 3% extract of Aloe vera. The product has the rod pattern which was the unusual features appear to originate from the unique crystal chemistry aspects. From the optical absorption spectrum, it has been shown that the CeO 2 rods have 3.847eV of direct band gap energy. The minimum inhibitory concentration (MIC) values of the synthesized compounds exhibited activity towards various microbial pathogens such as B. subtilis (15μg/mL), S. aureus (50μg/mL), S. epidermidis (20μg/mL), E. faecalis (25μg/mL) and towards E. coli (100μg/mL), K. pneumoniae (50μg/mL) and P. aeruginosa (75μg/mL) respectively. The tests on bacterial activities confirmed that the CeO 2 rods are suitable hand for the biological applications. The seashell structure and the phytochemical contents of A. vera might enhance its bacterial activities. Copyright © 2017 Elsevier B.V. All rights reserved.

Size determination and quantification of engineered cerium oxide nanoparticles by flow field-flow fractionation coupled to inductively coupled plasma mass spectrometry.

PubMed

Sánchez-García, L; Bolea, E; Laborda, F; Cubel, C; Ferrer, P; Gianolio, D; da Silva, I; Castillo, J R

2016-03-18

Facing the lack of studies on characterization and quantification of cerium oxide nanoparticles (CeO2 NPs), whose consumption and release is greatly increasing, this work proposes a method for their sizing and quantification by Flow Field-flow Fractionation (FFFF) coupled to Inductively Coupled Plasma-Mass Spectrometry (ICP-MS). Two modalities of FFFF (Asymmetric Flow- and Hollow Fiber-Flow Field Flow Fractionation, AF4 and HF5, respectively) are compared, and their advantages and limitations discussed. Experimental conditions (carrier composition, pH, ionic strength, crossflow and carrier flow rates) are studied in detail in terms of NP separation, recovery, and repeatability. Size characterization of CeO2 NPs was addressed by different approaches. In the absence of feasible size standards of CeO2 NPs, suspensions of Ag, Au, and SiO2 NPs of known size were investigated. Ag and Au NPs failed to show a comparable behavior to that of the CeO2 NPs, whereas the use of SiO2 NPs provided size estimations in agreement to those predicted by the theory. The latter approach was thus used for characterizing the size of CeO2 NPs in a commercial suspension. Results were in adequate concordance with those achieved by transmission electron microscopy, X-ray diffraction and dynamic light scattering. The quantification of CeO2 NPs in the commercial suspension by AF4-ICP-MS required the use of a CeO2 NPs standards, since the use of ionic cerium resulted in low recoveries (99 ± 9% vs. 73 ± 7%, respectively). A limit of detection of 0.9 μg L(-1) CeO2 corresponding to a number concentration of 1.8 × 1012 L(-1) for NPs of 5 nm was achieved for an injection volume of 100 μL. Copyright © 2016 Elsevier B.V. All rights reserved.

Synthesis of mesoporous cerium compound for CO2 capture

NASA Astrophysics Data System (ADS)

Liu, Guiqing; Tatsuda, Kou; Yoneyama, Yoshiharu; Tsubaki, Noritatsu

2017-11-01

A mesoporous adsorbent was simply synthesized by adding alkaline substances to cerium(III) nitric hydrate. The surface characteristics of the synthesized cerium compound were determined with BET, XRD and TEM analysis. It was found that although the specific surface areas of the synthesized cerium compounds were among about 120-200m2 per gram (BET area) which were smaller than the common used zeolite 13X (BET area 743 m2/g) and activated carbon (BET area 1079 m2/g), but the cerium compounds had excellent performances for CO2 adsorption as well as the CO2 desorption.

a Study of Nanocomposite Coatings on the Surface of Ship Exhaust Pipe

NASA Astrophysics Data System (ADS)

Shen, Yan; Sahoo, Prasanta K.; Pan, Yipeng

In order to improve the high temperature oxidation resistance of exhaust pipes, the nanocomposite coatings are carried out on the surface of exhaust pipe by pulsed current electrodeposition technology, and the microstructure and oxidation behavior of the nanocomposite coatings are investigated experimentally. This paper mainly focuses on the experimental work to determine the structural characteristics and oxidation resistance of nanocomposite coatings in presence of attapulgite and cerium oxide CeO2. The results show that the amount of the attapulgite-CeO2 has significant influence on the structural properties of nanocomposite coatings. The surface of coating becomes more compact and smooth with the increase of the amount of the attapulgite and CeO2. Furthermore, the anti-oxidation performances of the nanocomposite coatings formed with attapulgite and CeO2 were both better than those of the composite coatings formed without attapulgite and CeO2.

Method of preparing doped oxide catalysts for lean NOx exhaust

DOEpatents

Park, Paul W.

2004-03-09

The lean NOx catalyst includes a substrate, an oxide support material, preferably .gamma.-alumina deposited on the substrate and a metal or metal oxide promoter or dopant introduced into the oxide support material. The metal promoters or dopants are selected from the group consisting of indium, gallium, tin, silver, germanium, gold, nickel, cobalt, copper, iron, manganese, molybdenum, chromium cerium, and vanadium, and oxides thereof, and any combinations thereof. The .gamma.-alumina preferably has a pore volume of from about 0.5 to about 2.0 cc/g; a surface area of between 80 and 350 m.sup.2 /g; an average pore size diameter of between about 3 to 30 nm; and an impurity level of less than or equal to about 0.2 weight percent. In a preferred embodiment the .gamma.-alumina is prepared by a sol-gel method, with the metal doping of the .gamma.-alumina preferably accomplished using an incipient wetness impregnation technique.

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

PubMed

Najafpour, Mohammad Mahdi; Pashaei, Babak; Nayeri, Sara

2012-04-28

CaMnO(3) and Ca(2)Mn(3)O(8) were synthesized and characterized by SEM, XRD, FTIR and BET. Both oxides showed oxygen evolution activity in the presence of oxone, cerium(IV) ammonium nitrate and H(2)O(2). Oxygen evolution from water during irradiation with visible light (λ > 400 nm) was also observed upon adding these manganese oxides to an aqueous solution containing tris(2,2'-bipyridyl) ruthenium(II), as photosensitizer, and chloro pentaammine cobalt(III) chloride, as electron acceptor, in an acetate buffer. The amounts of dissolved manganese and calcium from CaMnO(3) and Ca(2)Mn(3)O(8) in the oxygen evolving reactions were reported and compared with other (calcium) manganese oxides. Proposed mechanisms of oxygen evolution and proposed roles for the calcium ions are also considered. This journal is © The Royal Society of Chemistry 2012

Layer-by-Layer Assembly of a Self-Healing Anticorrosion Coating on Magnesium Alloys.

PubMed

Fan, Fan; Zhou, Chunyu; Wang, Xu; Szpunar, Jerzy

2015-12-16

Fabrication of self-healing anticorrosion coatings has attracted attention as it has the ability to extend the service life and prevent the substrate from corrosive attack. However, a coating system with a rapid self-healing ability and an improved corrosion resistance is rarely reported. In this work, we developed a self-healing anticorrosion coating on a magnesium alloy (AZ31). The coating comprises a cerium-based conversion layer, a graphene oxide layer, and a branched poly(ethylene imine) (PEI)/poly(acrylic acid) (PAA) multilayer. We incorporated the graphene oxide as corrosion inhibitors and used the PEI/PAA multilayers to provide the self-healing ability to the coating systems. X-ray diffraction (XRD) and Raman spectroscopy were used to characterize the composition of the multilayers, and scanning electron microscopy (SEM) was used to analyze the surface morphology. The electrochemical impedance spectroscopy (EIS) results illustrate the improved corrosion resistance of the coating. The proposed coating also has a rapid self-healing ability in the presence of water.

Catalytic Combustion of Ethanol and Butanol

DTIC Science & Technology

2009-09-01

demonstrated 75% conversion of ethanol. I then selected a more active rhodium -coated alumina foam with a larger surface area and attained 100...catalysts composed of thermally stabilized, ion-exchanged zeolite, palladium on stabilized alumina, and catalysts doped with cerium (Ce) and nickel...platinum mesh weighed about 0.50 g and was roughly 0.5 mm thick. The rhodium (Rh)/aluminum oxide (Al2O3) foam contained 0.061 g of Rh and was prepared

Origin and tunability of unusually large surface capacitance in doped cerium oxide studied by ambient-pressure X-ray photoelectron spectroscopy

DOE PAGES

Gopal, Chirranjeevi Balaji; Gabaly, Farid El; McDaniel, Anthony H.; ...

2016-03-31

Here, the volumetric redox (chemical) capacitance of the surface of CeO 2–δ films is quantified in situ to be 100-fold larger than the bulk values under catalytically relevant conditions. Sm addition slightly lowers the surface oxygen nonstoichiometry, but effects a 10-fold enhancement in surface chemical capacitance by mitigating defect interactions, highlighting the importance of differential nonstoichiometry for catalysis.

A glassy carbon electrode modified with cerium phosphate nanotubes for the simultaneous determination of hydroquinone, catechol and resorcinol.

PubMed

Li, Zhen; Yue, Yuhua; Hao, Yanjun; Feng, Shun; Zhou, Xianli

2018-03-12

A nafion film containing cerium phosphate nanotubes was pasted onto a glassy carbon electrode (GCE) to obtain a sensor for hydroquinone (HQ). The morphologies and components of the coating were characterized by transmission electron microscopy, scanning electron microscopy and energy-dispersive spectroscopy. Cyclic voltammetry and differential pulse voltammetry (DPV) showed the specific surface of the electrode to be significantly increased and the electron transfer rate to be accelerated. The modified GCE was applied to the determination of hydroquinone (HQ) via DPV. The oxidation current increases linearly in the 0.23 μM to 16 mM HQ concentration range which is as wide as five orders of magnitude. The limit of detection is 0.12 μM (based on a signal-to-noise ratio of 3), and the sensitivity is 1.41 μA·μM -1  cm -2 . The method was further applied to the simultaneous determination of HQ, catechol and resorcinol. The potentials for the three species are well separated (20, 134, and 572 mV vs SCE). Average recoveries from (spiked) real water samples are between 95.2 and 107.0%, with relative standard deviations of 0.9~2.7% (for n = 3) at three spiking levels. The method was validated by independent assays using HPLC. Graphical abstract ᅟ.

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.

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

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.

Shock driven melting and resolidification upon release in cerium

NASA Astrophysics Data System (ADS)

Bolme, Cindy; Bronkhorst, Curt; Brown, Don; Cherne, Frank; Cooley, Jason; Furlanetto, Michael; Gleason, Arianna; Jensen, Brian; Owens, Charles; Ali, Suzanne; Fratanduono, Dayne; Galtier, Eric; Granados, Eduardo; Lee, Hae Ja; Nagler, Bob

2017-06-01

The temperature rise due to increasing entropy during shock compression and the corresponding temperature decrease due to isentropic expansion upon release cause the physics of melting and solidification under dynamic pressure changes to differ fundamentally from the more common liquid-solid transitions governed by thermal diffusion. We investigated laser shock driven melting and resolidification during release in cerium to examine the dynamics of these processes. Cerium was selected as the material of study due to the low pressure at which γ-cerium melts along the principle Hugoniot and due to cerium's anomalous melt boundary at low pressure, which facilitates its transition from liquid to solid during isentropic release. The structural phase of cerium was probed with X-ray diffraction using the LCLS X-ray free electron laser, which provided in situ measurements of the transition dynamics. The experimental results will be presented showing the resolidification occurring over 10s of ns.

Difference of EGCg adhesion on cell surface between Staphylococcus aureus and Escherichia coli visualized by electron microscopy after novel indirect staining with cerium chloride.

PubMed

Nakayama, Motokazu; Shigemune, Naofumi; Tsugukuni, Takashi; Tokuda, Hajime; Miyamoto, Takahisa

2011-07-01

We developed a novel method using indirect staining with cerium chloride for visualization of the catechin derivative epigallocatechin gallate (EGCg) on the surface of particles, i.e., polystyrene beads and bacterial cells, by electron microscopy. The staining method is based on the fact that in an alkaline environment, EGCg produces hydrogen peroxide, and then hydrogen peroxide reacts with cerium, resulting in a cerium hydroperoxide precipitate. This precipitate subsequently reacts with EGCg to produce larger deposits. The amount of precipitate is proportional to the amount of EGCg. Highly EGCg-sensitive Staphylococcus aureus and EGCg-resistant Escherichia coli were treated with EGCg under various pH conditions. Transmission electron microscopy observation showed that the amount of deposits on S. aureus increased with an increase in EGCg concentration. After treating bacterial cells with 0.5mg/mL EGCg (pH 6.0), attachment of EGCg was significantly lower to E. coli than to S. aureus. This is the first report that shows differences in affinity of EGCg to the cell surfaces of Gram-positive and -negative bacteria by electron microscopy. Copyright © 2011 Elsevier B.V. All rights reserved.

Hydrogen peroxide changes in ischemic and reperfused heart. Cytochemistry and biochemical and X-ray microanalysis.

PubMed Central

Slezak, J.; Tribulova, N.; Pristacova, J.; Uhrik, B.; Thomas, T.; Khaper, N.; Kaul, N.; Singal, P. K.

1995-01-01

Active oxygen species including hydrogen peroxide (H2O2) play a major role in ischemia-reperfusion injury. In the present study, changes in myocardial H2O2 content as well as its subcellular distribution were examined in rat hearts subjected to ischemia-reperfusion. Isolated perfused rat hearts were made globally ischemic for 20 or 30 minutes and were reperfused for different durations. H2O2 content in these hearts was studied biochemically and changes were correlated with the recovery of function. These hearts were also analyzed for subcellular distribution of H2O2. Optimal conditions of tissue processing as well as incubation medium were established for reacting cerium chloride with H2O2 to form cerium perhydroxide, an insoluble electron-dense product. The chemical composition of these deposits was confirmed by x-ray micro-analysis. Global ischemia caused complete contractile failure in minutes and after 30 minutes of ischemia, these was a > 250% increase in the myocardial H2O2 content. Depressed contractile function recovery in the early phase of reperfusion was accompanied by approximately a 600% increase in the myocardial H2O2 content. Brief pre-fixation with low concentrations of glutaraldehyde, inhibition of alkaline phosphatase, glutathione peroxidase, and catalase, post-fixation but no post-osmication, and no counterstaining yielded the best cytochemical definition of H2O2. In normal hearts, extremely small amounts of cerium hydroperoxide precipitates were located on the endothelial cells. X-ray microanalysis confirmed the presence of cerium in the reaction product. Ischemia resulted in a stronger reaction, particularly on the sarcolemma as well as abluminal side of the endothelial cells; and upon reperfusion, cerium precipitate reaction at these sites was more intense. In the reperfused hearts, the reaction product also appeared within mitochondria between the cristae as well as on the myofibrils, but Z-lines were devoid of any precipitate. The data support a significant increase in myocardial H2O2 during both the phase of ischemia and the first few minutes of reperfusion. A stronger reaction on the sarcolemma and abluminal side of endothelial cells may also indicate enhanced H2O2 accumulation as well as vulnerability of these sites to oxidative stress injury. Images Figure 1 Figure 2 Figure 4 Figure 5 Figure 6 Figure 7 Figure 8 Figure 9 Figure 10 PMID:7677188

Pyrazolates advance cerium chemistry: a CeIII/CeIV redox equilibrium with benzoquinone.

PubMed

Werner, Daniel; Deacon, Glen B; Junk, Peter C; Anwander, Reiner

2017-05-16

Two stable cerium(iv) 3,5-dialkylpyrazolate complexes are presented, namely dimeric [Ce(Me 2 pz) 4 ] 2 (Me 2 pz = 3,5-dimethylpyrazolate) and monomeric Ce(tBu 2 pz) 4 (tBu 2 pz = 3,5-di-tert-butylpyrazolate) along with their trivalent counterparts [Ce(Me 2 pz) 3 ] and [Ce(tBu 2 pz) 3 ] 2 . All complexes were obtained from protonolysis reactions employing the silylamide precursors Ce[N(SiHMe 2 ) 2 ] 4 and Ce[N(SiMe 3 ) 2 ] 3 . Treatment of homoleptic Ce IV and Ce III Me 2 pz complexes with 1,4-hydroquinone (H 2 hq) or 1,4-benzoquinone (bq), respectively, ultimately gave the same trimetallic Ce III species via a cerium redox equilibrium. The Ce III complex Ce 3 (Me 2 pz) 5 (pchd) 2 (L) (pchd = 1,4-bis(3,5-dimethylpyrazol-1-yl)cyclohex-2,5-diene-1,4-diolato; L = Me 2 pzH or (thf) 2 ) results from a di-1,4-pyrazolyl attack on pre-coordinated bq. The reduction of bq by [Ce(Me 2 pz) 3 (thf)] 2 , and re-oxidation by the resulting Ce IV species was supported by UV-vis spectroscopic investigations. Comparisons with the redox-innocent complexes [Ln(Me 2 pz) 3 (thf)] 2 (Ln = La and Pr) revealed far less selective reactions with bq, giving hexametallic and octametallic rare-earth metal side products containing 2-Me 2 pz substituted hq ligands.

Microwave synthesis of pure and doped cerium (IV) oxide (CeO2) nanoparticles for methylene blue degradation.

PubMed

El Rouby, W M A; Farghali, A A; Hamdedein, A

2016-11-01

Cerium (IV) oxide (CeO 2 ), samarium (Sm) and gadolinium (Gd) doped CeO 2 nanoparticles were prepared using microwave technique. The effect of microwave irradiation time, microwave power and pH of the starting solution on the structure and crystallite size were investigated. The prepared nanoparticles were characterized using X-ray diffraction, FT-Raman spectroscopy, and transmission electron microscope. The photocatalytic activity of the as-prepared CeO 2 , Sm and Gd doped CeO 2 toward degradation of methylene blue (MB) dye was investigated under UV light irradiation. The effect of pH, the amount of catalyst and the dye concentration on the degradation extent were studied. The photocatalytic activity of CeO 2 was kinetically enhanced by trivalent cation (Gd and Sm) doping. The results revealed that Gd doped CeO 2 nanoparticles exhibit the best catalytic degradation activity on MB under UV irradiation. For clarifying the environmental safety of the by products produced from the degradation process, the pathways of MB degradation were followed using liquid chromatography/mass spectroscopy (LC/MS). The total organic carbon content measurements confirmed the results obtained by LC/MS. Compared to the same nanoparticles prepared by another method, it was found that Gd doped CeO 2 prepared by hydrothermal process was able to mineralize MB dye completely under UV light irradiation.

Exceptional capability of nanosized CeO(2) materials to "dissolve" lanthanide oxides established by time-gated excitation and emission spectroscopy.

PubMed

Tiseanu, Carmen; Parvulescu, Vasile; Avram, Daniel; Cojocaru, Bogdan; Sanchez-Dominguez, Margarita

2014-05-28

The atomic scale homogeneity of Ce and Zr oxygen bonds represents the main reason for enhanced total oxygen storage capability of CeO2-ZrO2 (Ce/Zr = 1) as compared to that of CeO2. Here, we demonstrate that the addition of 10% Eu(3+) by wet impregnation on preformed nanosized CeO2-ZrO2 (Ce/Zr = 1) followed by calcination induces a remarkable homogeneity of 10% Eu(3+)-CeO2-ZrO2 solid solution. By use of time-resolved emission and excitation spectroscopies, the improvement of the nanoscale chemical and structural homogeneity of 10% Eu(3+)-CeO2-ZrO2 calcined at 1000 as compared to sample calcined at 750 °C is demonstrated. Based on the comparison of luminescence properties of 10% Eu(3+) impregnated on preformed nanosized CeO2-ZrO2 and CeO2, we also show that the presence of zirconium does not only preserve the ability of cerium oxide to "dissolve" lanthanide oxide, but also determines an important stabilization of defects (oxygen vacancies) generated upon Eu(3+) doping.

A Dual-Phase Ceramic Membrane with Extremely High H2 Permeation Flux Prepared by Autoseparation of a Ceramic Precursor.

PubMed

Cheng, Shunfan; Wang, Yanjie; Zhuang, Libin; Xue, Jian; Wei, Yanying; Feldhoff, Armin; Caro, Jürgen; Wang, Haihui

2016-08-26

A novel concept for the preparation of multiphase composite ceramics based on demixing of a single ceramic precursor has been developed and used for the synthesis of a dual-phase H2 -permeable ceramic membrane. The precursor BaCe0.5 Fe0.5 O3-δ decomposes on calcination at 1370 °C for 10 h into two thermodynamically stable oxides with perovskite structures: the cerium-rich oxide BaCe0.85 Fe0.15 O3-δ (BCF8515) and the iron-rich oxide BaCe0.15 Fe0.85 O3-δ (BCF1585), 50 mol % each. In the resulting dual-phase material, the orthorhombic perovskite BCF8515 acts as the main proton conductor and the cubic perovskite BCF1585 as the main electron conductor. The dual-phase membrane shows an extremely high H2 permeation flux of 0.76 mL min(-1)  cm(-2) at 950 °C with 1.0 mm thickness. This auto-demixing concept should be applicable to the synthesis of other ionic-electronic conducting ceramics. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Aerosol Physics Considerations for Using Cerium Oxide CeO 2 as a Surrogate for Plutonium Oxide PuO 2 in Airborne Release Fraction Measurements for Storage Container Investigations

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

Moore, Murray E.; Tao, Yong

Cerium oxide (CeO2) dust is recommended as a surrogate for plutonium oxide (PuO2) in airborne release fraction experiments. The total range of applicable particle sizes for PuO2 extends from 0.0032 μm (the diameter of a single PuO2 molecule) to 10 μm (the defined upper boundary for respirable particles). For particulates with a physical particle diameter of 1.0 μm, the corresponding aerodynamic diameters for CeO2 and PuO2 are 2.7 μm and 3.4 μm, respectively. Cascade impactor air samplers are capable of measuring the size distributions of CeO2 or PuO2 particulates. In this document, the aerodynamic diameters for CeO2 and PuO2 weremore » calculated for seven different physical diameters (0.0032, 0.02, 0.11, 0.27, 1.0, 3.2, and 10 μm). For cascade impactor measurements, CeO2 and PuO2 particulates with the same physical diameter would be collected onto the same or adjacent collection substrates. The difference between the aerodynamic diameter of CeO2 and PuO2 particles (that have the same physical diameter) is 39% of the resolution of a twelve-stage MSP Inc. 125 cascade impactor, and 34% for an eight-stage Andersen impactor. An approach is given to calculate the committed effective dose (CED) coefficient for PuO2 aerosol particles, compared to a corresponding aerodynamic diameter of CeO2 particles. With this approach, use of CeO2 as a surrogate for PuO2 material would follow a direct conversion based on a molar equivalent. In addition to the analytical information developed for this document, several US national labs have published articles about the use of CeO2 as a PuO2 surrogate. Different physical and chemical aspects were considered by these investigators, including thermal properties, ceramic formulations, cold pressing, sintering, molecular reactions, and mass loss in high temperature gas flows. All of those US national lab studies recommended the use of CeO2 as a surrogate material for PuO2.« less

Blue light emission from trivalent cerium doped in sol-gel silica glass

NASA Astrophysics Data System (ADS)

Tokumitsu, Seika; Murakami, Yukon; Oda, Hisaya; Kawabe, Yutaka

2017-02-01

Rare earths in glass matrices are promising for active optical devices as amplifiers and lasers. Emission originating from d-f transitions in sol-gel glass has not been studied very often, while those based on f-f transitions were widely utilized. However, d-f emission in rare earths is very important because of their strong oscillator strength and broad emission widths suitable for the application to scintillators and solid-state lasers. Co-doping of aluminum in sol-gel synthesis was known to be effective for the emission enhancement of trivalent terbium and europium. Recently, we applied aluminum co-doping to cerium and europium systems in sol-gel glass to succeed in the observation of strong blue light emission originating from d-f transitions. Glass samples were prepared with conventional sol-gel process where tetramethylorthosilicate was hydrolyzed in the mixture of water, ethanol and dimethylformamide with nitric acid catalyst. After adding cerium nitrate and aluminum nitrate, the solution experienced drying followed by calcination at 1,050°C under air environment. When molar ratio of cerium to silicon was adjusted at 0.1% and Al concentration was varied in 0.1 2.0%, transparent glass products showed bright and broad blue photoluminescence under UV illumination. The fluorescence lifetimes were found to be about 50 90 ns, indicating that the emission was due to d-f transitions. Considering the simplicity of the process, blue phosphors based on sol-gel glass will be very promising for future applications.

Technological pretreatment of the synchysite non-oxidized ore

NASA Astrophysics Data System (ADS)

Munkhtsetseg, B.; Burmaa, G.

2013-06-01

Mongolia has rich deposits of rare, precious, and poly-metallic ores. Nowadays, it is important to research separation of rare earth elements oxides concentrates from the ores, analyze their unique physical chemical characteristics, and purified it. Our investigation on raw materials focuses on rare earth non-oxidized ores. Main mineral in this rock sample is Synchysite (LnCa(CO3)2F. We did technological and thermal pretreatment: direct sulphurization (H2SO4), sulphurization with subsequent roasting (800°C+H2SO4), sulphurization prior to roasting (H2SO4+650°C). Sulphurization method based on dissolution of rare earth mineral into sulfuric acid (93%) according to the reaction. The amount of rare earth element oxides is almost 10 times greater (29.16%) after direct sulphurization process, almost 8 times greater (21.14%) after sulphurization with subsequent roasting, and almost 20 times greater (44.62%) after sulphurization prior to roasting process. After those technological pretreatment raw material's micro elements Thorium and Uranium contents are reduced as follows: H2SO4>800°C+H2SO4>H2SO4+650°C. These results show that cerium group rare earth elements have very good solubility in water at +2°C temperature and decreasing micro elements content uranium and thorium good pretreatment condition is prior to roasting (H2SO4+650°C) of synchysite non-oxidized ore.

Thermochemical cyclic system for splitting water and/or carbon dioxide by means of cerium compounds and reactions useful therein

DOEpatents

Bamberger, C.E.; Robinson, P.R.

A thermochemical cyclic process for producing hydrogen from water comprises reacting ceric oxide with monobasic or dibasic alkali metal phosphate to yield a solid reaction product, oxygen and water. The solid reaction product, alkali metal carbonate or bicarbonate, and water, are reacted to yield hydrogen, ceric oxide, carbon dioxide and trialkali metal phosphate. Ceric oxide is recycled. Trialkali metal phosphate, carbon dioxide and water are reacted to yield monobasic or dibasic alkali metal phosphate and alkali metal bicarbonate, which are recycled. The cyclic process can be modified for producing carbon monoxide from carbon dioxide by reacting the alkali metal cerous phosphate and alkali metal carbonate or bicarbonate in the absence of water to produce carbon monoxide, ceric oxide, carbon dioxide and trialkali metal phosphate. Carbon monoxide can be converted to hydrogen by the water gas shift reaction.

Thermochemical cyclic system for splitting water and/or carbon dioxide by means of cerium compounds and reactions useful therein

DOEpatents

Bamberger, Carlos E.; Robinson, Paul R.

1980-01-01

A thermochemical cyclic process for producing hydrogen from water comprises reacting ceric oxide with monobasic or dibasic alkali metal phosphate to yield a solid reaction product, oxygen and water. The solid reaction product, alkali metal carbonate or bicarbonate, and water, are reacted to yield hydrogen, ceric oxide, carbon dioxide and trialkali metal phosphate. Ceric oxide is recycled. Trialkali metal phosphate, carbon dioxide and water are reacted to yield monobasic or dibasic alkali metal phosphate and alkali metal bicarbonate, which are recycled. The cylic process can be modified for producing carbon monoxide from carbon dioxide by reacting the alkali metal cerous phosphate and alkali metal carbonate or bicarbonate in the absence of water to produce carbon monoxide, ceric oxide, carbon dioxide and trialkali metal phosphate. Carbon monoxide can be converted to hydrogen by the water gas shift reaction.

Critical indices for reversible gamma-alpha phase transformation in metallic cerium

NASA Astrophysics Data System (ADS)

Soldatova, E. D.; Tkachenko, T. B.

1980-08-01

Critical indices for cerium have been determined within the framework of the pseudobinary solution theory along the phase equilibrium curve, the critical isotherm, and the critical isobar. The results obtained verify the validity of relationships proposed by Rushbrook (1963), Griffiths (1965), and Coopersmith (1968). It is concluded that reversible gamma-alpha transformation in metallic cerium is a critical-type transformation, and cerium has a critical point on the phase diagram similar to the critical point of the liquid-vapor system.

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 dissolved oxygen (5 ppm) but the NH4 content is still high, which indicates a non-equilibrium condition. In this study, the cerium anomaly is alternatively utilized to evaluate the water redox state. The results demonstrate that the input water has the negative cerium anomaly of -0.16. Along the flow path, the cerium negative anomaly does not change in the first two cells and dramatically becomes -0.23 in cell 3. The trend of cerium anomaly is more close to the removal efficiency of NH4 rather than dissolve oxygen. Accordingly, cerium anomaly could become a better indicator of removal efficiency of constructed wetland.

Effect of Ce2O3, La2O3 and ZnO additives on the oxygenates conversion into liquid hydrocarbons

NASA Astrophysics Data System (ADS)

Kachalov, V. V.; Lavrenov, V. A.; Lishchiner, I. I.; Malova, O. V.; Tarasov, A. L.; Zaichenko, V. M.

2018-01-01

A selective modifying effect of cerium, magnesium and zinc oxide additives on the activity and the selectivity of a pentasil group zeolite catalyst in the reaction of conversion of oxygenates (methanol and dimethyl ether) to liquid hydrocarbons was found. It was found that zinc oxide contributes to the stable operation of the zeolite catalyst in the conversion of oxygenates in the synthesis gas stream and leads to the production of gasolines with low durene content (not more than 6.1 wt%). The obtained results demonstrate the rationale for producing hydrocarbons from synthesis gas without the stage of oxygenate separation with their subsequent conversion to synthetic gasoline.

Bio-inspired surfactant assisted nano-catalyst impregnation of Solid-Oxide Fuel Cell (SOFC) electrodes

DOE PAGES

Ozmen, Ozcan; Zondlo, John W.; Lee, Shiwoo; ...

2015-11-02

A bio-inspired surfactant was utilized to assist in the efficient impregnation of a nano-CeO₂ catalyst throughout both porous Solid Oxide Fuel Cells (SOFC’s) electrodes simultaneously. The process included the initial modification of electrode pore walls with a polydopamine film. The cell was then submersed into a cerium salt solution. The amount of nano-CeO₂ deposited per impregnation step increased by 3.5 times by utilizing this two-step protocol in comparison to a conventional drip impregnation method. The impregnated cells exhibited a 20% higher power density than a baseline cell without the nano-catalyst at 750°C (using humid H₂ fuel).

Hybrid layers deposited by an atmospheric pressure plasma process for corrosion protection of galvanized steel.

PubMed

Del Frari, D; Bour, J; Bardon, J; Buchheit, O; Arnoult, C; Ruch, D

2010-04-01

Finding alternative treatments to reproduce anticorrosion properties of chromated coatings is challenging since both physical barrier and self-healing effects are needed. Siloxane based treatments are known to be a promising way to achieve physical barrier coatings, mainly plasma polymerized hexamethyldisiloxane (ppHMDSO). In addition, it is known that cerium-based coatings can also provide corrosion protection of metals by means of self-healing effect. In this frame, innovative nanoAlCeO3/ppHMDSO layers have thus been deposited and studied. These combinations allow to afford a good physical barrier effect and active properties. Liquid siloxane and cerium-based particles mixture is atomized and introduced as precursors into a carrier gas. Gas mixture is then injected into an atmospheric pressure dielectric barrier discharge (DBD) where plasma polymerization of the siloxane precursor occurs. The influence of cerium concentration on the coating properties is investigated: coating structure and topography have been studied by scanning electron microscopy (SEM) and interferometry, and corrosion resistance of these different coatings is compared by electrochemistry techniques: polarization curves and electrochemical impedance spectroscopy (EIS). Potential self-healing property afforded by cerium in the layer was studied by associating EIS measurements and nanoscratch controlled damaging. Among the different combinations investigated, mixing of plasma polymerized HMDSO and AICeO3 nanoparticles seems to give promising results with a good physical barrier and interesting electroactive properties. Indeed, corrosion currents measured on such coatings are almost as low as those measured with the chromated film. Combination of nanoscratch damaging of layers with EIS experiments to investigate self-healing also allow to measure the active protection property of such layers.

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)

Cerium migration during PEM fuel cell assembly and operation

DOE PAGES

Baker, Andrew M.; Torraco, Dennis; Judge, Elizabeth J.; ...

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

Nanocomposite scintillator, detector, and method

DOEpatents

Cooke, D Wayne [Santa Fe, NM; McKigney, Edward A [Los Alamos, NM; Muenchausen, Ross E [Los Alamos, NM; Bennett, Bryan L [Los Alamos, NM

2009-04-28

A compact includes a mixture of a solid binder and at least one nanopowder phosphor chosen from yttrium oxide, yttrium tantalate, barium fluoride, cesium fluoride, bismuth germanate, zinc gallate, calcium magnesium pyrosilicate, calcium molybdate, calcium chlorovanadate, barium titanium pyrophosphate, a metal tungstate, a cerium doped nanophosphor, a bismuth doped nanophosphor, a lead doped nanophosphor, a thallium doped sodium iodide, a doped cesium iodide, a rare earth doped pyrosilicate, or a lanthanide halide. The compact can be used in a radiation detector for detecting ionizing radiation.

Extraction of rare earth oxides using supercritical carbon dioxide modified with Tri- n-butyl phosphate–nitric acid adducts

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

Baek, Donna L.; Fox, Robert V.; Case, Mary E.

A new tri- n-butylphosphate–nitric acid (TBP–HNO 3) adduct was prepared by combining TBP and fuming (90%) HNO 3. The adduct was characterized, and its phase-equilibrium behavior in supercritical carbon dioxide is reported. Supercritical carbon dioxide (sc-CO 2) was modified with this new adduct [TBP(HNO 3) 5.2(H 2O) 1.7], and the extraction efficacies of selected rare earth oxides (Y, Ce, Eu, Tb, and Dy) at 338 K and 34.5 MPa were compared with those obtained using an adduct formed from concentrated (70%) HNO 3 and TBP [TBP(HNO 3) 1.7(H 2O) 0.6]. All rare earth oxides tested with both adduct species couldmore » be extracted with the exception of cerium oxide. Furthermore, the water and acid concentrations in the different adducts were found to play a significant role in rare earth oxide extraction efficiency.« less

Oxide strengthened molybdenum-rhenium alloy

DOEpatents

Bianco, Robert; Buckman, Jr., R. William

2000-01-01

Provided is a method of making an ODS molybdenum-rhenium alloy which includes the steps of: (a) forming a slurry containing molybdenum oxide and a metal salt dispersed in an aqueous medium, the metal salt being selected from nitrates or acetates of lanthanum, cerium or thorium; (b) heating the slurry in the presence of hydrogen to form a molybdenum powder comprising molybdenum and an oxide of the metal salt; (c) mixing rhenium powder with the molybdenum powder to form a molybdenum-rhenium powder; (d) pressing the molybdenum-rhenium powder to form a molybdenum-rhenium compact; (e) sintering the molybdenum-rhenium compact in hydrogen or under a vacuum to form a molybdenum-rhenium ingot; and (f) compacting the molybdenum-rhenium ingot to reduce the cross-sectional area of the molybdenum-rhenium ingot and form a molybdenum-rhenium alloy containing said metal oxide. The present invention also provides an ODS molybdenum-rhenium alloy made by the method. A preferred Mo--Re-ODS alloy contains 7-14 weight % rhenium and 2-4 volume % lanthanum oxide.

Extraction of rare earth oxides using supercritical carbon dioxide modified with Tri- n-butyl phosphate–nitric acid adducts

DOE PAGES

Baek, Donna L.; Fox, Robert V.; Case, Mary E.; ...

2016-06-14

A new tri- n-butylphosphate–nitric acid (TBP–HNO 3) adduct was prepared by combining TBP and fuming (90%) HNO 3. The adduct was characterized, and its phase-equilibrium behavior in supercritical carbon dioxide is reported. Supercritical carbon dioxide (sc-CO 2) was modified with this new adduct [TBP(HNO 3) 5.2(H 2O) 1.7], and the extraction efficacies of selected rare earth oxides (Y, Ce, Eu, Tb, and Dy) at 338 K and 34.5 MPa were compared with those obtained using an adduct formed from concentrated (70%) HNO 3 and TBP [TBP(HNO 3) 1.7(H 2O) 0.6]. All rare earth oxides tested with both adduct species couldmore » be extracted with the exception of cerium oxide. Furthermore, the water and acid concentrations in the different adducts were found to play a significant role in rare earth oxide extraction efficiency.« less

Metal/metal oxide doped oxide catalysts having high deNOx selectivity for lean NOx exhaust aftertreatment systems

DOEpatents

Park, Paul W.

2004-03-16

A lean NOx catalyst and method of preparing the same is disclosed. The lean NOx catalyst includes a ceramic substrate, an oxide support material, preferably .gamma.-alumina, deposited on the substrate and a metal promoter or dopant introduced into the oxide support material. The metal promoters or dopants are selected from the group consisting of indium, gallium, tin, silver, germanium, gold, nickel, cobalt, copper, iron, manganese, molybdenum, chromium, cerium, vanadium, oxides thereof, and combinations thereof. The .gamma.-alumina preferably has a pore volume of from about 0.5 to about 2.0 cc/g; a surface area of between about 80 to 350 m.sup.2 /g; an average pore size diameter of between about 3 to 30 nm; and an impurity level of less than or equal to 0.2 weight percent. In a preferred embodiment the .gamma.-alumina is prepared by a sol-gel method, with the metal doping of the .gamma.-alumina preferably accomplished using an incipient wetness impregnation technique.

Cerium chloride stimulated controlled conversion of B-to-Z DNA in self-assembled nanostructures

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

Bhanjadeo, Madhabi M.; Academy of Scientific & Innovative Research; Nayak, Ashok K.

DNA adopts different conformation not only because of novel base pairs but also while interacting with inorganic or organic compounds. Self-assembled branched DNA (bDNA) structures or DNA origami that change conformation in response to environmental cues hold great promises in sensing and actuation at the nanoscale. Recently, the B-Z transition in DNA is being explored to design various nanomechanical devices. In this communication we have demonstrated that Cerium chloride binds to the phosphate backbone of self-assembled bDNA structure and induce B-to-Z transition at physiological concentration. The mechanism of controlled conversion from right-handed to left-handed has been assayed by various dyemore » binding studies using CD and fluorescence spectroscopy. Three different bDNA structures have been identified to display B-Z transition. This approach provides a rapid and reversible means to change bDNA conformation, which can be used for dynamic and progressive control at the nanoscale. - Highlights: • Cerium-induced B-to-Z DNA transition in self-assembled nanostructures. • Lower melting temperature of Z-DNA than B-DNA confirmed by CD spectroscopy. • Binding mechanism of cerium chloride is explained using fluorescence spectroscopy. • Right-handed to left-handed DNA conformation is also noticed in modified bDNA structure.« less

Incorporation of cerium oxide into hydroxyapatite coating regulates osteogenic activity of mesenchymal stem cell and macrophage polarization.

PubMed

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

2017-02-01

Biomedical coatings for orthopedic implants should facilitate osseointegration and mitigate implant-induced inflammatory reactions. Cerium oxide (CeO 2 ) ceramics possess anti-oxidative properties and can be used to decrease mediators of inflammation, which makes them attractive for biomedical applications. In our work, two kinds of CeO 2 incorporated hydroxyapatite coatings (HA-10Ce and HA-30Ce) were prepared via plasma spraying technique and the effects of CeO 2 addition on the responses of bone mesenchymal stem cells (BMSCs) and RAW264.7 macrophages were investigated. An increase in CeO 2 content in the HA coatings resulted in better osteogenic behaviors of BMSCs in terms of cell proliferation, alkaline phosphatase (ALP) activity and mineralized nodule formation. RT-PCR and western blot analysis suggested that the incorporation of CeO 2 may promote the osteogenic differentiation of BMSCs through the Smad-dependent BMP signaling pathway, which activated Runx2 expression and subsequently enhanced the expression of ALP and OCN. The expression profiles of macrophages cultured on the CeO 2 modified coating revealed a tendency toward a M2 phenotype, because of an upregulation of M2 surface markers (CD163 and CD206), anti-inflammatory cytokines (TNF-α and IL-6) and osteoblastogenesis-related genes (BMP2 and TGF-β1) as well as a downregulation of M1 surface markers (CCR7 and CD11c), proinflammatory cytokines (IL-10 and IL-1ra) and reactive oxygen species production. The results suggested the regulation of BMSCs behaviors and macrophage-mediated responses at the coating's surface were associated with CeO 2 incorporation. The incorporation of CeO 2 in HA coatings can be a valuable strategy to promote osteogenic responses and reduce inflammatory reactions.

Study of Degradation Kinetics of Parathion Methyl On Mixed Nanocrystalline Titania-Zirconium and Titania-Cerium Oxides

NASA Astrophysics Data System (ADS)

Kuráň, Pavel; Pšenička, Martin; Šťastný, Martin; Benkocká, Monika; Janoš, Pavel

2016-10-01

The unique surface properties of some nanocrystalline metal oxides and their application for removal of various toxic compounds were reported in early 1990s. Recently, a reliable method for the preparation of reactive cerium dioxide sorbent and its application for degradation of the organophosphate pesticides, such as parathion methyl, chlorpyrifos, dichlofenthion, fenchlorphos, and prothiofos, as well as of some chemical warfare agents-nerve gases soman and O-ethyl S-[2-(diisopropylamino) ethyl] methylphosphonothioate (VX) was published. This paper reports on the kinetics study of degradation of parathion methyl as a representative organophosphate on nanocrystalline metal oxides TiO2, ZrO2, CeO2 and their mixtures in different molar ratios of particular elements. The tested sorbents except of CeO2 were prepared by different methods (e.g. sol-gel, precipitation) in cooperation with Institute of Inorganic Chemistry (Rez, Czech Republic). The degradation kinetics of parathion methyl on tested sorbents was followed by HPLC equipped with diode array detector. The basic kinetics parameters (half-lives of parathion methyl degradation, rate constants of degradation product formation) were calculated for each sorbent from Weber-Morris equation of 1st order diffusion kinetic model. The results proved the ability of prepared sorbents to degrade parathion methyl under formation of 4-nitrophenol as the main degradation product. The most efficient sorbents were TiCe (2:8), TiCe (1:1), TiCe (0:1) (50-70 %) followed by TiZr (1:1), TiCe (8:2), TiZr (8:2), TiZr (2:8) (20-30%) and TiO2, ZrO2 (less than 5 %).

Antimony film sensor for sensitive rare earth metal analysis in environmental samples.

PubMed

Makombe, Martin; van der Horst, Charlton; Silwana, Bongiwe; Iwuoha, Emmanuel; Somerset, Vernon

2016-07-02

A sensor for the adsorptive stripping voltammetric determination of rare earth elements has been developed. The electrochemical procedure is based on the oxidation of the rare earth elements complexed with alizarin complexone at a glassy carbon electrode that was in situ modified with an antimony film, during an anodic scan from -0.2 V to 1.1 V (vs. Ag/AgCl) and deposition potential of -0.1 V (vs. Ag/AgCl). The factors influencing the adsorptive stripping capability were optimised, including the complexing agent concentration, plating concentration of antimony and deposition time. The detection of rare earth elements (La, Ce and Pr) were realised in 0.08 M sodium acetate (pH = 5.8) solution as supporting electrolyte, with 2 × 10(-6) M alizarin complexone and 1.0 mg L(-1) antimony solution. Under the optimised conditions, a deposition time of 360 s was obtained and a linear response was observed between 1 and 25 µg L(-1). The reproducibility of the voltammetric measurements was found to be within 5.0% RSD for 12 replicate measurements of cerium(III) concentration of 5 µg L(-1) using the same electrode surface. The detection limits obtained using stripping analysis was 0.06, 0.42 and 0.71 μg L(-1) for Ce(III), La(III) and Pr(III), respectively. The developed sensor has been successfully applied for the determination of cerium, lanthanum and praseodymium in municipal tap water samples.

Biogenic unmodified gold nanoparticles for selective and quantitative detection of cerium using UV-vis spectroscopy and photon correlation spectroscopy (DLS).

PubMed

Priyadarshini, E; Pradhan, N; Panda, P K; Mishra, B K

2015-06-15

The ability of self-functionalized biogenic GNPs towards highly selective colorimetric detection of rare earth element cerium is being reported for the first time. GNPs underwent rapid aggregation on addition of cerium indicated by red shift of SPR peak followed by complete precipitation. Hereby, this concept of co-ordination of cerium ions onto the GNP surface has been utilized for detection of cerium. The remarkable capacity of GNPs to sensitively detect Ce without proves beneficial compared to previous reports of colorimetric sensing. MDL was 15 and 35 ppm by DLS and UV-vis spectroscopy respectively, suggesting DLS to be highly sensitive and a practical alternative in ultrasensitive detection studies. The sensing system showed a good linear fit favouring feasible detection of cerium in range of 2-50 ppm. Similar studies further showed the superior selectivity of biogenic GNPs compared to chemically synthesized counterparts. The sensing system favours on-site analysis as it overcomes need of complex instrumentation, lengthy protocols and surface modification of GNP. Copyright © 2015 Elsevier B.V. All rights reserved.

Immobilization of simulated radioactive soil waste containing cerium by self-propagating high-temperature synthesis

NASA Astrophysics Data System (ADS)

Mao, Xianhe; Qin, Zhigui; Yuan, Xiaoning; Wang, Chunming; Cai, Xinan; Zhao, Weixia; Zhao, Kang; Yang, Ping; Fan, Xiaoling

2013-11-01

A simulated radioactive soil waste containing cerium as an imitator element has been immobilized by a thermite self-propagating high-temperature synthesis (SHS) process. The compositions, structures, and element leaching rates of products with different cerium contents have been characterized. To investigate the influence of iron on the chemical stability of the immobilized products, leaching tests of samples with different iron contents with different leaching solutions were carried out. The results showed that the imitator element cerium mainly forms the crystalline phases CeAl11O18 and Ce2SiO5. The leaching rate of cerium over a period of 28 days was 10-5-10-6 g/(m2 day). Iron in the reactants, the reaction products, and the environment has no significant effect on the chemical stability of the immobilized SHS products.

Synthesis and optical characterization of SrHfO 3:Ce and SrZrO 3:Ce nanoparticles

NASA Astrophysics Data System (ADS)

Rétot, H.; Bessière, A.; Kahn-Harari, A.; Viana, B.

2008-03-01

Nanoparticles have recently found application fields in various scopes, such as imaging (luminescent nanosensors), or for the production of laser or scintillating transparent ceramics. This work is related to this last field, with the target of medical imaging (positron emission tomography). Very dense rare earth doped mixed oxides were studied: SrZrO 3:Ce and SrHfO 3:Ce, which are particularly adapted to this application. The phase transformations and the very high melting points of these materials (respectively 2646 °C and 2730 °C) led us to study their synthesis as nanoparticles. Using the combustion method we have obtained, at temperatures less than 1000 °C, particles of very small dimensions (10-100 nm) without impurities. First characterization of the optical properties (under UV irradiation) of the cerium ion in these perovskite matrixes, realized on the nanopowders (absorption, emission and lifetime of the cerium ion), is presented here: for both compounds, an emission at 430 nm is observed under UV irradiation, with a short decay time; these particles prepared by combustion are thus interesting precursors for ceramic scintillators.

Mixed valency and site-preference chemistry for cerium and its compounds: A predictive density-functional theory study

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

Alam, Aftab; Johnson, Duane D.

Cerium and its technologically relevant compounds are examples of anomalous mixed valency, originating from two competing oxidation states—itinerant Ce4+ and localized Ce3+. Under applied stress, anomalous transitions are observed but not well understood. Here we treat mixed valency as an “alloy” problem involving two valences with competing and numerous site-occupancy configurations. We use density-functional theory with Hubbard U (i.e., DFT+U) to evaluate the effective valence and predict properties, including controlling the valence by pseudoternary alloying. For Ce and its compounds, such as (Ce,La)2(Fe,Co)14B permanent magnets, we find a stable mixed-valent α state near the spectroscopic value of νs=3.53. Ce valencymore » in compounds depends on its steric volume and local chemistry. For La doping, Ce valency shifts towards γ-like Ce3+, as expected from steric volume; for Co doping, valency depends on local Ce-site chemistry and steric volume. Our approach captures the key origins of anomalous valency and site-preference chemistry in complex compounds.« less

MOUND LABORATORY PROGRESS REPORT FOR JANUARY 1961

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

Eichelberger, J.F.

Work was begun to determine the physical properties of mica-filled diallyl phthalate. Both the impact and tensile strength values compared favorably wlth asbestos-filled DAP formulatlons. The tensile values compared with the upper limit tensile strength values for asbestos-filled formulations. Adiprene-ferric acetyl acetonate-polyol systems were developed as adhesives and their properties studied. Sources of kilogram quantities of Th/sup 2//sup 3//sup 0/ were investigated. The samples were analyzed by a direct CeF/sub 3/ precipitation procedurc or by a tributyl phosphate-cerium procedure. The half- life of Ra/sup 2//sup 2//sup 3/ was found to be 11.3700 plus or minus 0.0065 days. Differential thermal analysesmore » were made of lanthanum and praseodymium metals. Three preilminary determinations of the density of molten cerium were made by the vacuum pycnometer method. An average value of 6.58 was obtained. Leaching tests in water and in 0.1N HCl were continued on fibers of an experimental glass containing 10 wt.%n plutonium oxide. (M.C.G.)« less

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

PubMed

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

2015-10-01

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 (0.15mg/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 1day post-exposure. Morphological analysis of lung showed an increased inflammation, surfactant and collagen fibers after CeO2 (high dose at 3.5mg/kg) treatment at 28days 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 3days 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. Published by Elsevier Inc.

Structural, topographical and electrical properties of cerium doped strontium barium niobate (Ce:SBN60) ceramics

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

Raj, S. Gokul; Mathivanan, V.; Mohan, R.

2016-05-06

Tungsten bronze type cerium doped strontium barium niobate (Ce:SBN - Sr{sub 0.6}B{sub 0.4}Nb{sub 2}O{sub 6}) ceramics were synthesized by solid state process. Cerium was used as dopant to improve its electrical properties. Influence of Ce{sup +} ions on the photoluminescence properties was investigated in detail. The grain size topographical behavior of SBN powders and their associated abnormal grain growth (AGG) were completely analyzed through SEM studies. Finally dielectric, measurement discusses about the broad phase transition observed due to cerium dopant The results were discussed in detail.

Studies on copper-yttria nanocomposites: high-energy ball milling versus chemical reduction method.

PubMed

Joshi, P B; Rehani, Bharati; Naik, Palak; Patel, Swati; Khanna, P K

2012-03-01

Oxide dispersion-strengthened copper-base composites are widely used for applications demanding high tensile strength, high hardness along with good electrical and thermal conductivity. Oxides of metals like aluminium, cerium, yttrium and zirconium are often used for this purpose as fine and uniformly distributed dispersoid particles in soft and ductile copper matrix. Such composites find applications as electrical contacts, resistance-welding tips, lead wires, continuous casting moulds, etc. In this investigation an attempt has been made to produce copper-yttria nanocomposites using two different morphologies of copper powder and two different processing routes namely, high-energy milling and in-situ chemical reduction. The synthesized powders were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM) for their phase identification and morphological study. The nanocomposite powders in each case were subsequently processed to obtain bulk solids by classical powder metallurgy route of press-sinter-repress. The resultant bulk solid compacts were subjected to property evaluation. The study revealed that the properties of Cu-Y2O3 nanocomposites depend on the processing route used and in turn on the resultant powder morphology.

Scintillator material

DOEpatents

Anderson, David F.; Kross, Brian J.

1994-01-01

An improved scintillator material comprising cerium fluoride is disclosed. Cerium fluoride has been found to provide a balance of good stopping power, high light yield and short decay constant that is superior to known scintillator materials such as thallium-doped sodium iodide, barium fluoride and bismuth germanate. As a result, cerium fluoride is favorably suited for use as a scintillator material in positron emission tomography.

Scintillator material

DOEpatents

Anderson, David F.; Kross, Brian J.

1992-01-01

An improved scintillator material comprising cerium fluoride is disclosed. Cerium fluoride has been found to provide a balance of good stopping power, high light yield and short decay constant that is superior to known scintillator materials such as thallium-doped sodium iodide, barium fluoride and bismuth germanate. As a result, cerium fluoride is favorably suited for use as a scintillator material in positron emission tomography.

Synergistic properties of graphitic carbon nitride/cerium molybdate nanocomposites for enhanced photocatalytic activity

NASA Astrophysics Data System (ADS)

Bhargava, V. S.; Singh, Gajendar; Sharma, Manu

2018-05-01

A polymeric semiconductor (g-C3N4), based nanocomposites have been achieved much attention due to its excellent thermal, chemical stability and suitable band positions for water splitting. g-C3N4 based nanocomposites show good performance in the field of photocatalysis, sensors, Li-ion batteries, supercapacitors and water purification technology. In this work, a series of novel g-C3N4/CeM nano composites were synthesized using a facile one-step ultra-sonication method. X-ray diffraction (XRD) pattern confirms the formation of g-C3N4 and cerium molybdate. The photocatalytic activity of nanocomposites indicated the substantial degradation of Methylene Blue (MB) dye up to 97% over the surface of g-C3N4/CeM under visible light illumination. All the g-C3N4/CeM composites possess higher photocatalytic activity than pure cerium molybdate. The proposed mechanism demonstrated that the different weight ratios of photocatalyst were most likely attributed to a synergistic effect between g-C3N4 and CeM. This approach is very simple, cost effective, and free from any surfactant that makes it valuable catalyst for various future applications.

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.

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.

Boosting the oxidase mimicking activity of nanoceria by fluoride capping: rivaling protein enzymes and ultrasensitive F- detection

NASA Astrophysics Data System (ADS)

Liu, Biwu; Huang, Zhicheng; Liu, Juewen

2016-07-01

Nanomaterial-based enzyme mimics (nanozymes) are currently a new forefront of chemical research. However, the application of nanozymes is limited by their low catalytic activity and low turnover numbers. Cerium dioxide nanoparticles (nanoceria) are among the few with oxidase activity. Herein, we report an interesting finding addressing their limitations. The oxidase activity of nanoceria is improved by over 100-fold by fluoride capping, making it more close to real oxidases. The turnover number reached 700 in 15 min, drastically improved from ~15 turnovers for the naked particles. The mechanism is attributed to surface charge modulation and facilitated electron transfer by F- capping based on ζ-potential and free radical measurements. Ultrasensitive sensing of fluoride was achieved with a detection limit of 0.64 μM F- in water and in toothpastes, while no other tested anions can achieve the activity enhancement.Nanomaterial-based enzyme mimics (nanozymes) are currently a new forefront of chemical research. However, the application of nanozymes is limited by their low catalytic activity and low turnover numbers. Cerium dioxide nanoparticles (nanoceria) are among the few with oxidase activity. Herein, we report an interesting finding addressing their limitations. The oxidase activity of nanoceria is improved by over 100-fold by fluoride capping, making it more close to real oxidases. The turnover number reached 700 in 15 min, drastically improved from ~15 turnovers for the naked particles. The mechanism is attributed to surface charge modulation and facilitated electron transfer by F- capping based on ζ-potential and free radical measurements. Ultrasensitive sensing of fluoride was achieved with a detection limit of 0.64 μM F- in water and in toothpastes, while no other tested anions can achieve the activity enhancement. Electronic supplementary information (ESI) available: Methods, TMB oxidation kinetics and control experiments. See DOI: 10.1039/c6nr02730j

Cerium LIII-edge x-ray absorption study of the CexFe4-yCoySb12 skutterudites

NASA Astrophysics Data System (ADS)

Grandjean, Fernande; Long, Gary J.; Cortes, Robert; Morelli, Donald T.; Meisner, Gregory P.

2000-11-01

The cerium LIII-edge x-ray absorption near-edge spectra of the CexFe4-yCoySb12 compounds have been obtained at 295 K and unambiguously indicate that cerium is in the 4f1 electronic ground state for all values of 0.22<=x<=0.98 and 0.0<=y<=3.5. This stable trivalent state of cerium is in agreement with the proposed (CeFe4Sb12)1-α(□Co4Sb12)α, solid solution structure, in which the cerium atoms are always surrounded by twelve antimony first neighbors and six iron second neighbors, the observed magnetic properties of CeFe4Sb12 and Ce0.9Fe3CoSb12, and the electronic structure of CeFe4Sb12 obtained from band-structure calculations.

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.

Trivalent cerium coped crystals as tunable laser systems: two bad apples

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

Hamilton, D.S.

1985-01-01

The 5d-4f transitions of trivalent doped crystals have broad emission bands with large oscillator strengths and near unity quantum efficiency. These characteristics make cerium systems strong candidates for tunable solid state lasers. However, two such cerium crystals will probably never lase. The first is Ce/sup 3 +/:YAG where a strong excited state absorption quenches the lasing transition. Our recent measurements have indicated that the excited state absorption terminates in the YAG conduction band with a peak cross section of 1.0 x 10/sup -17/ cm/sup 2/ at 700 nm. Some of the general features of impurity ion to band spectra aremore » discussed. The second system is Ce/sup 3 +/:CaF/sub 2/ where a uv pump induced photochromic center is produced following excitation of the cerium ions. The initial measurements of cerium related transient absorptions in Ce/sup 3 +/:YLF are also presented.« less

A study on recovery of uranium in the anode basket residues delivered from the pyrochemical process of used nuclear fuel

NASA Astrophysics Data System (ADS)

Eun, H. C.; Kim, T. J.; Jang, J. H.; Kim, G. Y.; Park, S. B.; Yoon, D. S.; Kim, S. H.; Paek, S. W.; Lee, S. J.

2018-04-01

In this study, the chlorination of uranium oxide (UO2) using ammonium chloride and zirconium as chemical agents was conducted to recover the uranium in the anode basket residues from the pyrochemical process of used nuclear fuel. The chlorination of UO2 was predicted using thermodynamic equilibrium calculations. The experimental conditions for the chlorination were determined using a chlorination test with cerium oxide (CeO2). In the chlorination test, it was confirmed that UO2 was chlorinated into UCl3 at 320 °C, some UO2 remained without changes in the chemical form, and ZrO2, Zr2O, and ZrCl2 were generated as byproducts.

Kinetic determination of propranolol in tablets by oxidation with ceric sulphate.

PubMed

Sultan, S M; Altamrah, S A; Aziz Alrahman, A M; Alzamil, I Z; Karrar, M O

1989-01-01

A simple and accurate kinetic method for the determination of propranolol has been developed. Cerium(IV) sulphate (0.5 M) is used to oxidize propranolol in 2 M sulphuric acid at room temperature to the ketone form that absorbs light at a lambda max of 525 nm. The fixed-concentration method is used by recording the exact time, t(s), taken for the reaction to reach a fixed absorbance of 0.100. The unknown concentration, c(M), of propranolol is calculated from the equation: l/t = 0 0.000217 + 0.03 c. The method has been applied to the determination of propranolol in proprietary tablets and the results were compared with those obtained by the B.P. and other standard methods.

Development of chemically bonded phosphate ceramics for stabilizing low-level mixed wastes

NASA Astrophysics Data System (ADS)

Jeong, Seung-Young

1997-11-01

Novel chemically bonded phosphate ceramics have been developed by acid-base reactions between magnesium oxide and an acid phosphate at room temperature for stabilizing U.S. Department of Energy's low-level mixed waste streams that include hazardous chemicals and radioactive elements. Newberyite (MgHPOsb4.3Hsb2O)-rich magnesium phosphate ceramic was formed by an acid-base reaction between phosphoric acid and magnesium oxide. The reaction slurry, formed at room-temperature, sets rapidly and forms stable mineral phases of newberyite, lunebergite, and residual MgO. Rapid setting also generates heat due to exothermic acid-base reaction. The reaction was retarded by partially neutralizing the phosphoric acid solution by adding sodium or potassium hydroxide. This reduced the rate of reaction and heat generation and led to a practical way of producing novel magnesium potassium phosphate ceramic. This ceramic was formed by reacting stoichiometric amount of monopotassium dihydrogen phosphate crystals, MgO, and water, forming pure-phase of MgKPOsb4.6Hsb2O (MKP) with moderate exothermic reaction. Using this chemically bonded phosphate ceramic matrix, low-level mixed waste streams were stabilized, and superior waste forms in a monolithic structure were developed. The final waste forms showed low open porosity and permeability, and higher compression strength than the Land Disposal Requirements (LDRs). The novel MKP ceramic technology allowed us to develop operational size waste forms of 55 gal with good physical integrity. In this improved waste form, the hazardous contaminants such as RCRA heavy metals (Hg, Pb, Cd, Cr, Ni, etc) were chemically fixed by their conversion into insoluble phosphate forms and physically encapsulated by the phosphate ceramic. In addition, chemically bonded phosphate ceramics stabilized radioactive elements such U and Pu. This was demonstrated with a detailed stabilization study on cerium used as a surrogate (chemically equivalent but nonradioactive) of U and Pu as well as on actual U-contaminated waste water. In particular, the leaching level of mercury in the Toxicity Characteristic Leaching Procedure (TCLP) test was reduced from 5000 to 0.00085 ppm, and the leaching level of cerium in the long term leaching test (ANS 16.1 test) was below the detection limit. These results show that the chemically bonded phosphate ceramics process may be a simple, inexpensive, and efficient method for stabilizing low-level mixed waste streams.

Investigations of oxidative stress effects and their mechanisms in rat brain after systemic administration of ceria engineered nanomaterials

NASA Astrophysics Data System (ADS)

Hardas, Sarita S.

Advancing applications of engineered nanomaterials (ENM) in various fields create the opportunity for intended (e.g. drug and gene delivery) or unintended (e.g. occupational and environmental) exposure to ENM. However, the knowledge of ENM-toxicity is lagging behind their application development. Understanding the ENM hazard can help us to avoid potential human health problems associated with ENM applications as well as to increase their public acceptance. Ceria (cerium [Ce] oxide) ENM have many current and potential commercial applications. Beyond the traditional use of ceria as an abrasive, the scope of ceria ENM applications now extends into fuel cell manufacturing, diesel fuel additives and for therapeutic intervention as a putative antioxidant. However, the biological effects of ceria ENM exposure have yet to be fully defined. Both pro-and anti-oxidative effects of ceria ENM exposure are repeatedly reported in literature. EPA, NIEHS and OECD organizations have nominated ceria for its toxicological evaluation. All these together gave us the impetus to examine the oxidative stress effects of ceria ENM after systemic administration. Induction of oxidative stress is one of the primary mechanisms of ENM toxicity. Oxidative stress plays an important role in maintaining the redox homeostasis in the biological system. Increased oxidative stress, due to depletion of antioxidant enzymes or molecules and / or due to increased production of reactive oxygen (ROS) or nitrogen (RNS) species may lead to protein oxidation, lipid peroxidation and/or DNA damage. Increased protein oxidation or lipid peroxidation together with antioxidant protein levels and activity can serve as markers of oxidative stress. To investigate the oxidative stress effects and the mechanisms of ceria-ENM toxicity, fully characterized ceria ENM of different sizes (˜ 5nm, 15nm, 30nm, 55nm and nanorods) were systematically injected into rats intravenously in separate experiments. Three brain regions (hippocampus, cortex and cerebellum) were harvested from control and ceria treated rats after various exposure periods for oxidative stress assessment. The levels of oxidative stress markers viz. protein carbonyl (PC), 3-nitrotyrosine (3NT), and protein bound 4-hydroxy-2-trans-nonenal (HNE) were evaluated for each treatment in each control and treated rat organ. Further, the levels and activities of antioxidant proteins, such as catalase, glutathione peroxidase (GPx), glutathione reductase (GR), super oxide dismutase (SOD), were measured together with levels of heat shock proteins heme oxygenase -1 and 70 (HO-1 and Hsp-70). In addition, the levels of pro-inflammatory cytokines IL-1beta, TNF-alpha, pro-caspase-3, and autophagy marker LC-3A/B were measured by Western blot technique. In agreement with the literature-proposed model of oxidative stress hierarchy mechanism of ENM-toxicity, the statistical analysis of all the results revealed that the ceria ENM-induced oxidative stress mediated biological response strongly depends on the exposure period and to some extent on the size of ceria ENM. More specifically, a single intravenous injection of ceria ENM induced tier-1 (phase-II antioxidant) response after shorter exposure periods (1 h and 20 h) in rat brain. Upon failure of tier-1 response after longer exposure periods (1 d to 30 d), escalated oxidative stress consequently induced tier-2 and tier-3 oxidative stress responses. Based on our observations made at chronic exposure period (90 d) after the single i.v. injection of ceria ENM, we could extend the model of oxidative stress hierarchy mechanisms for ceria-ENM-induced toxicity. Considering the evaluation of all the oxidative stress indices measured in 3-brain regions, oxidative stress effects were more prominent in hippocampus and the least in cerebellum, but no specific pattern or any significant difference was deduced. Keyword: Ceria, cerium oxide, nanomaterial, nanoparticles, nanotoxicity, oxidative stress, phase-II enzymes.

Scintillator material

DOEpatents

Anderson, D.F.; Kross, B.J.

1992-07-28

An improved scintillator material comprising cerium fluoride is disclosed. Cerium fluoride has been found to provide a balance of good stopping power, high light yield and short decay constant that is superior to known scintillator materials such as thallium-doped sodium iodide, barium fluoride and bismuth germanate. As a result, cerium fluoride is favorably suited for use as a scintillator material in positron emission tomography. 4 figs.

Scintillator material

DOEpatents

Anderson, D.F.; Kross, B.J.

1994-06-07

An improved scintillator material comprising cerium fluoride is disclosed. Cerium fluoride has been found to provide a balance of good stopping power, high light yield and short decay constant that is superior to known scintillator materials such as thallium-doped sodium iodide, barium fluoride and bismuth germanate. As a result, cerium fluoride is favorably suited for use as a scintillator material in positron emission tomography. 4 figs.

An Economic Model and Experiments to Understand Aluminum-Cerium Alloy Recycling

NASA Astrophysics Data System (ADS)

Iyer, Ananth V.; Lim, Heejong; Rios, Orlando; Sims, Zachary; Weiss, David

2018-04-01

We provide an economic model to understand the impact of adoption, sorting and pricing of scrap on the recycling of a new aluminum-cerium (AlCe) alloy for use in engine blocks in the automobile industry. The goal of the laboratory portion of this study is to investigate possible effects of cerium contamination on well-established aluminum recycling streams. Our methodology includes three components: (1) focused data gathering from industry supply chain participants, (2) experimental data through laboratory experiments to understand the impact of cerium on existing alloys and (3) an economic model to understand pricing incentives on a recycler's separation of AlCe engine blocks.

Effects of PEG4000 template on sol-gel synthesis of porous cerium titanate photocatalyst

NASA Astrophysics Data System (ADS)

Zhang, Wenjie; Tao, Yingjie; Li, Chuanguo

2018-04-01

Porous cerium titanate was synthesized by sol-gel method, using polyethylene glycol (PEG4000) as template agent. Brannerite structured CeTi2O6 in monoclinic system is the major substance formed in the materials. Formation of CeO2 and rutile TiO2 depends on the amount of PEG4000. The addition of PEG4000 leads to production of fine particles in the samples, but it does not apparently affect the band gap energy. Pore volume of the cerium titanate sample continuously increases with rising PEG4000 amount. The sample obtained using 3.5 g PEG4000 has BET surface area of 16.2 m2/g and pore volume of 0.0232 cm3/g. The addition of PEG4000 can obviously promote photocatalytic activity of cerium titanate, which can be proven by both enhanced production of hydroxyl radical and ofloxacin degradation efficiency. As much as 95.2% of the initial ofloxacin molecules are removed from the solution after 50 min of photocatalytic degradation on the cerium titanate obtained using 3.5 g PEG4000, while only 48.4% ofloxacin is removed on cerium titanate obtained without PEG4000.

Alumina-zirconia machinable abutments for implant-supported single-tooth anterior crowns.

PubMed

Sadoun, M; Perelmuter, S

1997-01-01

Innovative materials and application techniques are constantly being developed in the ongoing search for improved restorations. This article describes a new material and the fabrication process of aesthetic machinable ceramic anterior implant abutments. The ceramic material utilized is a mixture of alumina (aluminum oxide) and ceria (cerium oxide) with partially stabilized zirconia (zirconium oxide). The initial core material is a cylinder with a 9-mm diameter and a 15-mm height, obtained by ceramic injection and presintering processes. The resultant alumina-zirconia core is porous and readily machinable. It is secured to the analog, and its design is customized by machining the abutment to suit the particular clinical circumstances. The machining is followed by glass infiltration, and the crown is finalized. The learning objective of this article is to gain a basic knowledge of the fabrication and clinical application of the custom machinable abutments.

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. Copyright © 2015 Elsevier Ltd. All rights reserved.

Radiation coloration resistant glass

DOEpatents

Tomozawa, M.; Watson, E.B.; Acocella, J.

1986-11-04

A radiation coloration resistant glass is disclosed which is used in a radiation environment sufficient to cause coloration in most forms of glass. The coloration resistant glass includes higher proportions by weight of water and has been found to be extremely resistant to color change when exposed to such radiation levels. The coloration resistant glass is free of cerium oxide and has more than about 0.5% by weight water content. Even when exposed to gamma radiation of more than 10[sup 7] rad, the coloration resistant glass does not lose transparency. 3 figs.

Radiation coloration resistant glass

DOEpatents

Tomozawa, Minoru; Watson, E. Bruce; Acocella, John

1986-01-01

A radiation coloration resistant glass is disclosed which is used in a radiation environment sufficient to cause coloration in most forms of glass. The coloration resistant glass includes higher proportions by weight of water and has been found to be extremely resistant to color change when exposed to such radiation levels. The coloration resistant glass is free of cerium oxide and has more than about 0.5% by weight water content. Even when exposed to gamma radiation of more than 10.sup.7 rad, the coloration resistant glass does not lose transparency.

Metal Residue Deposition from Military Pyrotechnic Devices and Field Sampling Guidance

DTIC Science & Technology

2012-05-01

0.002 26.4 NA 0.082 Cerium none given NA 0.002 NA NA Chromium Oxide 1308-38-9 NA NA NA 0.015 Cobalt Naphthenate 61789-51-3 NA NA NA 0.017 Copper...the 1980s, the constituents in the whistling booby trap simulators included 73% potassium perchlorate, 24% gallic acid , and 3 % red gum (McIntyre...Test 3, MI snow sample, Rep 3 M21 Flash Artillery Simulator 50 3785.8 2/5/10 All – indicates the entire volume of stained snow was removed . MI

Enhanced oxygen storage capacity of cation-ordered cerium-zirconium oxide induced by titanium substitution.

PubMed

Goto, Yoshihiro; Morikawa, Akira; Iwasaki, Masaoki; Miura, Masahide; Tanabe, Toshitaka

2018-04-03

Herein, we report on the synthesis of Ce0.5Zr0.5-xTixO2 oxygen storage materials prepared via a solution combustion method. Ce0.5Zr0.4Ti0.1O2 showed an outstanding oxygen storage capacity (1310 μmol-O per g) at 200 °C compared to conventional κ-Ce2Zr2O8 (650 μmol-O per g) due to its cation ordering and the formation of weakly bound oxygen atoms induced by Ti substitution.

238Pu recovery and salt disposition from the molten salt oxidation process

NASA Astrophysics Data System (ADS)

Remerowski, M. L.; Stimmel, Jay J.; Wong, Amy S.; Ramsey, Kevin B.

2000-07-01

We have begun designing and optimizing our recovery and recycling processes by experimenting with samples of "spent salt" produced by MSO treatment of surrogate waste in the reaction vessel at the Naval Surface Warfare Center-Indian Head. One salt was produced by treating surrogate waste containing pyrolysis ash spiked with cerium. The other salt contains residues from MSO treatment of materials similar to those used in 238Pu processing, e.g., Tygon tubing, PVC bagout bags, HDPE bottles. Using these two salt samples, we will present results from our investigations.

Optical properties of cerium doped oxyfluoroborate glass.

PubMed

Bahadur, A; Dwivedi, Y; Rai, S B

2013-06-01

Cerium doped oxyfluoroborate glasses have been prepared and its spectroscopic properties have been discussed. It is found that the absorption edge shifts towards the lower energy side for the higher concentration of cerium dopant. Optical band gap for these glasses have been calculated and it is found that the number of non-bridging oxygen increases with cerium content. The emission spectra of these glasses have been recorded using UV laser radiations (266 and 355 nm) and it is observed that these glasses show bright blue emission. On the basis of excitation and emission spectra we have reported the existence of at least two different emission centers of Ce(3+)ions. Copyright © 2013 Elsevier B.V. All rights reserved.

Electrolytic recovery of reactor metal fuel

DOEpatents

Miller, W.E.; Tomczuk, Z.

1994-09-20

A new electrolytic process and apparatus are provided using sodium, cerium or a similar metal in alloy or within a sodium beta or beta[double prime]-alumina sodium ion conductor to electrolytically displace each of the spent fuel metals except for cesium and strontium on a selective basis from the electrolyte to an inert metal cathode. Each of the metals can be deposited separately. An electrolytic transfer of spent fuel into the electrolyte includes a sodium or cerium salt in the electrolyte with sodium or cerium alloy being deposited on the cathode during the transfer of the metals from the spent fuel. The cathode with the deposit of sodium or cerium alloy is then shunted to an anode and the reverse transfer is carried out on a selective basis with each metal being deposited separately at the cathode. The result is that the sodium or cerium needed for the process is regenerated in the first step and no additional source of these reactants is required. 2 figs.

Electrolytic recovery of reactor metal fuel

DOEpatents

Miller, W.E.; Tomczuk, Z.

1993-02-03

This invention is comprised of a new electrolytic process and apparatus using sodium, cerium or a similar metal in an alloy or within a sodium beta or beta-alumina sodium ion conductor to electrolytically displace each of the spent fuel metals except for Cesium and strontium on a selective basis from the electrolyte to an inert metal cathode. Each of the metals can be deposited separately. An electrolytic transfer of spent fuel into the electrolyte includes a sodium or cerium salt in the electrolyte with sodium or cerium alloy being deposited on the cathode during the transfer of the metals from the spent fuel. The cathode with the deposit of sodium or cerium alloy is then changed to an anode and the reverse transfer is carried out on a selective basis with each metal being deposited separately at the cathode. The result is that the sodium or cerium needed for the process is regenerated in the first step and no additional source of these reactants is required.

Electrolytic recovery of reactor metal fuel

DOEpatents

Miller, William E.; Tomczuk, Zygmunt

1994-01-01

A new electrolytic process and apparatus are provided using sodium, cerium or a similar metal in alloy or within a sodium beta or beta"-alumina sodium ion conductor to electrolytically displace each of the spent fuel metals except for cesium and strontium on a selective basis from the electrolyte to an inert metal cathode. Each of the metals can be deposited separately. An electrolytic transfer of spent fuel into the electrolyte includes a sodium or cerium salt in the electrolyte with sodium or cerium alloy being deposited on the cathode during the transfer of the metals from the spent fuel. The cathode with the deposit of sodium or cerium alloy is then chanted to an anode and the reverse transfer is carried out on a selective basis with each metal being deposited separately at the cathode. The result is that the sodium or cerium needed for the process is regenerated in the first step and no additional source of these reactants is required.

Experimental determination of water activity for binary aqueous cerium(III) ionic solutions: application to an assessment of the predictive capability of the binding mean spherical approximation model.

PubMed

Ruas, Alexandre; Simonin, Jean-Pierre; Turq, Pierre; Moisy, Philippe

2005-12-08

This work is aimed at a description of the thermodynamic properties of actinide salt solutions at high concentration. The predictive capability of the binding mean spherical approximation (BIMSA) theory to describe the thermodynamic properties of electrolytes is assessed in the case of aqueous solutions of lanthanide(III) nitrate and chloride salts. Osmotic coefficients of cerium(III) nitrate and chloride were calculated from other lanthanide(III) salts properties. In parallel, concentrated binary solutions of cerium nitrate were prepared in order to measure experimentally its water activity and density as a function of concentration, at 25 degrees C. Water activities of several binary solutions of cerium chloride were also measured to check existing data on this salt. Then, the properties of cerium chloride and cerium nitrate solutions were compared within the BIMSA model. Osmotic coefficient values for promethium nitrate and promethium chloride given by this theory are proposed. Finally, water activity measurements were made to examine the fact that the ternary system Ce(NO3)3/HNO3/H2O and the quaternary system Ce(NO3)3/HNO3/N2H5NO3/H2O may be regarded as "simple solutions" (in the sense of Zdanovskii and Mikulin).

Comparison of subchronic immunotoxicity of four different types of aluminum-based nanoparticles.

PubMed

Park, Eun-Jung; Lee, Sang Jin; Lee, Gwang-Hee; Kim, Dong-Wan; Yoon, Cheolho; Lee, Byoung-Seok; Kim, Younghun; Chang, Jaerak; Lee, Kyuhong

2018-04-01

Nanoparticles (NPs) have recently emerged as an inhalable pollutant, owing to their applications, aluminum-based NPs (Al-NPs) have been prioritized for toxicity testing. In the current study, we compared the pulmonary biopersistence and subsequent toxicity of four different types of Al-NPs (two rod-type aluminum oxide NPs [AlONPs] with different aspect ratios [short (S)- and long (L)-AlONPs], spherical aluminum cerium oxide NPs [AlCeO 3 , AlCeONPs] and spherical γ-aluminum oxide hydroxide nanoparticles [AlOOHNPs]) 13weeks after a single intratracheal instillation, considering the importance of their properties in their toxicity. We found that the pulmonary biopersistence of Al-NPs was strengthened by a high aspect ratio in the rod-type AlONPs and by the presence of hydroxyl groups in the spherical-type Al-NPs. The highest toxicity was observed in the mice treated with AlOOHNPs, which showed low biostability. More importantly, we identified that the commercially available AlCeONPs were Al 2 O 3 -coated CeO 2 NPs, but not AlCeO 3 NPs, although they have been sold under the trade name of AlCeONPs. In conclusion, the aspect ratio and biostability may be important factors in the determination of the biopersistence of NPs and the subsequent biological response. In addition, the physicochemical properties of NPs should be examined in detail before their release into the market to prevent unexpected adverse health effects. Copyright © 2017 John Wiley & Sons, Ltd.

The potential of sedimentary foraminiferal rare earth element patterns to trace water masses in the past

NASA Astrophysics Data System (ADS)

Osborne, Anne H.; Hathorne, Ed C.; Schijf, Johan; Plancherel, Yves; Böning, Philipp; Frank, Martin

2017-04-01

Dissolved rare earth element (REE) concentration data from intermediate and deep seawater form an array characterized by higher middle-REE enrichments (MREE/MREE*) in the North Atlantic and a progressive increase in heavy-to-light REE ratios (HREE/LREE) as water masses age. The REEs in foraminifera are fractionated toward higher MREE/MREE* and lower HREE/LREE relative to seawater. Calculations based on a scavenging model show that the REE patterns in uncleaned core-top foraminifera resemble those adsorbed onto calcite, particulate organic material, and hydrous ferric oxides but the full extent of the REE fractionation measured in foraminifera was not reproduced by the model. However, differences in the HREE/LREE and MREE/MREE* ratios and the cerium anomaly between ocean basins are preserved and are in agreement with the seawater REE distribution. Under oxic conditions, the HREE/LREE and MREE/MREE* compositions of uncleaned foraminifera at the sediment/seawater boundary are preserved during burial but the cerium anomaly is sensitive to burial depth. In suboxic sedimentary environments, all uncleaned foraminiferal REE concentrations are elevated relative to core-top values indicating addition of REEs from pore waters. The HREE/LREE ratio is highest when sedimentation rates were greatest and when high Fe/Ca ratios in the uncleaned foraminifera indicate that Fe was mobile. In sediments that have not experienced suboxic conditions during burial, uncleaned foraminifera preserve the seawater signal taken up at the sediment/seawater interface and are therefore suggested to be a suitable archive of changes in the REE signal of past bottom waters.

New ways to develop biosensors towards addressing practical problems

NASA Astrophysics Data System (ADS)

Starodub, N. F.

2013-11-01

The main modern approaches which were realized at the development of new generation of biosensors intended for application in field of diagnostics, food quality control and environmental monitoring are presented. The main attention was paid to creation of the multi-parametrical and multi-functional enzymatic and immune biosensors which were realized for the complex diagnostics of diabetes, autoimmune state and for the control of process of sugar production. The label-free bioaffine devices based on the nano-porouse silicon (NPS) with the registration of specific formed signal by chemiluminescence (ChL) and photoresistivity and intended for the determination mycotoxins and diagnostics of retroviral bovine leukemia (RBL) are analyzed too. Improving of ion sensitive field effect transistors (ISFETs) through changing silicon nitride on the cerium oxide is discussed as perspective approach in case of micotoxins and Salmonella control. In the conclusion the possibility to replace biological sensitive elements by artificial ones is considered.

Using ToF-SIMS and EIS to evaluate green pretreatment reagent: Corrosion protection of aluminum alloy by silica/zirconium/cerium hybrid coating

NASA Astrophysics Data System (ADS)

Chang, Chun-Chao; Wang, Chiung-Chi; Wu, Chia-Wei; Liu, Shou-Ching; Mai, Fu-Der

2008-12-01

Increasing environmental concern has led to the restrictive use of chromate conversion coatings to protect Al-alloys from corrosion. Our research is under way to find environmentally compliant substitute coating such as Si/Zr/Ce hybrid coating. The corrosion protection effect of green pretreatment reagent consisted of Si-containing base solution, Ce- and Zr-containing sealing solutions on the corrosion protection of Al-alloys was studied with a 3.5% NaCl aqueous testing solution. The correlation between the corrosion resistance measured by electrochemical impedance spectroscopy (EIS) and surface chemical composition of the hybrid coating measured by time-of-flight secondary ion mass spectroscopy (ToF-SIMS) was studied. The proposed green pretreatment reagent was found improve the corrosion protection of Al-alloys, presumably due to the formation of protective oxide film acting as an oxygen barrier.

Comparative study of structural, optical and impedance measurements on V{sub 2}O{sub 5} and V-Ce mixed oxide thin films

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

Malini, D. Rachel; Sanjeeviraja, C., E-mail: sanjeeviraja@rediffmail.com

Vanadium pentoxide (V{sub 2}O{sub 5}) and Vanadium-Cerium mixed oxide thin films at different molar ratios of V{sub 2}O{sub 5} and CeO{sub 2} have been deposited at 200 W rf power by rf planar magnetron sputtering in pure argon atmosphere. The structural and optical properties were studied by taking X-ray diffraction and transmittance and absorption spectra respectively. The amorphous thin films show an increase in transmittance and optical bandgap with increase in CeO{sub 2} content in as-prepared thin films. The impedance measurements for as-deposited thin films show an increase in electrical conductivity with increase in CeO{sub 2} material.

10 CFR Appendix B to Part 30 - Quantities 1 of Licensed Material Requiring Labeling

Code of Federal Regulations, 2012 CFR

2012-01-01

... Iodine-126 1 Iodine-129 0.1 Iodine-131 1 Iodine-132 10 Iodine-133 1 Iodine-134 10 Iodine-135 10 Iridium... Arsenic-73 100 Arsenic-74 10 Arsenic-76 10 Arsenic-77 100 Barium-131 10 Barium-133 10 Barium-140 10... Carbon-14 100 Cerium-141 100 Cerium-143 100 Cerium-144 1 Cesium-131 1,000 Cesium-134m 100 Cesium-134 1...

10 CFR Appendix B to Part 30 - Quantities 1 of Licensed Material Requiring Labeling

Code of Federal Regulations, 2014 CFR

2014-01-01

... Iodine-126 1 Iodine-129 0.1 Iodine-131 1 Iodine-132 10 Iodine-133 1 Iodine-134 10 Iodine-135 10 Iridium... Arsenic-73 100 Arsenic-74 10 Arsenic-76 10 Arsenic-77 100 Barium-131 10 Barium-133 10 Barium-140 10... Carbon-14 100 Cerium-141 100 Cerium-143 100 Cerium-144 1 Cesium-131 1,000 Cesium-134m 100 Cesium-134 1...

10 CFR Appendix B to Part 30 - Quantities 1 of Licensed Material Requiring Labeling

Code of Federal Regulations, 2013 CFR

2013-01-01

... Iodine-126 1 Iodine-129 0.1 Iodine-131 1 Iodine-132 10 Iodine-133 1 Iodine-134 10 Iodine-135 10 Iridium... Arsenic-73 100 Arsenic-74 10 Arsenic-76 10 Arsenic-77 100 Barium-131 10 Barium-133 10 Barium-140 10... Carbon-14 100 Cerium-141 100 Cerium-143 100 Cerium-144 1 Cesium-131 1,000 Cesium-134m 100 Cesium-134 1...

Molecular and physiological responses to titanium dioxide ...

EPA Pesticide Factsheets

- Changes in tissue transcriptomes and productivity of Arabidopsis thaliana were investigated during exposure of plants to two widely-used engineered metal oxide nanoparticles, titanium dioxide (nano-titanium) and cerium dioxide (nano-cerium). Microarray analyses confirmed that exposure to either nanoparticle altered the transcriptomes of rosette leaves and roots, with comparatively larger numbers of differentially expressed genes (DEGs) found under nano-titania exposure. Nano-titania induced more DEGs in rosette leaves, whereas roots had more DEGs under nano-ceria exposure. MapMan analyses indicated that while nano-titania up-regulated overall and secondary metabolism in both tissues, metabolic processes under nano-ceria remained mostly unchanged. Gene enrichment analysis indicated that both nanoparticles mainly enriched ontology groups such as responses to stress (abiotic and biotic), and defense responses (pathogens), and responses to endogenous stimuli (hormones). Nano-titania specifically induced genes associated with photosynthesis, whereas nano-ceria induced expression of genes related to activating transcription factors, most notably those belonging to the ethylene responsive element binding protein family. Interestingly, there were also increased numbers of rosette leaves and plant biomass under nano-ceria exposure, but not under nano-titania. Other transcriptomic responses did not clearly relate to responses observed at the organism level. This may b

Long term effects of cerium dioxide nanoparticles on the nitrogen removal, micro-environment and community dynamics of a sequencing batch biofilm reactor.

PubMed

Xu, Yi; Wang, Chao; Hou, Jun; Wang, Peifang; Miao, Lingzhan; You, Guoxiang; Lv, Bowen; Yang, Yangyang; Zhang, Fei

2017-12-01

The influences of cerium dioxide nanoparticles (CeO 2 NPs) on nitrogen removal in biofilm were investigated. Prolonged exposure (75d) to 0.1mg/L CeO 2 NPs caused no inhibitory effects on nitrogen removal, while continuous addition of 10mg/L CeO 2 NPs decreased the treatment efficiency to 53%. With the progressive concentration of CeO 2 NPs addition, the removal efficiency could nearly stabilize at 67% even with the continues spike of 10mg/L. The micro-profiles of dissolved oxygen, pH, and oxidation reduction potential suggested the developed protection mechanisms of microbes to progressive CeO 2 NPs exposure led to the less influence of microenvironment, denitrification bacteria and enzyme activity than those with continuous ones. Furthermore, high throughput sequencing illustrated the drastic shifted communities with gradual CeO 2 NPs spiking was responsible for the adaption and protective mechanisms. The present study demonstrated the acclimated microbial community was able to survive CeO 2 NPs addition more readily than those non-acclimated. Copyright © 2017 Elsevier Ltd. All rights reserved.

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. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Properties of Cerium Hydroxides from Matrix Infrared Spectra and Electronic Structure Calculations.

PubMed

Fang, Zongtang; Thanthiriwatte, K Sahan; Dixon, David A; Andrews, Lester; Wang, Xuefeng

2016-02-15

Reactions of laser ablated cerium atoms with hydrogen peroxide or hydrogen and oxygen mixtures diluted in argon and condensed at 4 K produced the Ce(OH)3 and Ce(OH)2 molecules and Ce(OH)2(+) cation as major products. Additional minor products were identified as the Ce(OH)4, HCeO, and OCeOH molecules. These new species were identified from their matrix infrared spectra with D2O2, D2, and (18)O2 isotopic substitution and correlating observed frequencies with values calculated by density functional theory. We find that the amounts of Ce(OH)3 and of the Ce(OH)2(+) cation increase on UV (λ > 220 nm) photolysis, while Ce(OH)2, Ce(OH)4, and HCeO are photosensitive. The observed major species for Ce are in the +III or +II oxidation state, and the minor product, Ce(OH)4, is in the +IV oxidation state. The calculations for the vibrational frequencies with the B3LYP functional agree well with the experiment. The NBO analysis shows significant backbonding to the metal 4f and 5d orbitals for the closed shell species. Most open shell species have the excess spin in the 4f with paired spin in the 5d due to backbonding. The heats of formation of the observed species were derived from the available data from experiment and the calculated reaction energies. The major products in this study are different from similar reactions for Th where the tetrahydroxide was the major species.

Pulmonary toxicity of well-dispersed cerium oxide nanoparticles following intratracheal instillation and inhalation

NASA Astrophysics Data System (ADS)

Morimoto, Yasuo; Izumi, Hiroto; Yoshiura, Yukiko; Tomonaga, Taisuke; Oyabu, Takako; Myojo, Toshihiko; Kawai, Kazuaki; Yatera, Kazuhiro; Shimada, Manabu; Kubo, Masaru; Yamamoto, Kazuhiro; Kitajima, Shinichi; Kuroda, Etsushi; Kawaguchi, Kenji; Sasaki, Takeshi

2015-11-01

We performed inhalation and intratracheal instillation studies of cerium dioxide (CeO2) nanoparticles in order to investigate their pulmonary toxicity, and observed pulmonary inflammation not only in the acute and but also in the chronic phases. In the intratracheal instillation study, F344 rats were exposed to 0.2 mg or 1 mg of CeO2 nanoparticles. Cell analysis and chemokines in bronchoalveolar lavage fluid (BALF) were analyzed from 3 days to 6 months following the instillation. In the inhalation study, rats were exposed to the maximum concentration of inhaled CeO2 nanoparticles (2, 10 mg/m3, respectively) for 4 weeks (6 h/day, 5 days/week). The same endpoints as in the intratracheal instillation study were examined from 3 days to 3 months after the end of the exposure. The intratracheal instillation of CeO2 nanoparticles caused a persistent increase in the total and neutrophil number in BALF and in the concentration of cytokine-induced neutrophil chemoattractant (CINC)-1, CINC-2, chemokine for neutrophil, and heme oxygenase-1 (HO-1), an oxidative stress marker, in BALF during the observation time. The inhalation of CeO2 nanoparticles also induced a persistent influx of neutrophils and expression of CINC-1, CINC-2, and HO-1 in BALF. Pathological features revealed that inflammatory cells, including macrophages and neutrophils, invaded the alveolar space in both studies. Taken together, the CeO2 nanoparticles induced not only acute but also chronic inflammation in the lung, suggesting that CeO2 nanoparticles have a pulmonary toxicity that can lead to irreversible lesions.

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.

First demonstration of 10 keV-width energy-discrimination K-edge radiography using a cadmium-telluride X-ray camera with a tungsten-target tube

NASA Astrophysics Data System (ADS)

Watanabe, Manabu; Sato, Eiichi; Abderyim, Purkhet; Abudurexiti, Abulajiang; Hagiwara, Osahiko; Matsukiyo, Hiroshi; Osawa, Akihiro; Enomoto, Toshiyuki; Nagao, Jiro; Sato, Shigehiro; Ogawa, Akira; Onagawa, Jun

2011-05-01

Energy-discrimination X-ray camera is useful to perform monochromatic radiography using polychromatic X-rays. This X-ray camera was developed to carry out K-edge radiography using cerium and gadolinium-based contrast media. In this camera, objects are irradiated by a cone beam from a tungsten-target X-ray generator, and penetrating X-ray photons are detected by a cadmium-telluride detector with amplifiers. Both optimal photon-energy level and energy width are selected using a multichannel analyzer, and the photon number is counted by a counter card. Radiography was performed by the detector scanning using an x- y stage driven by a two-stage controller, and radiograms were shown on a personal computer monitor. In radiography, tube voltage and current were 90 kV and 5.8 μA, respectively, and the X-ray intensity was 0.61 μGy/s at 1.0 m from the X-ray source. The K-edge energies of cerium and gadolinium are 40.3 and 50.3 keV, respectively, and 10 keV-width enhanced K-edge radiography was performed using X-ray photons with energies just beyond K-edge energies of cerium and gadolinium. Thus, cerium K-edge radiography was carried out using X-ray photons with an energy range from 40.3 to 50. 3 keV, and gadolinium K-edge radiography was accomplished utilizing photon energies ranging from 50.3 to 60.3 keV.

Effect of variable cerium concentration on photoluminescence behaviour in ZrO2 phosphor synthesized by combustion synthesis method

NASA Astrophysics Data System (ADS)

Dubey, Vikas; Kaur, Jagjeet

2016-05-01

Present paper reports synthesis and characterization of trivalent cerium (Ce3+) doped zirconium dioxide (ZrO2) phosphors. Effect of variable concentration of cerium on photoluminescence (PL) is studied. Samples were prepared by combustion synthesis technique which is suitable for less time taking techniques also for large scale production for phosphors. Starting material used for sample preparation are Zr(NO3)3 and Ce(NO3)3 and urea used as a fuel. All prepared phosphor with variable concentration of Ce3+ (0.1 to 2mol%) was studied by photoluminescence analysis it is found that the excitation spectra of prepared phosphor shows broad excitation centred at 390nm. The excitation spectra with variable concentration of Ce3+ show strong peaks at 447nm. Spectrophotometric determinations of peaks are evaluated by Commission Internationale de I'Eclairage technique. Using this phosphor, the desired CIE values including emissions throughout the violet (390 nm) and blue (427 nm) of the spectra were achieved. Efficient blue light emitting diodes were fabricated using Ce3+ doped phosphor based on near ultraviolet (NUV) excited LED lights.

Synthesis and characterization of cerium- and gallium-containing borate bioactive glass scaffolds for bone tissue engineering.

PubMed

Deliormanlı, Aylin M

2015-02-01

Bioactive glasses are widely used in biomedical applications due to their ability to bond to bone and even to soft tissues. In this study, borate based (13-93B3) bioactive glass powders containing up to 5 wt% Ce2O3 and Ga2O3 were prepared by the melt quench technique. Cerium (Ce+3) and gallium (Ga+3) were chosen because of their low toxicity associated with bacteriostatic properties. Bioactive glass scaffolds were fabricated using the polymer foam replication method. In vitro degradation and bioactivity of the scaffolds were evaluated in SBF under static conditions. Results revealed that the cerium- and gallium-containing borate glasses have much lower degradation rates compared to the bare borate glass 13-93B3. In spite of the increased chemical durability, substituted glasses exhibited a good in vitro bioactive response except when the Ce2O3 content was 5 wt%. Taking into account the high in vitro hydroxyapatite forming ability, borate glass scaffolds containing Ce+3 and Ga+3 therapeutic ions are promising candidates for bone tissue engineering applications.

Effect of oxidizing adulterants on human urinary steroid profiles.

PubMed

Kuzhiumparambil, Unnikrishnan; Fu, Shanlin

2013-02-01

Steroid profiling is the most versatile and informative technique adapted by doping control laboratories for detection of steroid abuse. The absolute concentrations and ratios of endogenous steroids including testosterone, epitestosterone, androsterone, etiocholanolone, 5α-androstane-3α,17β-diol and 5β-androstane-3α,17β-diol constitute the significant characteristics of a steroid profile. In the present study we report the influence of various oxidizing adulterants on the steroid profile of human urine. Gas chromatography-mass spectrometry analysis was carried out to develop the steroid profile of human male and female urine. Oxidants potassium nitrite, sodium hypochlorite, potassium permanganate, cerium ammonium nitrate, sodium metaperiodate, pyridinium chlorochromate, potassium dichromate and potassium perchlorate were reacted with urine at various concentrations and conditions and the effect of these oxidants on the steroid profile were analyzed. Most of the oxidizing chemicals led to significant changes in endogenous steroid profile parameters which were considered stable under normal conditions. These oxidizing chemicals can cause serious problems regarding the interpretation of steroid profiles and have the potential to act as masking agents that can complicate or prevent the detection of the steroid abuse. Copyright © 2012 Elsevier Inc. All rights reserved.

Evaluation of Non-Chromate Passivations on Electroplated gamma-Phase Zinc Nickel

NASA Astrophysics Data System (ADS)

Volz, Steven Michael

This research focused on the corrosion response and electrochemical behavior of electroplated low hydrogen embrittlement alkaline gamma-phase zinc nickel with passivation layers. The motivation was the need to replace hexavalent chromium conversion coatings in military grade electrical systems with a more environment friendly alternative. The passivation layers were employed for the purpose of mitigating corrosion attack while maintaining low contact resistance. Trivalent chromium-based passivations and cerium-based passivations were compared against the currently used hexavalent chromium conversion coating. The coating systems were compared using electrochemical impedance spectroscopy, cyclic potentiodymanic scans, salt spray exposure testing, electrical resistance measurements, microstructure analysis, and compositional analysis. Coating systems with lower open circuit had a lower corrosion current and performed better during salt spray testing. All of the systems evaluated had corrosion products consistent with oxidized zinc compounds but the morphology of the passivation was dependent on the passivation. The electrical contact resistance ranged from 1 to 108 mO/cm 2, after salt spray testing. Two versions of Trivalent chromium-based passivations, were able to meet military performance specifications after corrosion testing.

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.

Kinetic and catalytic analysis of mesoporous metal oxides on the oxidation of Rhodamine B

NASA Astrophysics Data System (ADS)

Xaba, Morena S.; Noh, Ji-Hyang; Mokgadi, Keabetswe; Meijboom, Reinout

2018-05-01

In this study, we demonstrate the synthesis and catalytic activity of different mesoporous transition metal oxides, silica (SiO2), copper oxide (CuO), chromium oxide (Cr2O3), iron oxide (Fe2O3) cobalt oxide (Co3O4), cerium oxide (CeO2) and nickel oxide (NiO), on the oxidation of a pollutant dye, Rhodamine B (RhB). These metal oxides were synthesized by inverse micelle formation method and characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray diffraction (XRD), adsorption-desorption isotherms (BET) and H2-temperature programmed reduction (TPR). UV-vis spectrophotometry was used to monitor the time-resolved absorbance of RhB at λmax = 554 nm. Mesoporous copper oxide was calcined at different final heating temperatures of 250, 350, 450 and 550 °C, and each mesoporous copper oxide catalyst showed unique physical properties and catalytic behavior. Mesoporous CuO-550 with the smallest characteristic path length δ, proved to be the catalyst of choice for the oxidation of RhB in aqueous media. We observed that the oxidation of RhB in aqueous media is dependent on the crystallite size and characteristic path length of the mesoporous metal oxide. The Langmuir-Hinshelwood model was used to fit the experimental data and to prove that the reaction occurs on the surface of the mesoporous CuO. The thermodynamic parameters, EA, ΔH#, ΔS# and ΔG# were calculated and catalyst recycling and reusability were demonstrated.

Combined Advanced Finishing and UV-Laser Conditioning for Producing UV-Damage-Resistant Fused Silica Optics

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

Menapace, J A; Penetrante, B; Golini, D

2001-11-01

Laser induced damage initiation on fused silica optics can limit the lifetime of the components when used in high power UV laser environments. Foe example in inertial confinement fusion research applications, the optics can be exposed to temporal laser pulses of about 3-nsec with average fluences of 8 J/cm{sup 2} and peak fluences between 12 and 15 J/cm{sup 2}. During the past year, we have focused on optimizing the damage performance at a wavelength of 355-nm (3{omega}), 3-nsec pulse length, for optics in this category by examining a variety of finishing technologies with a challenge to improve the laser damagemore » initiation density by at least two orders of magnitude. In this paper, we describe recent advances in improving the 3{omega} damage initiation performance of laboratory-scale zirconium oxide and cerium oxide conventionally finished fused silica optics via application of processes incorporating magnetorheological finishing (MRF), wet chemical etching, and UV laser conditioning. Details of the advanced finishing procedures are described and comparisons are made between the procedures based upon large area 3{omega} damage performance, polishing layer contamination, and optical subsurface damage.« less

Dispersion of Nanomaterials in Aqueous Media: Towards Protocol Optimization.

PubMed

Kaur, Inder; Ellis, Laura-Jayne; Romer, Isabella; Tantra, Ratna; Carriere, Marie; Allard, Soline; Mayne-L'Hermite, Martine; Minelli, Caterina; Unger, Wolfgang; Potthoff, Annegret; Rades, Steffi; Valsami-Jones, Eugenia

2017-12-25

The sonication process is commonly used for de-agglomerating and dispersing nanomaterials in aqueous based media, necessary to improve homogeneity and stability of the suspension. In this study, a systematic step-wise approach is carried out to identify optimal sonication conditions in order to achieve a stable dispersion. This approach has been adopted and shown to be suitable for several nanomaterials (cerium oxide, zinc oxide, and carbon nanotubes) dispersed in deionized (DI) water. However, with any change in either the nanomaterial type or dispersing medium, there needs to be optimization of the basic protocol by adjusting various factors such as sonication time, power, and sonicator type as well as temperature rise during the process. The approach records the dispersion process in detail. This is necessary to identify the time points as well as other above-mentioned conditions during the sonication process in which there may be undesirable changes, such as damage to the particle surface thus affecting surface properties. Our goal is to offer a harmonized approach that can control the quality of the final, produced dispersion. Such a guideline is instrumental in ensuring dispersion quality repeatability in the nanoscience community, particularly in the field of nanotoxicology.

Dispersion of Nanomaterials in Aqueous Media: Towards Protocol Optimization

PubMed Central

Kaur, Inder; Ellis, Laura-Jayne; Romer, Isabella; Tantra, Ratna; Carriere, Marie; Allard, Soline; Mayne-L'Hermite, Martine; Minelli, Caterina; Unger, Wolfgang; Potthoff, Annegret; Rades, Steffi; Valsami-Jones, Eugenia

2017-01-01

The sonication process is commonly used for de-agglomerating and dispersing nanomaterials in aqueous based media, necessary to improve homogeneity and stability of the suspension. In this study, a systematic step-wise approach is carried out to identify optimal sonication conditions in order to achieve a stable dispersion. This approach has been adopted and shown to be suitable for several nanomaterials (cerium oxide, zinc oxide, and carbon nanotubes) dispersed in deionized (DI) water. However, with any change in either the nanomaterial type or dispersing medium, there needs to be optimization of the basic protocol by adjusting various factors such as sonication time, power, and sonicator type as well as temperature rise during the process. The approach records the dispersion process in detail. This is necessary to identify the time points as well as other above-mentioned conditions during the sonication process in which there may be undesirable changes, such as damage to the particle surface thus affecting surface properties. Our goal is to offer a harmonized approach that can control the quality of the final, produced dispersion. Such a guideline is instrumental in ensuring dispersion quality repeatability in the nanoscience community, particularly in the field of nanotoxicology. PMID:29364209

Role of epithelial-mesenchymal transition (EMT) and fibroblast function in cerium oxide nanoparticles-induced lung fibrosis

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

Ma, Jane

The emission of cerium oxide nanoparticles (CeO{sub 2}) from diesel engines, using cerium compounds as a catalyst to lower the diesel exhaust particles, is a health concern. We have previously shown that CeO{sub 2} induced pulmonary inflammation and lung fibrosis. The objective of the present study was to investigate the modification of fibroblast function and the role of epithelial-mesenchymal transition (EMT) in CeO{sub 2}-induced fibrosis. Male Sprague-Dawley rats were exposed to CeO{sub 2} (0.15 to 7 mg/kg) by a single intratracheal instillation and sacrificed at various times post-exposure. The results show that at 28 days after CeO{sub 2} (3.5 mg/kg)more » exposure, lung fibrosis was evidenced by increased soluble collagen in bronchoalveolar lavage fluid, elevated hydroxyproline content in lung tissues, and enhanced sirius red staining for collagen in the lung tissue. Lung fibroblasts and alveolar type II (ATII) cells isolated from CeO{sub 2}-exposed rats at 28 days post-exposure demonstrated decreasing proliferation rate when compare to the controls. CeO{sub 2} exposure was cytotoxic and altered cell function as demonstrated by fibroblast apoptosis and aggregation, and ATII cell hypertrophy and hyperplasia with increased surfactant. The presence of stress fibers, expressed as α-smooth muscle actin (SMA), in CeO{sub 2}-exposed fibroblasts and ATII cells was significantly increased compared to the control. Immunohistofluorescence analysis demonstrated co-localization of TGF-β or α-SMA with prosurfactant protein C (SPC)-stained ATII cells. These results demonstrate that CeO{sub 2} exposure affects fibroblast function and induces EMT in ATII cells that play a role in lung fibrosis. These findings suggest potential adverse health effects in response to CeO{sub 2} nanoparticle exposure. - Highlights: • CeO{sub 2} exposure induced lung fibrosis. • CeO{sub 2} were detected in lung tissue, alveolar type II (ATII) cells and fibroblasts. • CeO{sub 2} caused ATII cell hypertrophy and hyperplasia and altered fibroblast function. • Increased α-SMA in CeO{sub 2}-exposed lung fibroblasts indicating myofibroblast formation. • CeO{sub 2} induced EMT in ATII cells demonstrated as increased α-SMA expression.« less

Cerium oxide nanozyme modulate the ‘exercise’ redox biology of skeletal muscle

NASA Astrophysics Data System (ADS)

Arya, Aditya; Sethy, Niroj Kumar; Gangwar, Anamika; Bhargava, Neelima; Dubey, Amarish; Roy, Manas; Srivastava, Gaurav; Singh, Sushil Kumar; Das, Mainak; Bhargava, Kalpana

2017-05-01

‘Exercise’ is a double-edged sword for the skeletal muscle. Small amount of ROS generated during mild exercise, is essential for normal force generation; whereas large quantity of ROS generated during intense exercise, may cause contractile dysfunction, resulting in muscle weakness and fatigue. One of the key question in skeletal muscle physiology is ‘could antioxidant therapy improve the skeletal muscle endurance? A question, which has resulted in contradictory experimental findings till this date. This work has addressed this ‘very question’ using a synthetic, inorganic, antioxidant nano-material viz., ‘cerium oxide nanozyme’ (CON). It has been introduced in the rat by intramuscular injection, and the skeletal muscle endurance has been evaluated. Intramuscular injections of CON, concurrent with exercise, enhanced muscle mass, glycogen and ATP content, type I fiber ratio, thus resulting in significantly higher muscle endurance. Electron microscope studies confirmed the presence of CON in the vicinity of muscle mitochondria. There was an increase in the number and size of the muscle mitochondria in the CON treated muscle, following exercise, as compared to the untreated group with only exercised muscle. Quantitative proteomics data and subsequent biological network analysis studies, identified higher levels of oxidative phosphorylation, TCA cycle output and glycolysis in CON supplemented exercised muscle over only exercised muscle. This was further associated with significant increase in the mitochondrial respiratory capacity and muscle contraction, primarily due to higher levels of electron transport chain proteins like NDUFA9, SDHA, ATP5B and ATP5D, which were validated by real-time PCR and western blotting. Along with this, persistence of CON in muscle was evaluated with ICP-MS analysis, which revealed clearance of the particles after 90 d, without exhibiting any inflammation or adverse affects on the health of the experimental animals. Thus a higher physiological endurance of the CON supplemented exercised muscle’ opens new avenues in skeletal muscle therapeutic, space and sports medicine.

High-Temperature Desulfurization of Heavy Fuel-Derived Reformate Gas Streams for SOFC Applications

NASA Technical Reports Server (NTRS)

Flytzani-Stephanopoulos, Maria; Surgenor, Angela D.

2007-01-01

Desulfurization of the hot reformate gas produced by catalytic partial oxidation or autothermal reforming of heavy fuels, such as JP-8 and jet fuels, is required prior to using the gas in a solid oxide fuel cell (SOFC). Development of suitable sorbent materials involves the identification of sorbents with favorable sulfidation equilibria, good kinetics, and high structural stability and regenerability at the SOFC operating temperatures (650 to 800 C). Over the last two decades, a major barrier to the development of regenerable desulfurization sorbents has been the gradual loss of sorbent performance in cyclic sulfidation and regeneration at such high temperatures. Mixed oxide compositions based on ceria were examined in this work as regenerable sorbents in simulated reformate gas mixtures and temperatures greater than 650 C. Regeneration was carried out with dilute oxygen streams. We have shown that under oxidative regeneration conditions, high regeneration space velocities (greater than 80,000 h(sup -1)) can be used to suppress sulfate formation and shorten the total time required for sorbent regeneration. A major finding of this work is that the surface of ceria and lanthanan sorbents can be sulfided and regenerated completely, independent of the underlying bulk sorbent. This is due to reversible adsorption of H2S on the surface of these sorbents even at temperatures as high as 800 C. La-rich cerium oxide formulations are excellent for application to regenerative H2S removal from reformate gas streams at 650 to 800 C. These results create new opportunities for compact sorber/regenerator reactor designs to meet the requirements of solid oxide fuel cell systems at any scale.

CHEMICAL SOLUTION DEPOSITION BASED OXIDE BUFFERS AND YBCO COATED CONDUCTORS

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

Paranthaman, Mariappan Parans

We have reviewed briefly the growth of buffer and high temperature superconducting oxide thin films using a chemical solution deposition (CSD) method. In the Rolling-Assisted Biaxially Textured Substrates (RABiTS) process, developed at Oak Ridge National Laboratory, utilizes the thermo mechanical processing to obtain the flexible, biaxially oriented copper, nickel or nickel-alloy substrates. Buffers and Rare Earth Barium Copper Oxide (REBCO) superconductors have been deposited epitaxially on the textured nickel alloy substrates. The starting substrate serves as a template for the REBCO layer, which has substantially fewer weak links. Buffer layers play a major role in fabricating the second generation REBCOmore » wire technology. The main purpose of the buffer layers is to provide a smooth, continuous and chemically inert surface for the growth of the REBCO film, while transferring the texture from the substrate to the superconductor layer. To achieve this, the buffer layers need to be epitaxial to the substrate, i.e. they have to nucleate and grow in the same bi-axial texture provided by the textured metal foil. The most commonly used RABiTS multi-layer architectures consist of a starting template of biaxially textured Ni-5 at.% W (Ni-W) substrate with a seed (first) layer of Yttrium Oxide (Y2O3), a barrier (second) layer of Yttria Stabilized Zirconia (YSZ), and a Cerium Oxide (CeO2) cap (third) layer. These three buffer layers are generally deposited using physical vapor deposition (PVD) techniques such as reactive sputtering. On top of the PVD template, REBCO film is then grown by a chemical solution deposition. This article reviews in detail about the list of oxide buffers and superconductor REBCO films grown epitaxially on single crystal and/or biaxially textured Ni-W substrates using a CSD method.« less

Ab initio MCHF structural calculations of Mg-like cerium

NASA Astrophysics Data System (ADS)

Wajid, Abdul; Jabeen, S.; Husain, Abid

2018-05-01

Energy levels and emission line wavelengths of high-Z materials are useful for impurity diagnostics in the next generation fusion devices. For this here we have calculated E1, M2 transitions, oscillator strengths, and transition probabilities for transitions among the terms belonging to the 2p63s2, 2p63s3p, 2p63p2 and 2p63s3d for the Magnesium like cerium (Ce XLVII) using the GRASP2K package based on the fully relativistic multi-configuration Dirac-Fock method. The electron correlation effects, Breit interaction and quantum electrodynamics effects to the atomic state wave functions and the corresponding energies have been taken into account.

Protective conversion coating on mixed-metal substrates and methods thereof

DOEpatents

O'Keefe, Matthew J.; Maddela, Surender

2016-09-06

Mixed-metal automotive vehicle bodies-in-white comprising ferrous metal surfaces, zinc surfaces, aluminum alloy surfaces, and magnesium alloy surfaces are cleaned and immersed in an aqueous bath comprising an adhesion promoter and an aqueous electrocoat bath (the adhesion promoter may be in the electrocoat bath. The adhesion promoter, which may be a cerium salt, is selected to react with each metal in the body surfaces to form an oxide layer that provides corrosion resistance for the surface and adherence for the deposited polymeric paint coating. The body is cathodic in the electrocoat deposition.

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

Ozmen, Ozcan; Zondlo, John W.; Lee, Shiwoo

A bio-inspired surfactant was utilized to assist in the efficient impregnation of a nano-CeO₂ catalyst throughout both porous Solid Oxide Fuel Cells (SOFC’s) electrodes simultaneously. The process included the initial modification of electrode pore walls with a polydopamine film. The cell was then submersed into a cerium salt solution. The amount of nano-CeO₂ deposited per impregnation step increased by 3.5 times by utilizing this two-step protocol in comparison to a conventional drip impregnation method. The impregnated cells exhibited a 20% higher power density than a baseline cell without the nano-catalyst at 750°C (using humid H₂ fuel).

Redetermination of dicerium(III) tris-(sulfate) tetra-hydrate.

PubMed

Xu, Xin

2007-12-06

Ce(2)(SO(4))(3)(H(2)O)(4) was obtained hydro-thermally from an aqueous solution of cerium(III) oxide, trimethyl-amine and sulfuric acid. The precision of the structure determination has been significantly improved compared with the previous result [Dereigne (1972 ▶). Bull. Soc. Fr. Mineral. Cristallogr.95, 269-280]. The coordination about the two Ce atoms is achieved by seven and six bridging O atoms from sulfate anions. Each S atom makes four S-O-Ce linkages through bridging O atoms. The coordination sphere of each Ce is completed by two water molecules, which act as terminal ligands.

FUSED SALT PROCESS FOR RECOVERY OF VALUES FROM USED NUCLEAR REACTOR FUELS

DOEpatents

Moore, R.H.

1960-08-01

A process is given for recovering plutonium from a neutron-irradiated uranium mass (oxide or alloy) by dissolving the mass in an about equimolar alkali metalaluminum double chloride, adding aluminum metal to the mixture obtained at a temperature of between 260 and 860 deg C, and separating a uranium-containing metal phase and a plutonium-chloride- and fission-product chloridecontaining salt phase. Dissolution can be expedited by passing carbon tetrachloride vapors through the double salt. Separation without reduction of plutonium from neutron- bombarded uranium and that of cerium from uranium are also discussed.

Nano-Enriched and Autonomous Sensing Framework for Dissolved Oxygen.

PubMed

Shehata, Nader; Azab, Mohammed; Kandas, Ishac; Meehan, Kathleen

2015-08-14

This paper investigates a nano-enhanced wireless sensing framework for dissolved oxygen (DO). The system integrates a nanosensor that employs cerium oxide (ceria) nanoparticles to monitor the concentration of DO in aqueous media via optical fluorescence quenching. We propose a comprehensive sensing framework with the nanosensor equipped with a digital interface where the sensor output is digitized and dispatched wirelessly to a trustworthy data collection and analysis framework for consolidation and information extraction. The proposed system collects and processes the sensor readings to provide clear indications about the current or the anticipated dissolved oxygen levels in the aqueous media.

Homoleptic Ce(III) and Ce(IV) Nitroxide Complexes: Significant Stabilization of the 4+ Oxidation State

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

Bogart, Justin A.; Lewis, Andrew J.; Medling, Scott A.

2014-06-25

Electrochemical experiments performed on the complex Ce-IV[2-((BuNO)-Bu-t)py](4), where [2-((BuNO)-Bu-t)py](-) = N-tert-butyl-N-2-pyridylnitroxide, indicate a 2.51 V stabilization of the 4+ oxidation state of Ce compared to [(Bu4N)-Bu-n](2)[Ce(NO3)(6)] in acetonitrile and a 2.95 V stabilization compared to the standard potential for the ion under aqueous conditions. Density functional theory calculations suggest that this preference for the higher oxidation state is a result of the tetrakis(nitroxide) ligand framework at the Ce cation, which allows for effective electron donation into, and partial covalent overlap with, vacant 4f orbitals with delta symmetry. The results speak to the behavior of CeO2 and related solid solutions inmore » oxygen uptake and transport applications, in particular an inherent local character of bonding that stabilizes the 4+ oxidation state. The results indicate a cerium(IV) complex that has been stabilized to an unprecedented degree through tuning of its ligand-field environment.« less

Self-interaction-corrected local-spin-density calculations for rare earth materials

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

Svane, A.; Temmerman, W.M.; Szotek, Z.

2000-04-20

The ab initio self-interaction-corrected (SIC) local-spin-density (LSD) approximation is discussed with emphasis on the ability to describe localized f-electron states in rare earth solids. Two methods for minimizing the SIC-LSD total energy functional are discussed, one using a unified Hamiltonian for all electron states, thus having the advantages of Bloch's theorem, the other one employing an iterative scheme in real space. Results for cerium and cerium compounds as well as other rare earths are presented. For the cerium compounds the onset of f-electron delocalization can be accurately described, including the intricate isostructural phase transitions in elemental cerium and CeP. Inmore » Pr and Sm the equilibrium lattice constant and zero temperature equation of state is greatly improved in comparison with the LSD results.« less